Fatty Acid Composition of a Maternal Diet and Erythrocyte Phospholipid Status in Latvian Pregnant Women.

BACKGROUND AND OBJECTIVES: Dietary fats are essential for maternal and fetal health. Fatty acids (FAs) in erythrocytes characterize the FA profile, which is influenced by diet and other factors. The aim of this study was to evaluate the association between the main FAs in erythrocyte membrane phospholipids and their influencing factors-dietary fat and supplement intake and lifestyle factors-in Latvian pregnant women. MATERIALS AND METHODS: This cross-sectional study included 236 pregnant and postpartum women. The data were collected from medical documentation, a food frequency questionnaire, and a questionnaire on demographic, lifestyle, health status, and nutritional habits in outpatient clinics and maternity departments. FAs in erythrocyte membrane phospholipids were determined using gas chromatography. RESULTS: Correlations were found between dietary SFAs and erythrocyte SFAs (r = -0.140, p = 0.032) and PUFAs (r = 0.167, p = 0.01) and between dietary PUFAs and erythrocyte MUFAs (r = -0.143, p = 0.028). Dietary SFAs, MUFAs, and PUFAs positively correlated with the studied n-3 and n-6 FAs in erythrocytes. Vitamin D correlated positively with MUFA and negatively with total PUFA and AA in erythrocytes. There was a negative correlation between dietary vitamin A and linoleic acid in erythrocytes. Physical activity negatively correlated with erythrocyte MUFAs and positively with erythrocyte PUFAs. Alcohol consumption positively correlated with erythrocyte SFAs and negatively with erythrocyte PUFAs. CONCLUSIONS: There are indications that some dietary FAs may be correlated with erythrocyte FAs. Possible influencing factors for this association are alcohol, physical activity, vitamin D, and vitamin A.

Merging Copper(I) Photoredox Catalysis and Iodine(III) Chemistry for the Oxy-monofluoromethylation of Alkenes.

A simple process for the oxy-monofluoromethylation of alkenes is described. In combination with visible-light copper(I) photoredox catalysis, an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands serves as a powerful source of a monofluoromethyl (CH2 F) radical, enabling the step economical synthesis of γ-fluoro-acetates from a broad range of olefinic substrates under mild conditions. Applications to late-stage diversification of alkenes derived from complex molecules, amino acids and the synthesis of fluoromethylated heterocycles are also demonstrated.

Fluorohalomethylsulfonium Salts as a Fluorohalocarbene Source.

Synthesis of fluoroorganic compounds is of great importance due to their extensive application in medicinal chemistry, agrochemicals, and materials. Herein, we report efficient synthesis of novel diaryl fluorohalomethyl sulfonium salts. The application showcased proficient reagents for Freon-free fluorochloro-, fluorobromo-, and fluoroiodocarbene transfer to alkenes. The developed mild, room temperature conditions for the cyclopropanation do not require any metal catalysts and allow synthetic access to diverse cyclopropanes.

The Intake of Omega-3 Fatty Acids, the Omega-3 Index in Pregnant Women, and Their Correlations with Gestational Length and Newborn Birth Weight.

BACKGROUND: During pregnancy, the demand for omega-3 fatty acids, notably docosahexaenoic acid (DHA), escalates for both maternal and foetal health. Insufficient levels can lead to complications and can affect foetal development. This study investigated omega-3 status and its relation to dietary intake in pregnant Latvian women, along with its impact on gestational duration and newborn birth weight. METHODS: The study comprised 250 pregnant and postpartum women with a mean age of 31.6 ± 4.8 years. Nutrition and omega-3 supplementation data were collected through a questionnaire covering 199 food items and 12 supplements. Fatty acids in erythrocyte membrane phospholipids were analysed via gas chromatography with flame ionization detection. RESULTS: The median omega-3 fatty acid intake, including eicosapentaenoic acid (EPA) and DHA from diet and supplements, was 0.370 g/day, which is deemed sufficient. However, the median weekly fish intake (126.0 g) and daily nut/seed intake (7.4 g) were insufficient. The median omega-3 supplement intake was 1.0 g/day. No correlation between omega-3 supplement intake and the omega-3 index was observed. There was a weak correlation between the DHA intake from fish and the omega-3 index (r = 0.126, p = 0.047), while a significant correlation between the total EPA and DHA intake from various sources and the omega-3 index was noted (r = 0.163, p = 0.01). Most women (61.6%) had an omega-3 index < 4%, while 34.8% had an index between 4 and 8%, and only 3.6% had an index > 8%. Notably, significant differences in EPA levels and the omega-3 index were found among respondents with differing infant birth weights (p < 0.05). CONCLUSIONS: The omega-3 intake during pregnancy adheres to the established guidelines, although fish consumption remains insufficient. A preconception evaluation of the omega-3 index is advocated to optimize prenatal intake. The indications suggest potential correlations between EPA levels, the omega-3 index, and infant birth weight.

