•Discrimination of the origin of rice samples by HR-ICP-MS multi-element fingerprinting.•Classification of rice samples was by a radar plot and a multivariate data analysis.•Thai jasmine white rice ...was differentiated from foreign rice and classified according to regions of origin.
Rice is a staple food for nearly half the world’s population. The discrimination of geographical origin of rice in order to its authenticity is essential to prevent mislabeling and adulteration problems. The multi-element fingerprinting has a great potential for the differentiation of rice grains. A study of the capability of the high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) methodology for multi-element fingerprinting of rice has been carried out. A total of 31 Thai jasmine rice and 5 foreign (France, India, Italy, Japan and Pakistan) rice samples were analysed by high resolution ICP-MS after acid digestion. Accuracy of the whole procedure was verified by the analysis of rice flour standard reference material (NIST SRM 1568a). The concentrations of 21 elements were evaluated and used as chemical indicator to discriminate the origin of rice samples. The classification of rice samples was carried out based on elemental composition by a radar plot and multivariate data analysis, including principal component analysis (PCA) and discriminant analysis (DA). Thai jasmine rice can be differentiated from foreign rice samples by radar plots and multivariate data analysis. Furthermore, the DA can differentiate Thai jasmine rice samples according to each region of origin (northern, northeastern or central regions of Thailand). Therefore, multi-element fingerprinting combined with the use of multivariate statistical techniques can be considered as a powerful tool for rice authentication.
•Monitoring of sulfonamides and their metabolites in >300 of meat samples collected in Lebanon.•Detection of sulfonamides in different incurred meat samples by LC–QqQ MS.•Confirmation of sulfonamides ...by LC–LTQ Orbitrap.•Identification of putative metabolites by LC–LTQ Orbitrap.•Estimation of the toxicity of detected sulfonamides and their metabolites by in silico tests.
The extensive and unregulated use of antibacterial drugs in animal farms in Lebanon can lead to detrimental consequences for the public health. To monitor the levels of sulfonamides and their metabolites in farms in Lebanon, a total of 304 meat samples were collected and analyzed using liquid chromatography coupled to triple quadrupole and hybrid linear ion trap-Orbitrap mass spectrometry following QuEChERS-based extraction. Sulfonamide residues could be detected in forty-six samples, ten of which contained a concentration of sulfaquinoxaline (151.4–1196.7μgkg−1 in chicken samples) and sulfadiazine (109.8μgkg−1 in a beef sample) exceeding the European Union-based maximum residue level by 1–12 folds, and thus were unfit for human consumption. Several acetylated, hydroxylated, and/or sulfated metabolites were identified, some of which were not previously detected in edible tissues. Most identified metabolites exhibited potential toxicity equivalent or higher than that of the parent molecule as estimated by in silico tests.
In the search of new robust and environmental-friendly analytical methods able to answer quantitative issues in pharmacology, we explore liquid chromatography (LC) associated with elemental mass ...spectrometry (ICP-MS) to monitor peptides in such complex biological matrices. The novelty is to use mass spectrometry to replace radiolabelling and radioactivity measurements, which represent up-to now the gold standard to measure organic compound concentrations in life science. As a proof of concept, we choose the vasopressin (AVP)/V1A receptor system for model pharmacological assays. The capacity of ICP-MS to provide highly sensitive quantitation of metallic and hetero elements, whatever the sample medium, prompted us to investigate this technique in combination with appropriate labelling of the peptide of interest. Selenium, that is scarcely present in biological media, was selected as a good compromise between ICP-MS response, covalent tagging ability using conventional sulfur chemistry and peptide detection specificity. Applying selenium monitoring by elemental mass spectrometry in pharmacology is challenging due to the very high salt content and organic material complexity of the samples that produces polyatomic aggregates and thus potentially mass interferences with selenium detection. Hyphenation with a chromatographic separation was found compulsory. Noteworthy, we aimed to develop a straightforward quantitative protocol that can be performed in any laboratory equipped with a standard macrobore LC-ICP-MS system, in order to avoid time-consuming sample treatment or special implementation of instrumental set-up, while allowing efficient suppression of all mass interferences to reach the targeted sensitivity. Significantly, a quantification limit of 57 ng Se L-1 (72 femtomoles of injected Se) was achieved, the samples issued from the pharmacological assays being directly introduced into the LC-ICP-MS system. The established method was successfully validated and applied to the measurement of the vasopressin ligand affinity for its V1A receptor through the determination of the dissociation constant (Kd) which was compared to the one recorded with conventional radioactivity assays.
