New insights into the role of sediments in microplastic inputs from the Northern Dvina River (Russia) to the White and Barents Seas.

The Northern Dvina River is one of the main sources of microplastic pollution entering to the White and Barents Seas. The coastal and bottom sediments of this river play an important role as a transfer link of microplastics. With Py-GC/MS and µFT-IR methods, it was found that the sediments contain up to 350 mg/kg or 650 particles/kg of microplastic (dry weight). The unique hydrologic conditions of the river branching area contribute to the formation of a microplastic pollution hotspot. The hotspot accumulates >30 % of microplastic pollution, mainly ABS plastic particles smaller than 0.3 mm with roughness and cracks, which increases the hazard class (from II to IV) of microplastic pollution. Obtained data and high annual variability of pollution indicates that this area acts as a place of accumulation, degradation and gradual release of microplastics into the White and Barents Seas, i.e. into the Arctic region.

Polycyclic aromatic hydrocarbons in the Siberian Arctic seas sediments.

Polycyclic Aromatic Hydrocarbons (PAHs) are among the main persistent organic pollutants in the Arcticwhich enter the polar region from lower latitudes by air transport and ocean currents and accumulate in marine sediments. This work represents the first study in 25 years of the least studied and hard-to-reach areas of Siberian arctic seas. Sixteen priority PAHs as well as 1- and 2-methylnaphthalenes were analyzed by gas chromatography - tandem mass spectrometry in the twenty-four sediment samples taken from Kara, Laptev and East Siberian Seas in October 2020. The obtained sum concentrations ranged from 31 to 223 ng/ g with the greatest contribution of phenanthrene, benzo[b]fluoranthene, benzo[k]fluoranthene, as well as naphthalene and its methyl derivatives while the greatest PAH levels were observed in Laptev Sea. No correlations between sum PAH concentration, total organic carbon and black carbon contents were found. The toxic equivalent in benzo[a]pyrene units was from 2.2-18.2 ng/ g that shows the general safe environmental situation in the region. The overall PAH level is comparable with the data obtained in 1990s which indicates a long-term persistence of pollution despite an overall decline in global PAH emissions. The main sources of PAHs involve mainly coal/biomass and liquid fuel combustion with weaker contribution of petroleum sources.

Features of the Chemical Composition and Structure of Birch Phloem Dioxane Lignin: A Comprehensive Study.

Understanding the chemical structure of lignin in the plant phloem contributes to the systematics of lignins of various biological origins, as well as the development of plant biomass valorization. In this study, the structure of the lignin from birch phloem has been characterized using the combination of three analytical techniques, including 2D NMR, Py-GC/MS, and APPI-Orbitrap-HRMS. Due to the specifics of the phloem chemical composition, two lignin preparations were analyzed: a sample obtained as dioxane lignin (DL) by the Pepper's method and DL obtained after preliminary alkaline hydrolysis of the phloem. The obtained results demonstrated that birch phloem lignin possesses a guaiacyl-syringyl (G-S) nature with a unit ratio of (S/G) 0.7-0.9 and a higher degree of condensation compared to xylem lignin. It was indicated that its macromolecules are constructed from ß-aryl ethers followed by phenylcoumaran and resinol structures as well as terminal groups in the form of cinnamic aldehyde and dihydroconiferyl alcohol. The presence of fatty acids and flavonoids removed during alkaline treatment was established. Tandem mass spectrometry made it possible to demonstrate that the polyphenolic components are impurities and are not incorporated into the structure of lignin macromolecules. An important component of phloem lignin is lignin-carbohydrate complexes incorporating xylopyranose moieties.

Data of polycyclic aromatic hydrocarbons concentration in the Siberian Arctic seas sediments.

Polycyclic Aromatic Hydrocarbons (PAHs) are one of the most dangerous persistent organic pollutants in the Arctic. They have different sources and pathways of entering in to the environment. Because of their lipophilic properties, PAHs can easily accumulate in marine sediments. This work gives a new data about concentration of PAHs in Siberian arctic seas. Sixteen priority PAHs as well as 1- and 2-methylnaphthalenes were analyzed by gas chromatography - tandem mass spectrometry in the twenty-four sediment samples taken from Kara, Laptev and East Siberian Seas in October 2020. The obtained sum concentrations ranged from 31 to 223 ng g-1 with the greatest contribution of phenanthrene, benzo[b]fluoranthene, benzo[k]fluoranthene, as well as naphthalene and its methyl derivatives while the greatest PAH levels were observed in Laptev Sea. The toxic equivalent in benzo[a]pyrene units was from 2.2-18.2 ng g-1. Total organic carbon (TOC) and black carbon (BC) content in arctic were in the ranges of 0.18-1.98 % and 0.03-0.40 %, respectively. The overall PAH level shows negligible harm to the environment.