Summary recommendations on "Analytical methods for substances in the Watch List under the Water Framework Directive".

The Watch List (WL) is a monitoring program under the European Water Framework Directive (WFD) to obtain high-quality Union-wide monitoring data on potential water pollutants for which scarce monitoring data or data of insufficient quality are available. The main purpose of the WL data collection is to determine if the substances pose a risk to the aquatic environment at EU level and subsequently to decide whether a threshold, the Environmental Quality Standards (EQS) should be set for them and, potentially to be listed as priority substance in the WFD. The first WL was established in 2015 and contained 10 individual or groups of substances while the 4th WL was launched in 2022. The results of monitoring the substances of the first WL showed that some countries had difficulties to reach an analytical Limit of Quantification (LOQ) below or equal to the Predicted No-Effect Concentrations (PNEC) or EQS. The Joint Research Centre (JRC) of the European Commission (EC) organised a series of workshops to support the EU Member States (MS) and their activities under the WFD. Sharing the knowledge among the Member States on the analytical methods is important to deliver good data quality. The outcome and the discussion engaged with the experts are described in this paper, and in addition a literature review of the most important publications on the analysis of 17-alpha-ethinylestradiol (EE2), amoxicillin, ciprofloxacin, metaflumizone, fipronil, metformin, and guanylurea from the last years is presented.

Occurrence of brominated persistent organic pollutants (PBDD/DFs, PXDD/DFs, and PBDEs) in Baltic wild salmon ( Salmo salar ) and correlation with PCDD/DFs and PCBs.

The contamination profiles of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), diphenyl ethers (PBDEs), and mixed monobromo/chloro dibenzo-p-dioxins (PXDDs) and dibenzofurans (PXDFs) were determined in the tissue of Baltic wild salmon and compared with those of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs). Out of the analyzed PXDD/DFs, only the 3-B-2,7,8-triCDF was detected (in the concentration range of 0.039-0.075 pg g(-1) fresh weight (f.w.)). The toxic equivalents (TEQs) for analyzed PBDD/DFs (0.074-0.142 pg TEQ g(-1) f.w.) were found to contribute on average 2.1% to the total PCDD/DF-PBDD/DF-TEQ. The total concentrations of 27 PBDE congeners were in the range of 1.3-5.6 ng g(-1) f.w., with an average of 3.3 ng g(-1) f.w. The levels of PCDD/DFs and PCBs were found to be in the range of 4.53-14.6 pg WHO(2005)-PCDD/DF-PCB-TEQ g(-1) f.w., and concentrations of these compounds in most of the analyzed samples were above the maximum levels specified in Commission Regulation (EU) No. 1259/2011. Good correlation was observed between WHO(2005)-PCDD/DF-TEQ and WHO(2005)-PCB-TEQ (r(2) = 0.98), and these parameters were well correlated with the total sum of PBDE concentrations (r(2) = 0.91 and r(2) = 0.94, respectively). The results suggest that the consumption of Baltic wild salmon has no crucial impact on the average POP intake for typical Latvians.

Application of nano-LC - nano-ESI - Orbitrap-MS for trace determination of four priority PFAS in food products considering recently established tolerable weekly intake (TWI) limits.

