D. A. Khundzhua

Spectral Characterization of Fungal Metabolites in Aqueous Medium with Humus Substances

The work is targeted to confirm participation of microscopic fungi in transformation of humus substances in aquatic environments. The research is focused on the spectroscopic study of the collection of fungal strains with different pigmentation of mycelium. Spectral properties of fungal metabolites were measured and compared to that of natural aquatic nonliving organic matter and commercial humus substances in aqueous solutions. The experiments revealed that the effect of microscopic fungi growing in the culture medium with added humate appeared as changes in the humic-type fluorescence: its characteristics became more similar to that of nonliving organic matter in natural waters than to original humate preparation. The experiments demonstrated degradation of coal-originated humate due to microbial activity into compounds of smaller molecular size and increased heterogeneity. We resume that transformation of humus substances by fungal cultures can be monitored and characterized using spectral measurements.

Fluorescence of dissolved organic matter as a marker for distribution of desalinated waters in the Kara Sea and bays of Novaya Zemlya archipelago

The optical properties and distribution of dissolved organic matter in the surface waters of the Kara Sea and bays of Novaya Zemlya archipelago were studied during the 63th cruise of the R/V Akademik Mstislav Keldysh. The fluorescence of dissolved organic matter has been studied over wide excitation (230–550 nm) and emission (240–650 nm) wavelength ranges. Based on the results of fluorescence measurements, we propose a simple technique for estimating the relative content of humic compounds entering the Kara Sea shelf region with Ob and Yenisei river runoff. We have found that the blue shift parameters of the DOM fluorescence are Δ270–310 = 28 ± 2 nm and Δ355–310 = 29 ± 2 nm. The highest contents of humic compounds in surface waters were measured on the transect across the desalinated layer of the Kara Sea, near the continental slope on the transect along the St. Anna Trough, and in the area of Sedova, Oga and Tsivol’ki bays. Traces of labile terrigenous organic matter were found in the region of the Voronin Trough, in the bays of the Severny Island of Novaya Zemlya, as well as in some freshwater reservoirs and ice samples of the archipelago. We established a conservative distribution of dissolved organic matter, whose content in water varied from 1.25 to 8.55 mg/L.

Fluorescence and Raman Spectroscopy Study of Humic Acids in Iron Chloride Solutions and Magnetite/HA Nanoparticles

Spectral properties of water-dispersible sorbent produced from humic acids (HA) extracted from brown coal and magneto-active nanoparticles were measured for the samples of different magnetite/HA ratio and the way of their preparation. The influence of iron (III) ions on spectral properties of HA in aqueous solution was investigated using Stern-Volmer plots describing HA fluorescence quenching. The Stern-Volmer dependences were found to be linear at concentration of iron (III) ions smaller 20 μmol/L and nonlinear at higher concentrations.

Excitation-Dependent Fluorescence Quantum Yield for Freshwater Chromophoric Dissolved Organic Matter from Northern Russian Lakes

Advanced fluorescence analysis within the wide range of excitation wavelengths from 230 to 510 nm accompanied with chromatography was used to study natural chromophoric dissolved organic matter (CDOM) from three freshwater Karelian lakes. The influence of excitation wavelength (λex) on fluorescence quantum yield and emission maximum position was determined. The CDOM fluorescence quantum yield has reached a minimum at λex∼270–280 nm and a maximum at λex∼340–360 nm. It was monotonously decreasing after 370 nm towards longer excitation wavelengths. Analytical reversed-phase high-performance liquid chromatography with multiwavelength fluorescence detector characterized distribution of fluorophores between hydrophilic/hydrophobic CDOM parts. This technique revealed “hidden” protein-like fluorophores for some CDOM fractions, in spite of the absence of protein-like fluorescence in the initial CDOM samples. The humic-like fluorescence was documented for all hydrophilic and hydrophobic CDOM chromatographic peaks, and its intensity was decreasing along with peaks’ hydrophobicity. On contrary, the protein-like fluorescence was found only in the hydrophobic peaks, and its intensity was increasing along with peaks’ hydrophobicity. This work provides new data on the CDOM optical properties consistent with the formation of supramolecular assemblies controlled by association of low-molecular size components. In addition, these data are very useful for understanding the CDOM function in the environment.

