Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDD), dechlorane-related compounds (DRCs), and emerging brominated flame retardants (EBFRs) in foods: The levels, profiles, and dietary intake in Latvia.

This study was performed to assess the Latvian population exposure to polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDD), dechlorane-related compounds (DRCs), and emerging brominated flame retardants (EBFRs). Food items including fish, fish products, meat, dairy products, cereals and bread, eggs, vegetable oils, and sweets were analyzed for the content of these contaminants, followed by per capita intake calculations and risk assessment. The highest dietary exposure for general population was observed in the case of HBCDD, .reaching an estimated daily intake (EDI) value of 2.92 ng kg-1 b.w. (or 3.35 ng kg-1 b.w. if an outlying data point is included), followed by PBDEs with EDI of 1.24 ng kg-1 b.w., including ~25% contribution of PBDE-209 to the overall EDI from PBDEs. DRCs and EBFRs were secondary contributors to the total intake of selected flame retardants (FRs), with the observed EDIs of 0.46 and 0.47 ng kg-1 b.w, respectively. The obtained occurrence data and risk characterization according to the European Food Safety Authority (EFSA) approach showed the calculated margin of exposure (MOE) values higher than the critical values for PBDE-47, -99 and -153as well as for HBCDD, indicating that the estimated dietary exposures are unlikely to be of significant health concern for the Latvian population. At the same time, it should be pointed out that the risk assessment was performed only for five out of the twenty-five selected halogenated flame retardants (HFRs), while cumulative effects due to the potential presence of other HFRs and their biodegradation products were not considered.

Polychlorinated naphthalenes (PCNs) in food products in Latvia: Congener-specific analysis, occurrence, and dietary exposure of the general population.

A study was performed to evaluate the dietary exposure of the Latvian population to polychlorinated naphthalenes (PCNs). Based on the toxicological characteristics, provisional levels of occurrence, congener patterns, and the availability of analytical standards, twenty-six congeners were included in the analysis. Considering the planar structure of PCNs, an analytical protocol on the basis of destructive clean-up and isolation of analytes on carbon was applied, while GC-HRMS and isotope dilution were used for the detection and quantification of analytes. Commonly consumed foods were analyzed for the content of PCNs, followed by per capita intake calculations. By applying the available in vitro relative potency (REP) factors, putative toxic equivalents (TEQ) were determined, in order to assess the "dioxin-like" effect arising from the presence of PCNs in food. The daily intake (EDI) for total PCNs (∑PCN) and PCN-TEQ for the general population were calculated to be 116 pg kg-1 body weight (b.w.) and 0.036 pg TEQ kg-1 b.w., respectively. Fish and fish products were found to provide the main contribution to the dietary "dioxin-like" burden of PCNs, constituting ∼60% of the total PCN-TEQ intake. For some fish samples, PCN-TEQ could additionally contribute up to ∼3% to the regulated PCDD/F-PCB-TEQ, while for other matrices this contribution could be lower by an order of magnitude. The obtained data indicated that the estimated dietary exposure to PCNs is likely to be of low concern, although PCN-TEQ could be recognized as a contributor to the overall "dioxin-like" TEQ loading that results from the exposure to halogenated aromatics.

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.

Multi-analyte method for the analysis of legacy and alternative brominated and chlorinated flame retardants in food products of animal origin using gas chromatography - magnetic sector high resolution mass spectrometry.

An analytical method was developed and validated for the analysis of 32 halogenated flame retardants (HFRs), including 13 polybrominated diphenyl ethers (PBDEs), 9 dechlorane-related compounds (DRCs) and 10 of the so-called alternative BFRs in food samples of animal origin. Gas chromatography (GC) coupled with magnetic sector high resolution mass spectrometry (HRMS) was used for the instrumental analysis. Intralaboratory validation of the developed method was performed in terms of recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ). Where possible, trueness was verified by the analysis of reference materials (RMs). For analytes with available isotopically labeled surrogates, recoveries in the range of 70-120% and repeatability rates below 20% were observed, while for compounds quantitated using absolute calibration the values of recovery ranged from 59 to 153% and the repeatability in terms of RSDs was in the range of 1-26%. The values measured for the four analyzed RMs agreed with the provided consensus values, revealing that the recovery of reference concentrations for compounds with assigned consensus values was in 72-119% range. The elaborated method met the sensitivity criteria according to the Commission Recommendation, 2014/118/EU on the monitoring of BFRs in food products. The developed method was successfully applied for the analysis of numerous food samples. The analyses revealed ubiquitous presence of PBDEs and the majority of DRCs in the analyzed samples, while alternative BFRs were detected only occasionally.