An analytical method was developed and validated for the analysis of four priority perfluoroalkyl substances (PFAS), namely, perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulfonic acid (PFHxS), and perfluorooctanesulfonate (PFOS) in food products using nanoscale liquid chromatography (nano-LC) coupled with nanoscale electrospray ionization (nano-ESI) and Orbitrap mass spectrometry (Orbitrap-MS) detection. The efficiency of two different nano-LC setups for chromatographic separation of selected PFAS was evaluated. The optimal LC separation of analytes was achieved using a reversed phase C18 (RP-C18) nano bore column with an integrated emitter. The effect of matrix concentration factor on signal suppression/enhancement was evaluated for different matrices. The method validation indicated analyte recoveries in the range 83-118% and within-laboratory reproducibility from 7 to 18%, while reanalysis of the materials from proficiency tests (PTs) showed that the accuracy of the obtained concentrations ranged from 85 to 124% of the provided consensus values. The method limits of quantification (m-LOQs) were set as first validation levels ranging from 0.001 to 0.3 ng g-1 sample depending on the type of the food group. The observed method performance characteristics met the criteria stated in Commission Regulation (EU) 2022/1428, Commission Recommendation (EU) 2022/1431, as well as Guidance Document on Analytical Parameters for the Determination of Per- and Polyfluoroalkyl Substances (PFAS) in Food and Feed with regards to the compliance testing of PFAS maximum levels (MLs) and monitoring purposes. The elaborated method was applied for the analysis of selected priority PFAS in different food groups collected from the Latvian retail market.

Synthetic Access to Fluorocyclopropylidenes.

Herein we report an approach for the straightforward preparation of fluorocyclopropylidene group from aldehydes and ketones via Julia-Kocienski olefination using the newly developed reagent 5-((2-fluorocyclopropyl)sulfonyl)-1-phenyl-1H-tetrazole. Derivatization of monofluorocyclopropylidene compounds includes hydrogenation to deliver fluorocyclopropylmethyl compounds and fluorinated cyclobutanones. The utility of the described method is demonstrated by the synthesis of a fluorocyclopropyl-containing analogue of ibuprofen. Bioisosteric replacement of isobutyl with the fluorocyclopropyl group may be used for tuning biological properties of drug molecules.

Data on occurrence of perfluoroalkyl substances in influents and effluents collected from different wastewater treatment plants in Latvia.

The data set provided in this paper contains occurrence data of 17 perfluoroalkyl substances (PFAS) (including 10 perfluorinated carboxylic acids and 7 perfluorinated sulfonic acids) in influent and effluent samples collected from 43 wastewater treatment plants (WWTPs) located in different cities in Latvia. Samples were collected in the period June-July 2021. In each WWTP one influent and one effluent sample were collected on the same day. Extraction and clean-up of the samples were performed using solid phase extraction (SPE) on a weak-anion SPE phase. Observed extracts were analysed using high performance liquid chromatography coupled with Orbitrap high resolution mass spectrometry (HPLC-Orbitrap-MS) on the content of selected PFAS representatives. The collected data are with fundamental scientific value and can be applied for local data analysis. The data set is useful for the estimation of overall background levels of PFAS and evaluation of local city WWTPs wastewater remediation efficiency towards the removal of PFAS contamination.

Iron-Catalyzed Fluoromethylene Transfer from a Sulfonium Reagent.

Herein, we report the first example of an iron porphyrin catalyzed fluoromethylene transfer from (2,4-dimethylphenyl)(fluoromethyl)(phenyl)sulfonium tetrafluoroborate to unactivated alkenes. The fluorocarbene or fluoromethylene synthon is the smallest "organic" node in a molecular graph of the organofluorine compounds. In this work, we present alternative solution to unavailable fluorodiazomethane (CHFN2), a missing one-carbon C1 piece in fluorine chemistry, by using a fluoromethylsulfonium reagent.

Occurrence of selected per- and polyfluorinated alkyl substances (PFASs) in food available on the European market - A review on levels and human exposure assessment.

