Direct injection Fourier transform ion cyclotron resonance mass spectrometric method for high throughput quantification of quinolones in poultry.

Many recent studies have shown high detection frequencies of quinolone antibiotics in poultry, as well as an increasing incidence of antimicrobial resistance. The main purpose of this project was to develop a fast and reliable analytical method for the detection of quinolones in poultry meat. In order to develop a rapid quantitative confirmation method, ion cyclotron resonance mass spectrometer was used. First, the sample preparation procedure was simplified by reducing the procedure to extraction and freezing out steps. Second, the chromatographic separation step was excluded and mass spectrometric parameters were optimised. Third, the method was validated by fortifying a blank matrix at four levels (0.5, 1, 1.5, and 2 times the maximum residue limit (MRL) or level of interest in those cases when no MRL was established). As a result, the overall analysis time was reduced to less than an hour. The validation study revealed that the method is capable of detection and confirmation of ten quinolone compounds in poultry above the detection capability (CCß) of the procedure. Finally, the developed method was applied to 19 commercially available chicken meat samples. None of the samples contained quinolones above the limit of quantification (LOQ) of the method. Analysis of treated chickens revealed that the developed method is suitable for the determination of ciprofloxacin and enrofloxacin. The developed method could be one of the fastest quantitative confirmatory methods for the analysis of quinolones available so far.

Mycotoxins in herbal teas marketed in Latvia and dietary exposure assessment.

The occurrence of 12 mycotoxins has been analysed by liquid chromatography - time of flight mass spectrometry in the batch of 60 herbal teas purchased from drugstores in Latvia. Among the dry tea samples, 90% were positive for one to eight mycotoxins. Enniatin B and deoxynivalenol (DON) were the most frequently detected mycotoxins in 55% and 45% of the samples, respectively. DON reached the highest level, from 129 µg kg-1 in herbal blend to 5,463 µg kg-1 in wormwood tea. Ochratoxin A (OTA) and aflatoxin B1 (AFB1) were found in 10% and 20% of the samples at the concentrations ranged between 2.99-30.3 µg kg-1 and 3.40-23.7 µg kg-1. Studies of the tea infusion process indicated that 32-100% of DON and zearalenone present in dry teas were extracted into the infusions. Dietary exposure assessment was performed, using the determined mycotoxin levels and the available consumption data.

Determination of residues and metabolites of more than 140 pharmacologically active substances in meat by liquid chromatography coupled to high resolution Orbitrap mass spectrometry.

This study reports an analytical method for simultaneous identification, screening and quantification of 164 residues and metabolites of pharmacologically active substances belonging to such therapeutic classes as anti-infectious (antibiotics and chemotheurapeutics), anti-inflammatory and antiparasitic agents (against protozoa, endo- and ectoparasites), corticoids and agents acting on the nervous and reproductive systems, substances with hormonal and thyreostatic action, and beta agonists. Different sample preparation procedures were compared and optimised for the detection of selected veterinary drugs in chicken, porcine and bovine meat by ultra-high performance liquid chromatography coupled to high-resolution Orbitrap mass spectrometry. The optimised instrumental method and sample preparation procedures were validated by fortifying blank matrix at four levels (0.5, 1.0, 1.5, and 2 times the maximum residue limit (MRL)), or at concentrations as low as possible for substances without an MRL. The evaluated performance parameters were selectivity, matrix effect, method and instrument limits of quantification, accuracy, and repeatability. A total of 130 selected compounds in chicken meat, 127 compounds in bovine meat and 123 compounds in porcine meat samples could be quantified with accuracy ranging from 70 to 120% and RSDs less than 30%. Finally, the method was successfully used to detect and quantify veterinary drug residues in real samples found to be suspect using the non-selective qualitative test for the detection of inhibitor substances. The results were confirmed using the relevant one-residue confirmatory methods revealing concentrations of residues higher than MRLs established for several samples.

Occurrence of polybrominated diphenyl ethers, perfluorinated compounds, and nonsteroidal anti-inflammatory drugs in freshwater mussels from Latvia.

The occurrence of polybrominated diphenyl ethers (PBDE), perfluorinated compounds (PFC), and nonsteroidal anti-inflammatory drugs (NSAID) in Latvian freshwater ecosystems was evaluated by using filter-feeding mussels as bioindicators. Twenty four samples of mussels were collected from freshwater bodies throughout the territory of Latvia during the summer of 2017. PBDE contamination was ubiquitous, reaching the highest total concentration of 193.2 pg g-1 w.w. BDE-209 was the most abundant compound, followed by penta-BDE components BDE-49, -100, -99, -153, -154, and -47 in decreasing order. The levels of PFCs in Latvian mussels were generally lower than those reported from other regions. Perfluorooctanoic acid (PFOA) was more common in mussels than perfluorooctane sulfonate (PFOS). Ibuprofen was the only NSAID detected in mussels during this study (detection frequency 50%). The observed concentrations of this compound varied between 0.52 and 109 ng g-1 w.w., being noticeably higher than reported by other authors. Overall, the results indicate that among the three analysed groups of contaminants, ibuprofen is present in Latvian freshwater environment at relatively high levels and further monitoring should be carried out.

Determination of acidic non-steroidal anti-inflammatory drugs in aquatic samples by liquid chromatography-triple quadrupole mass spectrometry combined with carbon nanotubes-based solid-phase extraction.