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.

Evaluation of analytical performance of gas chromatography coupled with atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS) in the target and non-targeted analysis of brominated and chlorinated flame retardants in food.

A new analytical method was established and validated for the analysis of eighteen halogenated flame retardants (HFRs)in food products. Gas chromatography (GC) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) employing atmospheric pressure chemical ionization (APCI) was used for the identification and quantitation of contaminants. Intra-laboratory validation of the method was performed with respect to recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ), and trueness was verified where possible by analysis of reference materials (RMs). The validation results indicated recoveries of analytes between 59 and 115%, the repeatability in terms of relative standard deviations (RSDs) in the range of 5-15% and linearity with correlation coefficients of ≥0.99 between the i-LOQ and 250 pg injected on-column. The method i-LOQs ranged from ∼1 pg to ∼5 pg injected on-column, while m-LOQs were in the range of 0.002-0.04 ng g-1 sample. The measured values for RMs agreed with the provided values, giving the accuracy of obtained concentrations in the range of 92-133% with RSD range of 2-15% and were in agreement with the results obtained with the reference method based on magnetic sector GC-HRMS. For the majority of the compounds, the method met a limit of quantification criterion stated in the Commission Recommendation, 2014/118/EU on monitoring BFRs in food. The developed method was demonstrated to be suitable for qualitative screening of suspect target contaminants presented in the samples by the post-run treatment of raw data and confirmation by isotope cluster analysis.

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.

Emerging brominated flame retardants and dechlorane-related compounds in European eels (Anguilla anguilla) from Latvian lakes.

Fifteen halogenated flame retardants (HFRs) including seven emerging brominated flame retardants (EBFRs) and eight dechlorane-related compounds (DRCs) were analyzed in eels (Anguilla anguilla) sampled from five Latvian lakes. Out of the seven EBFRs, hexabromocyclododecane (HBCD) and decabromodiphenyl ethane (DBDPE) were found in eels in quantifiable concentrations, up to 6.58 and 33.0 ng g-1 lipid weight (l.w.), respectively. The mean total concentration of DRCs (∑DRC) in the samples was 0.62 ng g-1 l.w. and the geographical distribution of DRC contamination was nearly uniform among the selected lakes. Dechlorane 602 (Dec 602) was the predominant component, whereas the composition of mixture containing syn- and anti-Dechlorane Plus (DP) stereoisomers showed a pronounced enrichment of the anti-DP isomer and was close to the composition of OxyChem® DP commercial product. The determined concentrations of HFRs were lower than in other studies of aquatic biota from Europe and Asia, and the obtained results reflect the acceptable environmental status of Latvian lakes with regard to the total content of HBCD (∑HBCD), considering the environmental quality standards (EQS) stated in the Directive 2013/39/EU. The highest ∑HBCD levels were observed in eels from lakes corresponding to the industrialization of those areas, while the results of principal component analysis (PCA) showed that the concentration of HBCD depended on the particular sampling lake, reflecting non-uniform contamination of the Latvian environment with this EBFR.

Brominated flame retardants and toxic elements in the meat and liver of red deer (Cervus elaphus), wild boar (Sus scrofa), and moose (Alces alces) from Latvian wildlife.

In order to evaluate the contamination status of terrestrial biota in Latvia, muscle and liver tissues of red deer (Cervus elaphus), wild boar (Sus scrofa), and moose (Alces alces) were analyzed for the content of polybrominated diphenyl ethers (PBDE), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), as well as cadmium and lead. The highest mean concentrations of PBDEs (46.6pgg-1 wet weight (w.w.)), cadmium (0.95mgkg-1 w.w.), and lead (0.22mgkg-1 w.w.) were observed in the tissues of moose, while the wild boar samples contained the highest levels of HBCD, with the mean concentration equal to 264pgg-1 w.w. in muscle tissues. Generally low mean concentrations of TBBPA from 0.52 to 4.54pgg-1 w.w. were observed. The liver tissue of all analyzed specimens was found to contain higher concentrations of contaminants, compared to muscle tissue. The congener profile of PBDEs in the analyzed tissues indicated that the recently used "penta-BDE" formulation was a probable source, while components of HBCD, "octa-BDE", and "deca-BDE" technical mixtures are likely to undergo congener-specific or diastereomer-specific bioaccumulation or metabolic degradation. Considering the reports from other regions, it can be concluded that the terrestrial biota in Latvia is less affected by the studied contaminants.

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.

Determination of steroidal oestrogens in tap water samples using solid-phase extraction on a molecularly imprinted polymer sorbent and quantification with gas chromatography-mass spectrometry (GC-MS).