Per- and polyfluorinated alkyl substances (PFASs) are considered emerging persistent organic pollutants, which are chemically, thermally, and biologically stable, or degrade to persistent end products. Dietary intake is considered as one of the main human exposure pathways of these chemicals and, having entered the human body, PFASs are not metabolised and accumulate in tissues, while their toxicological properties may cause various health problems. Several studies on the occurrence of PFASs in various food types have been conducted, including the assessment of dietary exposure. The most important sources were fish, meat, eggs, fruits, and vegetables. Fruits and vegetables recently showed relatively high levels of PFASs, and have become a more significant source of PFASs than meat. In 2020, the European Food Safety Authority (EFSA) published an opinion, setting the tolerable weekly intake (TWI) of 4.4 ng kg-1 b.w. for the sum of perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulphonic acid (PFHxS), and perfluorooctanesulphonic acid (PFOS). The emphasis in this paper is on the systematization of available information on the distribution of PFASs and their levels in different food, with a special interest in data from the Europe. The current legislation and estimated dietary intakes by the general population are described. While the available information on tolerably daily intakes estimated in a number of European countries often exceeds the newly established EFSA TWI, a critical evaluation of performance characteristics of the reviewed analytical methodologies revealed the insufficient sensitivity of quantification procedures for accurate risk assessment according to the guidelines proposed by EFSA.

Legacy and alternative brominated, chlorinated, and organophosphorus flame retardants in indoor dust-levels, composition profiles, and human exposure in Latvia.

Flame retardants (FRs) are additives used in consumer products to reduce flammability, even though they can easily contaminate the indoor environment. Since it is common for people in modern cities to spend up to 85% of time indoors, the quality of the indoor environment is critical for human health. In this study, polybrominated diphenyl ethers (PBDEs), organophosphorus flame retardants (OPFRs), emerging brominated flame retardants (EBFRs), and dechlorane-related compounds (DRCs) were measured in household dust samples (n = 34) from Latvia, followed by human exposure assessment. Among all studied compounds, OPFRs showed the highest concentrations (1380-133,000 ng g-1). Despite the phase-out of PBDEs, they were the second most significant flame retardants in the studied dust samples (468-25,500 ng g-1) and the predominant compound was BDE-209. The concentrations of EBFRs were in the range of 120-7295 ng g-1, with the most abundant contaminant being DBDPE, which is widely used as a substitute for the deca-BDE formulation. DRCs were the least common flame retardants in the Latvian indoor environments, with concentrations ranging 22.4-192 ng g-1. Although the concentrations of specific FRs are known to vary between different countries, the levels and patterns observed in dust samples from Latvia were similar to those reported from Central Europe. Human exposure was evaluated as the estimated daily intake (EDI). The calculated exposure to most of the FRs was several orders of magnitude lower than the available reference dose (RfD) values.

Rapid determination of pharmaceuticals in wastewater by direct infusion HRMS using target and suspect screening analysis.

A wide-scope screening of active pharmaceutical ingredients (APIs) and their transformation products (TPs) in wastewater can yield valuable insights and pinpoint emerging contaminants that have not been previously reported. Such information is relevant to investigate their occurrence and fate in various environmental compartments. In this study, we explored the applicability of direct infusion high resolution mass spectrometry (DI-HRMS) for comprehensive and rapid detection of APIs and their TPs in wastewater samples. The method was developed using a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) system and incorporated both wide-scope suspect screening and semi-quantitative determination of selected analytes. The identification strategy was based on the following criteria: narrow accurate mass window (±1.25 ppm) for two most abundant full-MS signals, isotopic pattern fit and additional confirmation on the basis of MS2 spectra at three fragmentation levels. The tentative identification of suspects and target compounds relied on an in-house database containing more than 500 different APIs and TPs. The measured fragment spectra were matched against experimental MS2 patterns obtained from a publicly available spectral library (MassBank of North America) and in-silico generated fragmentation features (from the CFM-ID algorithm). In total, 79 suspects were identified and 24 target compounds were semi-quantified in 72 wastewater samples. The highest detection frequencies in treated wastewater effluents were observed for diclofenac, metoprolol and telmisartan, while hydroxydiclofenac, dextrorphan, and carbamazepine metabolites were the most frequently detected TPs. The obtained API profiles were in accordance with the national consumption statistics and the origin of wastewater samples. The developed method is suitable for rapid screening of APIs in wastewater and can be used as a complementary tool to characterize API emissions from wastewater treatment facilities and to identify problematic compounds that require more rigorous monitoring.