Absorption and fluorescence of hydrophobic components of dissolved organic matter in several Karelian lakes with stratified structures

Hydrophobic components of cromophoric dissolved organic matter (CDOM) extracted from water samples and sediments taken in several relic basins located on Karelian shoreline of the White Sea were analyzed using spectroscopic techniques. Those water reservoirs exist at various stages of isolation from the White Sea and represent complex stratified systems of fresh and marine water layers not completely mixing trough the year. Basins separating from the White Sea are the unique natural objects for investigations of properties CDOM, its transformation in the process of turning the marine ecosystem into freshwater environment. CDOM occurring in all types of natural water represents a significant reservoir of organic carbon and plays a key role in the carbon cycle on the Earth. However, aquatic CDOM and nonliving organic matter in sediments from relic separating basins still have not been studied. The target of this work was to study absorption and fluorescence spectra of hydrophobic components of aquatic CDOM from different water depth and sediments in several separated basins of the Kandalaksha Gulf of the White Sea located near the N.A. Pertsov White Sea Biological Station.

Fluorescence quantum yield of CDOM in coastal zones of the Arctic seas

ABSTRACT Along with traditional optical indices, calculated from absorption and fluorescence spectra to describe chromophoric dissolved organic matter (CDOM) naturally occurring in water, the fluorescence quantum yield (FQY) becomes significant. Knowledge of CDOM optical properties is important for satellite remote sensing as well as for lidar ground-true measurements. The FQY as a function of excitation wavelength within 240–500 nm range for a variety of the Arctic shelf waters was determined for the first time in order to identify the characteristic chromophores peculiar to different regions of the Arctic basin affected by freshwater runoff. The surface water samples were collected during several cruises in 2015–2017 in the following sites: the mouth areas of the Khatanga and Lena Rivers (the Laptev Sea), the delta area of the Northern Dvina River (the White Sea), desalinated waters of the Kara Sea (influenced by freshwater of the Ob and Yenisei Rivers) and the East Siberian Sea (influenced by freshwaters of the Indigirka and Kolyma Rivers), as well the shelf areas of those seas not affected by terrigenous runoff. To characterize DOM, conventional optical indices SR, HIX, and BIX were calculated. In most cases, important humic character of DOM was established, while the contribution of autochthonous organic matter varied from low to intermediate level. For the samples with terrestrial impact, the FQY decreased from excitation at 240 nm to 270–280 nm and then increased, demonstrating two peaks at 340 and 380 nm, with constant decrease towards longer excitation wavelengths; at λex = 380 nm FQY varied from 1.4% to 3.1%. In some cases, additional maximum at 270 nm of FQY-excitation dependency was observed as an indicator of autochthonous nature of biological material. Minimal FQY was measured for the White Sea surface waters, the maximal for the Laptev and East Siberian seas.

An analysis of dissolved organic matter from freshwater Karelian Lakes using reversed-phase high-performance liquid chromatography with online absorbance and fluorescence analysis

The spectral and optical properties of the fractionated components of dissolved organic matter (DOM) of three freshwater lakes in Karelia were studied using reversed-phase high-performance liquid chromatography (RP-HPLC) with online detection of fluorescence and absorption spectra. It is shown that the DOM fractions are qualitatively similar, but differ quantitatively in the ratio of components and consist of at least three types of fluorophores: (1) hydrophilic “humic-like” fluorophore(s) with the emission maximum in the region of 420 nm and an absorption band at 260–270 nm; (2) hydrophobic “humic-like” fluorophore(s) with the emission maximum at approximately 450 nm that has no characteristic absorption maxima in the region from 220 to 400 nm; and (3) a “protein-like” fluorophore with the emission maximum in the region of 340–350 nm, which is typical of proteins and peptides containing tryptophan.