A multi residue analysis was developed for screening, quantification and confirmation of 36 priority organic compounds included in the 2000/60/EC European Water Framework Directive. The compounds ...analyzed included 19 pesticides, 8 PAH, 5 endocrine-disruptors and 4 organochlorine compounds. The method was developed in three steps. First, automated off-line solid-phase extraction using Strata X cartridges was optimized to trap simultaneously the 36 studied compounds. Second, the more volatile compounds were analysed by gas chromatography coupled to mass spectrometry with electron impact ionisation in selected ion monitoring mode (SIM). Third, the last 20 compounds were detected and quantified, in one run, by liquid chromatography coupled to fluorescence detector and tandem mass spectrometry. The excellent selectivity and sensitivity allowed us satisfactory quantification and confirmation at levels as low as 0.2–67ngL−1 with recoveries between 59 and 105%. Such methodology was then applied to French surface waters: all the waters present organic contaminants, and their concentration varied according to the origin and nature of substances.
Chloride is often considered as the main chlorine form in soils. However, recent studies show that chlorine is mostly present in soils as naturally produced organically bound molecules. The relative ...contribution of biotic, including microbial, and abiotic processes to formation of organically bound chlorine remains poorly understood. We performed a37Cl spiking batch experiment with a forest soil incubated under abiotic and biotic conditions over two time periods to simultaneously monitor the formation of organically bound chlorine from natural and tracer chlorine. To compare biotic and abiotic conditions without biased effect of sterilization technique for abiotic control, the soil was irradiated and reinoculated or not with soil microflora. Fifteen days after microbial inoculation, the natural non-extractable organic chlorine content in the inoculated soil was significantly higher than in the sterile soil, showing that microbial activity contributed to formation of organically bound chlorine. However, no significant difference was noted between the two incubation periods. The same trend was noted for tracer chlorine, yet without a significant difference. The present study shows that chlorination is mediated by microbial activity, but there is also some indication of abiotic formation of organically bound chlorine, with a non-extractable organic tracer chlorine formation of about 6% just after spiking in abiotic conditions.
•Inorganic 37Cl was used to trace organically bound chlorine formation in soil incubation.•Irradiated forest soil was inoculated or not with soil microflora.•Organically bound chlorine was higher in inoculated than in sterile soil.•Abiotic processes also contribute to organic chlorine formation.
•Development of new rapid analytical method for 22 compounds of sulfonamides and their metabolites.•Combination QuEChERS–LC–LTQ-Orbitrap was applied.•A comprehensive qualitative and quantitative ...method was proposed.•Full validation of proposed method according to 2002/657/EC decision criteria.•Method was applied to a certified reference material and real animal tissues samples.
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 (R2<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 N4-acetyl metabolites using multi-stage high mass accuracy mass spectrometry.
One of the factors that may explain nowadays honeybees’ colonies losses is the increasing presence of chemicals in the environment. The aim of this study is to obtain a global view of the presence of ...environmental contaminants in beehives and, develop a fast, cheap and sensitive tool to analyze environmental contaminants in apiarian matrices. A multi residue analysis was developed to quantify 80 environmental contaminants, pesticides and veterinary drugs, belonging to different chemical classes, in honeys, honeybees and pollens. It consists in a single extraction, based on a modified “QuEChERS method”, followed by gas chromatography coupled with Time of Flight mass spectrometry (GC-ToF) and liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS). The “QuEChERS method” combines salting-out liquid-liquid extraction with acetonitrile and a dispersive-SPE clean up. It was adjusted to honey and especially to honeybee and pollen, by adding a small fraction of hexane in acetonitrile to eliminate lipids that interfere with mass spectrometry analysis. This method, combined with accurate and sensitive detection, allowed quantification and confirmation at levels as low as 10
ng/g, with recoveries between 60 and 120%. Application to more than 100 samples of each matrix was achieved for a global view of pesticide presence in the honeybee environment. Relatively high percentages of honeys, honeybees and pollens were found to be contaminated by pesticides used to combat varroa but also by fungicides like carbendazim and ubiquitous contaminants.
Mollusks are very sensitive to aquatic environmental alterations and then, are important bio-indicators for monitoring the contamination of water bodies. Iodinated X-ray contrast media (ICMs) are ...ubiquitously present in the aquatic environment, primarily due to their high consumption for diagnosis purposes, high injection levels, low biodegradability, and low removal rates by wastewater treatment plants. Although these compounds are assumed to be of low toxicity, aquatic organisms are continuously exposed to these agents, which may result in adverse effects as ICMs can act as iodine source and disrupt the endocrine system. Thus, the evaluation of their environmental risk, especially on aquatic fauna is of great interest.