Permanent photodoping of plasmonic gallium-ZnO nanocrystals.

Donor dopants in oxide semiconductors are compensated not only by valuable electrons but also by other point defects, leading to a decrease in electric conductivity and infrared absorption. We demonstrate that the electron compensation mechanism in Ga doped ZnO nanocrystals can be promoted by photodoping. Unexpectedly, the electrons from photodoping are stable in the open air for months.

Addressing Main Challenges Regarding Short- and Medium-Chain Chlorinated Paraffin Analysis Using GC/ECNI-MS and LC/ESI-MS Methods.

The risk assessment of chlorinated paraffins (CPs), chemicals of widespread industrial use, is struggling without standardized analytical methods to obtain reliable occurrence data. Indeed, scientists face analytical challenges that hinder the comparability of analytical methods, among them uncontrolled ionization efficiency and lack of quantification standards. In this study, our goal was to investigate potential issues faced when comparing data from different mass spectrometry platforms and quantification methods. First, the injection of the same set of single-chain length standards in three different instrumental mass spectrometry set-ups (liquid chromatography-electrospray-Orbitrap (LC/ESI-HRMS), liquid chromatography-electrospray-time-of-flight (LC/ESI-MS), and gas chromatography-electron capture negative ion-Orbitrap (GC/ECNI-HRMS)) revealed a shift of homologue response patterns even in-between LC/ESI-based set-ups, which was more pronounced for CPs of low chlorination degree. This finding emphasizes the need for a comprehensive description of instrument parameters when publishing occurrence data. Second, the quantification of a data set of samples with four quantification methods showed that quantification at the sum SCCP and MCCP levels presented good comparability, while quantification at the homologue level remained unsatisfactory. In light of those results, we suggest that (i) response pattern comparison should only be performed between similar instrumental set-ups, (ii) experimental chlorination degrees should be used when quantifying according to the %Cl (instead of those provided by the suppliers), and (iii) concentration results should be expressed as the sum of SCCPs and MCCPs primarily, with an indication on the match between samples and quantification standards (for example their chlorine content).

Application of Dopant-Assisted Atmospheric Pressure Photoionisation HPLC-MS Method for the Sensitive Determination of Polycyclic Aromatic Hydrocarbons in Dark Chocolate.

Multiple food research studies have shown that the polycyclic aromatic hydrocarbon (PAHs) are frequently found in processed cocoa products and chocolate. In a present study a method based on dopant-assisted atmospheric pressure photoionisation (DA-APPI) combined with a liquid chromatography/high-resolution mass spectrometer (HPLC-HRMS) for high-sensitivity analysis of four EU marker PAHs in dark chocolate samples was developed and fully validated according to the performance criteria set in EU guidelines. PAHs detection was achieved by HRMS in positive electrospray ionization mode with toluene used as a dopant to enhance the ionization efficiency of non-polar PAHs. The on-column instrument detection limits ranged from 0.8 to 1.2 pg for all four marker compounds. The method detection limits ranged from 0.016 to 0.024 µg kg-1 expressed on fat basis. The elaborated method was successfully applied to the analysis of four EU marker PAHs in dark chocolate samples. The presence of benzo[a]anthracene, benzo[b]fluoranthene and chrysene revealed at detectable levels in 100% of the samples, while benzo[a]pyrene was revealed in 77% of the samples, with its content ranging from 0.08 to 2.90 µg kg-1 fat.

The impact of baking on chlorinated paraffins: Characterization of C10-C17 chlorinated paraffins in oven-baked pastry products and unprocessed pastry dough by HPLC-ESI-Q-TOF-MS.