Structural characterization of the lignin from Saxifraga (Saxifraga oppositifolia L.) stems.

As a renewable source of unique aromatic compounds, lignin attracts the attention of many researchers. However, for its successful application, it is necessary to have a clear and accurate idea of its chemical structure. Therefore, it is necessary to expand knowledge about the structure of lignins of various nature using the informative analytical methods. The aim of this study was to characterize the dioxane lignin of the Saxifraga oppositifolia L. - the northernmost angiosperm. The lignin of plants growing in the Arctic zone may differ significantly from other plants, both due to species differences and peculiarities of growing conditions. Studies were conducted on an isolated lignin preparation obtained by the Pepper's method. Analysis of Py-GC/MS data and NMR spectroscopy showed that saxifrage lignin belongs to GH-type. This is evidenced by a significant proportion of p-hydroxyphenyl units (40%), while the content of syringyl units is about 14%. The major substructures of the studied lignin were ß-aryl ether, phenylcoumaran, and resinol. It was found that the γ­carbon of the lignin side chains are partly acetylated, and forms ester bonds with the p-hydroxybenzoate structure. In addition, the NMR spectrum showed a signal of the phenylglycoside evidenced the presence of the lignin-carbohydrate complex.

Identification of avobenzone by-products formed by various disinfectants in different types of swimming pool waters.

The increased use of sunscreens and other cosmetics containing UV filters causes human and environmental burden. Avobenzone is a widely used UV filter. In its pure form it is known to undergo several transformations including photo-isomerisation, photodegradation, and halogenation. Over 60 disinfection by-products were identified as transformation products of avobenzone in different disinfection reactions of chlorination and bromination in fresh and seawater. Two occasional samples of swimming pool water demonstrated the presence of some of these by-products at noticeable levels as judged by GC-MS peak areas. Although the toxicity of the majority of these products remain unknown, chlorinated phenols and acetophenones are known to be rather toxic. Aquatic bromination of avobenzone resulted in the identification of 33 disinfection by-products (DBPs). Many of them contain bromine in the molecular structure. Addition of copper salt slightly decreases conversion rate simultaneously increasing the levels of major brominated products. Photostability of 3 commercial sunscreen products (solar protection factor 30) containing avobenzone was studied under different experimental conditions including UVA/UVB, UVC photostimulation and chlorination. The commercial sunscreen products have completely different enhancing and inhibitory effect on avobenzone degradation under UVC light. The complex composition of commercial products caused also a protective shield in case of chlorinated solutions of commercial formulations exposed to chlorine and UVA/UVB light at the same time.

Peat burning - An important source of pyridines in the earth atmosphere.

Studies of the chemical composition of atmospheric aerosols, rain water and snow in various regions of the globe quite often show the presence of pyridine and a number of its low mass derivatives. Nevertheless, the sources of those compounds in the environment have not yet been established and definitely require elucidation, supported by reliable experimental results. In the present work the chemical composition of peat combustion products as one of the important sources of atmospheric aerosol emission is studied by two-dimensional gas chromatography - high-resolution mass spectrometry with a focus on the detection of pyridine derivatives. Twenty-five compounds of this class were reliably identified and quantified in laboratory experiments on peat burning. Among them 3-hydroxypyridine predominates, while the rest analytes are mostly represented by alkyl derivatives: pyridine, 2-methylpyridine, 3-methylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2-ethylpyridine, lutidines (in order of decreasing concentration). The distribution of these combustion products coincides with that obtained earlier in environmental studies carried out in Arctic, Central Russia and France. The experiments on peat thermal decomposition by pyrolysis GC-MS demonstrated that the maximum concentrations as well as the number of detected analytes were found under conditions of oxygen lack and a temperature of about 500 °C, i.e. characteristic conditions of peat wildfires. The observed levels of pyridines' emission recalculated on the peat dry weight exceeded 200 mg kg-1. Considering hundreds of millions tons of peat burning in megafires over 20,000 tons of pyridines penetrate the Earth atmosphere annually. The obtained results allow concluding that peat burning may be the major and still underestimated source of pyridine and lower alkylpyridines in the Earth atmosphere.