A solid-phase extraction (SPE) method based on multi-walled carbon nanotubes (CNT) was developed for the determination of 12 acidic non-steroidal anti-inflammatory drugs (NSAIDs) in surface waters and tap water. Pristine and functionalised CNTs were evaluated as sorbent materials. Batch experiments were used to optimise sorption and desorption conditions (sorbent type and amount, adsorption time, pH). The adsorption equilibrium was reached after 8 to 48 h duration, which increased with the pH of solution. Non-agglomerated pristine CNTs (20 mg) showed the most optimal adsorption (94 to 100%) for all of the analytes after a 30-min contact period in acidified water solutions (100 mL). The compounds retained at those conditions were recovered by 40 to 95% by using 5% ammonium hydroxide in methanol as the desorbing solution at ambient conditions. A comprehensive liquid chromatography coupled to triple quadrupole mass spectrometry (LC-QqQ-MS/MS) was used for the analysis of real water samples. The method showed sufficient recovery (65-125%) and good precision (2-14% relative standard deviation (RSD)). The limits of detection and quantification ranged between 0.01 and 1.3 ng L-1 and 0.04 and 3.9 ng L-1. Only diclofenac and ibuprofen were found in the analysed surface water samples from Latvia (n = 10) and Norway (n = 14). Diclofenac was found at 1.7-8.4 ng L-1 concentration in two samples of surface waters, whereas the concentrations of ibuprofen ranged between 1.0 and 9.2 ng L-1 in seven samples collected in Norway and 3.9-17 ng L-1 in three samples from Latvia.

Determination of pharmaceutical residues and assessment of their removal efficiency at the Daugavgriva municipal wastewater treatment plant in Riga, Latvia.

Pharmaceutical products (PPs) belong to emerging contaminants that may accumulate along with other chemical pollutants in wastewaters (WWs) entering industrial and/or urban wastewater treatment plants (WWTPs). In the present study, the technique of ultra-high-performance liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (Orbitrap-HRMS) was applied for the analysis of 24 multi-class PPs in WW samples collected at different technological stages of Daugavgriva WWTP located in Riga, Latvia. Caffeine and acetaminophen levels in the range of 7,570-11,403 ng/L and 810-1,883 ng/L, respectively, were the predominant compounds among 19 PPs determined in the WW. The results indicate that aerobic digestion in biological ponds was insufficiently effective to degrade most of the PPs (reduction efficiency <0-50.0%) with the exception of four PPs that showed degradation efficiency varying from 55.0 to 99.9%. Tests of short-term chemical and enzymatic hydrolysis for PP degradation in WW samples were performed, and the results reflected the complexity of different degradation mechanisms and physicochemical transformations of PPs. The toxicological studies of WW impact on Daphnia magna indicated gradual reduction of the total toxicity through the treatment stages at the WWTP.

Ultra high performance liquid chromatography-time-of-flight high resolution mass spectrometry in the analysis of hexabromocyclododecane diastereomers: method development and comparative evaluation versus ultra high performance liquid chromatography coupled to Orbitrap high resolution mass spectrometry and triple quadrupole tandem mass spectrometry.

An efficient ultra high performance liquid chromatography (UHPLC)-time-of-flight high resolution mass spectrometry (TOF-HRMS) method was elaborated for the determination of hexabromocyclododecane (HBCD) diastereomers in fish samples and compared against UHPLC-Orbitrap-HRMS and UHPLC-triple quadrupole (QqQ) tandem MS (MS/MS) techniques. The TOF-HRMS analyzer was operated at high resolution (>10000 full width at half maximum (FWHM)) with scanning the m/z range from 600 to 700, to achieve picogram quantitation limits. The effects of various operational parameters on the instrumental response were systematically investigated. Evaluation of the influence of sample clean-up procedure steps on signal suppression effect including removal of the matrix components by means of destructive acidic treatment or non-destructive gel permeation chromatography (GPC), and additional Florisil column chromatography step showed that the analytical response of UHPLC-TOF-HRMS system is much more affected by the presence of matrix components in the final extracts in comparison with UHPLC-Orbitrap-HRMS and UHPLC-QqQ-MS/MS systems. The method was robustly validated and used for the analysis of eel (Anquilla anquilla) samples originating from a Latvian lake. UHPLC-TOF-HRMS showed a suitable performance under the optimized conditions: recoveries for three selected diastereomers in the range of 99-116%; repeatability and intermediate precision expressed as relative standard deviation (RSD) in the ranges of 2.3-7.1% and 2.9-8.1%, respectively. The elaborated method achieved instrumental limits of quantification (i-LOQ) of 0.9-4.5pg on column that were suitable for the trace analysis of three HBCD diastereomers, corresponding to the method limits of quantification (m-LOQ) of 7.0-29pgg(-1) wet weight (w.w.). The efficiency of UHPLC-TOF-HRMS method was evaluated by comparing the performance characteristics and analytical data from real samples with the validation data and real sample results obtained by applying UHPLC-Orbitrap-HRMS and UHPLC-QqQ-MS/MS techniques for the analysis of HBCD in the same fish samples. Statistical assessment of the experimental data by means of the Fiedman's test revealed that UHPLC-TOF-HRMS, UHPLC-QqQ-MS/MS and UHPLC-Orbitrap-HRMS techniques produced adequate and similar results regarding the HBCD content in fish samples. The presence of HBCD diastereomers was confirmed in all the analyzed eels at concentrations up to 554pgg(-1) w.w. for total HBCD and a diastereomer pattern typical for aquatic biota was observed with strong predominance of α-HBCD. The UHPLC-TOF-HRMS is an appropriate technique for diastereomer-specific quantification of HBCD content in fish samples.