This study presents an HPLC-ESI-Q-TOF method for simultaneous quantification of short-chain chlorinated paraffins (SCCPs, C10-13) and an additional characterization of medium-chain chlorinated paraffins (MCCPs, C14-17) in oven-baked pastry products (n = 38) and unprocessed pastry dough material (n = 15). Almost 2 times higher SCCP levels were found in the dough material. ΣSCCP concentrations in products ranged from 0.3 ng g-1 to 23.0 ng g-1 (mean: 6.3 ng g-1), while the results for dough ranged from 5.8 ng g-1 to 22.8 ng g-1 (mean: 12.9 ng g-1). Regardless of the sample matrix, the most abundant CP homologue groups were hepta- and octa-chlorinated undecanes and dodecanes. The average chlorination degree found in dough samples fell within a range of 55-60% (w/w). Meanwhile, a slight decrease of CP chlorination degree was observed for oven-baked products, in particular for C10-C12 SCCPs, thus indicating that thermal decomposition of CPs occurs even under relatively mild conditions.

Development and optimization of confirmatory liquid chromatography-Orbitrap mass spectrometry method for the determination of 17 anticoccidials in poultry and eggs.

A new sensitive and selective multi-residue method based on liquid chromatography - Orbitrap high resolution mass spectrometry (LC-Orbitrap-HRMS) was developed and validated for the determination of 17 anticoccidials in poultry and eggs. Instrumental parameters were optimized by the means of statistical experimental designs to improve the sensitivity, precision, and repeatability of the method. Further optimization of auto-tuned MS parameters led to an increase of signal intensity by 10% to 99% for 16 out of 17 analytes. The sample preparation procedure included extraction from muscle tissue and egg samples with acetonitrile, followed by preconcentration, reconstitution, and filtration. Validation was performed according to the Commission Decision 2002/657/EC. The occurrence of anticoccidials in eggs and poultry was assessed by using the developed analytical procedure within the Latvian national monitoring program, revealing quantifiable residues for 6 analytes (marker residue of nicarbazin - 4,4'-dinitrocarbanilide (DNC), salinomycin, narasin, toltrazuril, and its two metabolites).

Development and optimization of gas chromatography coupled to high resolution mass spectrometry based method for the sensitive determination of Dechlorane plus and related norbornene-based flame retardants in food of animal origin.

An analytical method has been developed for the trace determination of 10 dechlorane-related compounds (DRCs) in food products by gas chromatography - high resolution mass spectrometry (GC-HRMS). The highest sensitivity of this instrumental analysis method was achieved by selection of the GC column type, optimization of the heated zones within the instrument, and adjusting the electron impact energy. The efficiency of solid phase extraction as clean-up procedure was also optimized. Two different types of cartridges - neutral silica gel and Florisil®, as well as seven organic solvents or their mixtures - n-hexane, cyclohexane, acetone, toluene, n-hexane/ethyl acetate, n-hexane/acetone, and n-hexane/dichloromethane - were evaluated. The analytical method was characterized as selective, precise, accurate, and linear over the concentration ranges from 1.00 to 100 pg µL-1 for DRCs. Ultra-trace level sensitivity was achieved with the instrumental limits of quantification (i-LOQs) varying from ∼0.01 pg to âˆ¼ 1 pg and method limits of quantification (m-LOQs) by the analysis of 10 g of sample varying from ∼0.04 to âˆ¼ 5 pg g-1. The developed method was successfully applied for the analysis of food samples and the analyses revealed the presence of majority of selected DRCs, with the Dechlorane Plus (DP) isomers occurring to a greater extent, pointing to the highest levels in cod liver and other fish products.

Polycyclic aromatic hydrocarbons in traditionally smoked meat products from the Baltic states.

A total of 77 traditionally smoked meat samples produced in Latvia, Lithuania, and Estonia were tested for the occurrence of four EU regulated polycyclic aromatic hydrocarbons (PAHs). Levels of PAHs exceeding the EU maximum levels for benzo[a]pyrene and for the sum of four PAHs (PAH4) were detected in 46% and 48% of the samples originating from Latvia. The detected BaP levels in smoked meats ranged from 0.05 to 166 µg kg-1, while the PAH4 content ranged from 0.42 to 628 µg kg-1. The mean dietary exposure to PAHs was estimated at the levels of 5.4 ng BaP/kg bw/day and 36 ng PAH4/kg bw/day. The margin of exposure (MOE) approach was utilised to assess the risks to Latvian consumers due to PAHs and the obtained MOEs were in a range of 7205-24,434, thus indicating a potential concern for consumer health for specific population groups.