An analytical method was established and validated for the analysis of steroidal oestrogens in tap water samples. Gas chromatography coupled to high-resolution mass spectrometry (GC-HRMS) and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) were used for the identification/quantification of selected compounds and the analytical performance of these techniques was evaluated. Liquid-liquid extraction (LLE) and solid-phase extraction (SPE) with a molecularly imprinted polymer (MIP) stationary phase that was highly selective for oestrogens were used for the extraction of 100-mL aliquots of water samples. The recoveries of analytes with the described methods ranged from 92 to 114 %, while the repeatability in terms of relative standard deviations (RSDs) was in the range from 2.1 to 15.2 % (n = 5). It was concluded that SPE with MIP that was highly selective for oestrogens in combination with GC-HRMS detection is more preferable for the analysis of oestrogens in tap water samples. The typical oestrogen, 17ß-estradiol (17ß-E2), was detected above the method limit of quantification (m-LOQ) in 5 of 14 analysed tap water samples at concentrations from 0.09 to 0.15 ng L(-1). Despite that 17α-ethynylestradiol (17α-EE2) was not quantified in this study above m-LOQ, the presence of this chemical was qualitatively confirmed in some of the analysed samples.

Trace determination of perfluorooctane sulfonate and perfluorooctanoic acid in environmental samples (surface water, wastewater, biota, sediments, and sewage sludge) using liquid chromatography - Orbitrap mass spectrometry.

An analytical method was established and validated for the analysis of the most frequently monitored representatives among the group of perfluorinated compounds (PFAS), namely, perfluorooctanoic acid (PFOA) and prefluorooctane sulfonate (PFOS) in environmental samples (surface water, wastewater, sediments, sewage sludge, and biota). High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing a heated electrospray ionization (HESI) interface operated in negative mode was used for the quantitative determination of these contaminants. HPLC separation of analytes was achieved using a reversed phase C18 (RP-C18) analytical column. The efficiency of various solid phase extraction (SPE) columns for the pre-concentration and clean-up as well as the performance of different ionization sources and detection modes for the instrumental determination were evaluated. The validation results indicate recoveries of analytes between 88 and 116%, while the intra-day and inter-day precision parameters in terms of relative standard deviations (RSDs) were in the range of 1.0-5.9% and 1.5-7.3%, respectively. The measured values for certified reference material (CRM) agreed with the provided reference values, revealing the accuracy of obtained concentrations in the range of 107-108%. The trueness of the method was verified by a successful participation in a proficiency testing (PT) program. These performance characteristics of the method permit reliable monitoring of PFOS and its derivatives in environmental samples according to the environmental quality standard (EQS) criteria regarding the maximum allowable concentrations and taking into account the annual average concentrations stated in Directive 2013/39/EU. The elaborated method was applied for the routine analysis of selected PFAS in environmental samples from the Baltic region.

Analytical capabilities of high performance liquid chromatography - Atmospheric pressure photoionization - Orbitrap mass spectrometry (HPLC-APPI-Orbitrap-MS) for the trace determination of novel and emerging flame retardants in fish.

A new analytical method was established and validated for the analysis of 27 brominated flame retardants (BFRs), including so called "emerging" and "novel" BFRs (EBFRs and NBFRs) in fish samples. High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing atmospheric pressure photoionization (APPI) interface operated in negative mode was used for the identification/quantitation of contaminants. HPLC-Orbitrap-MS analysis provided a fast separation of selected analytes within 14 min, thus demonstrating a high throughput processing of samples. The developed methodology was tested by intralaboratory validation in terms of recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ), and where possible, trueness was verified by analysis of certified reference materials (CRMs). Recoveries of analytes were between 80 and 119%, while the repeatability in terms of relative standard deviations (RSDs) was in the range from 1.2 to 15.5%. The measured values for both analyzed CRMs agreed with the provided consensus values, revealing the recovery of reference concentrations in 72-119% range. The elaborated method met the sensitivity criterion according to Commission Recommendation 2014/118/EU on monitoring of BFRs in food products for majority of the compounds. The concentrations of polybrominated diphenyl ethers (PBDEs) in real samples determined by HPLC-APPI-Orbitrap-MS method and validated gas chromatography-high-resolution mass spectrometry (GC-HRMS) method were found to be in a good agreement.

Method development for the simultaneous determination of polybrominated, polychlorinated, mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls and polybrominated diphenyl ethers in fish.