To this end, we first compared the accumulation behavior, based on iodine analysis, of two ICM exhibiting different osmolality, diatrizoic acid and iohexol in Dreissena polymorpha bivalves exposed under laboratory conditions at concentrations of 0, 100, and 1000 μg/L during 4 and 7 days. This study was the first to provide information on iodine concentration in whole soft tissues and several organs in control zebra mussels. Moreover, it showed, after exposure, an increase of iodine content mainly in the digestive glands, followed by gills and gonads, highlighting that ICMs actually enter the organisms. Thus, bioaccumulation of ICMs studies were then performed, by liquid chromatography coupled to tandem mass spectrometry, on entire mollusks and digestive glands of organisms exposed at 0, 10, 100, and 1000 μg/L of both ICMs during 21 days, followed by 4 days of depuration. These first data on ICMs concentrations in zebra mussels, showed a clear accumulation of ICMs in mussels as a function of relative exposure level, as well as a rapid depuration. Osmolality did not seem to have a significant impact on the accumulation level, but a slight difference was observed on the accumulation pattern between both ICMs.
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•Basal iodine level is determined in organs of D. polymorpha bivalves for the first time.•Iodine concentration increases in different bivalve's tissues due to ICMs exposure.•Iodine accumulation is highest in the digestive glands.•For the first time the entering of ICMs in bivalves is demonstrated.•DTZ and IO both accumulate in bivalve whole tissues and digestive glands.
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► The use of bimodal chromatographic separation enlarged amount of compounds identified. ► The method allowed the largest scale ever (>60 compounds) speciation analysis of selenium ...metabolites in Se-rich yeast. ► The estimated concentration of compounds was given.
A high efficiency chromatographic separation on a porous graphitic carbon stationary phase was developed for a large-scale separation of selenium metabolites in Se-rich yeast prior to their identification by electrospray hybrid quadrupole trap/Orbitrap mass spectrometry (Orbitrap MSn). The reversed-phase (RP) separation mode offered distinctly higher separation efficiency than the hydrophilic ion interaction (HILIC) mode. The latter was nevertheless complementary and useful to validate the detection of several compounds. The method allowed the detection of 64 metabolites including 30 SeSe or SeS conjugates (3 triple S/Se/S ones) and 14 selenoethers. 21 previously unreported metabolites were detected on the basis of the selenium isotopic pattern usually matched with the sub-ppm mass accuracy. 9 of these metabolites were subsequently identified using the multi-stage high mass accuracy (<5ppm) mass spectrometry. The identified metabolites (and their groups) were quantified on-line by ICP-MS fitted with a frequency-matching generator allowing a quasi-uniform response over the large (20–90%) acetonitrile mobile phase concentration range. The morphology of HPLC–ICP-MS chromatograms was remarkably similar to that of HPLC multi-ion extracted ESI-MS chromatograms. The detection limits obtained by ICP MS and ESI MS were 1 and 2ppb, respectively.
Pressurized intraperitoneal aerosol chemotherapy (PIPAC) is a technique to directly deliver chemotherapeutic drugs in the abdomen for the treatment of peritoneal metastases. Pressurization improves ...the treatment efficacy but increases the risk of exposure for the medical/non-medical staff who can be exposed by dermal or ocular contact, or inhalation of aerosols containing the cytotoxic drugs. The aim of this study was to evaluate the risk of exposure for the medical/non-medical staff (nurses, surgeons, anaesthesiologists and cleaning personnel; n = 13) during PIPAC with oxaliplatin performed according to the protocol recommended in France. Blood samples were collected 1 h before and immediately after PIPAC, and urine samples 1 h before, and then 3 h and the morning after PIPAC. In the control, non-exposed group (n = 7), only one urine and blood sample were collected. Surface contamination in the operating room was assessed in water- and Surfanios-impregnated wipe samples. The total elemental platinum in each sample was quantified by inductively coupled plasma mass spectrometry, using a method adapted to quantify trace amounts (ng.L−1) in very low volumes (100 μl). No surface contamination was detected. Although 25% of urine samples in the exposed group contained platinum, no statistical difference was observed in urine and plasma samples collected before and after PIPAC and with the control group samples. These findings suggest that the French PIPAC protocol does not increase the risk of exposure to platinum in all staff categories involved. This protocol could be considered in future occupational policies and consensus statements.
Trial registration: NCT04014426
•First investigation of oxaliplatin exposure risk of medical staff during PIPAC in the environment and biological samples.•Methodology developed to quantify ultra-trace platinum levels in biological samples and on surfaces.•Surface contamination is absent including on the hot spots (i.e. the injector).•There is no statistical difference of biological samples before and after running the PIPAC protocol.•PIPAC with oxaliplatin under the French safety protocol is safe.
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