An analytical methodology was developed for simultaneous determination of five groups of persistent organic pollutants (POPs) including polybrominated, polychlorinated and mixed brominated-chlorinated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs, PCDD/DFs and PXDD/DFs, respectively), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in fish samples. The presented analytical approach was based on well established and robust method for determination of PCDD/DFs and PCBs, which was augmented with gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) to include PBDEs, as well as poorly investigated PBDD/DFs and PXDD/DFs at toxicologically significant levels. Intensive clean-up and fractionation procedures in combination with optimized instrumental parameters provided reliable detection and quantification of these compounds. The application of (13)C12-labeled surrogates of analyzed compounds allowed the internal standardization and accurate measurement of selected contaminants. The developed procedure was validated while taking into account the Commission Regulation (EU) 252/2012 requirements for PCDD/DFs and PCBs, and was used to measure the occurrence of priority POPs in Baltic wild salmon.

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.

Polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in food and feed in Latvia in 2009-2011.

During 2009-2011 a monitoring programme for 17 polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and 12 dioxin-like polychlorinated biphenyls (DL-PCBs) was conducted in the Latvian food and feed market. Using ISO 17025-accredited analytical methodology, investigation of 121 food (milk, dairy products, meat, eggs, fish, fish products) and 66 feed samples (fish meal and oil, compound and mineral feed, vegetable and animal fats) was performed. Most samples showed contamination below the European Commission (EC) Regulation No. 1881/2006 and Commission Directive 2006/13/EC limits. Average total toxicological equivalent (total-TEQ(1998)) concentrations within the food sample groups, except fish and fish products, ranged between 0.41 and 15.1 pg total-TEQ(1998) g(-1) fat. Fish and fish products showed contamination levels from 0.18 to 46.0 pg total-TEQ(1998) g(-1) fresh weight (f.w.). Fifty-seven per cent of cod liver samples were non-compliant. The most contaminated feed samples were fish meal and fish oil. A comparison with WHO-TEF(2005) data is given.

New perspectives on diastereoselective determination of hexabromocyclododecane traces in fish by ultra high performance liquid chromatography-high resolution orbitrap mass spectrometry.

A new analytical method is presented for diastereoisomer-specific identification and quantitation of hexabromocyclododecanes (HBCD) in fish samples. The method is based on extraction of the target analytes from samples with a mixture of organic solvents, with further three-stage clean-up including destructive removal of matrix components with sulphuric acid and acid-impregnated silica gel, and Florisil adsorption column chromatography. Ultra high performance liquid chromatography (UPLC) coupled with high resolution (HR) Orbitrap mass spectrometry featuring heated electrospray ionization (HESI-II) interface operated in negative ion mode was employed for the identification/quantitation of contaminants. The developed methodology was robustly validated in terms of recovery, repeatability, intermediate precision, linear calibration ranges, limits of detection and quantitation, and used for analysis of twenty five Baltic wild salmon (Salmo salar) samples. Under the optimized conditions, recoveries for selected analytes were within the range of 91.4-103.6%, and the repeatability and intermediate precision in terms of relative standard deviations (RSDs) were in the ranges 1.6-8.3% and 1.6-12.5%, respectively, for all three validation levels. The elaborated method achieved instrumental limits of quantification (i-LOQ) of 1.3-3.0pg on column for three HBCD diastereoisomers corresponding to the method LOQ of 0.005-0.012ngg(-1) wet weight (w.w.) The presence of HBCD diastereoisomers was confirmed in all the analyzed Baltic salmon samples in the concentration range of 0.39-3.82ngg(-1) w.w. with an average of 1.59ngg(-1) w.w. for total HBCD. The diastereomer pattern typical for aquatic biota was observed with strong predominance of α-HBCD. The newly developed methodology could be employed for a regular diastereomer-specific monitoring of HBCD content in fish samples, representing a good alternative to existing LC-MS/MS methods in terms of sensitivity and accuracy, and providing further possibilities for inclusion of other contaminants in the scope of analysis.

Toxicity assessment and biodegradation potential of water-soluble sludge containing 2,4,6-trinitrotoluene.

The water-soluble phase of trinitrotoluene-containing sludge (SLP) was characterized with regard to trinitrotoluene (TNT) concentration, ecotoxicity, and a model biodegradation experiment as evaluation criteria for further development of appropriate treatment technologies. SLP contained 67.8 mg TNT/l. The results of germination and root-elongation tests indicated that SLP had a species-specific phytotoxic effect. The results of a 21 day degradation experiment demonstrated TNT conversion to 4-amino-2,6-DNT and 2-amino-4,6-DNT, with a simultaneous reduction in the total concentration of nitroaromatics. Addition of inoculum stimulated the TNT degradation process. The presence of the sludge solid phase inhibited microbial activity. Measurement of microbial enzyme activity was used to assess changes in the microbial community during the biodegradation process.