Andrey I. Konstantinov

Molecular Mapping of Sorbent Selectivities with Respect to Isolation of Arctic Dissolved Organic Matter as Measured by Fourier Transform Mass Spectrometry

The objectives of this study were to identify molecular features characteristic to arctic DOM from the Kolyma River basin and to elucidate structural imprints induced by a choice of the sorption technique. To achieve this goal, DOM was isolated from the Kolyma River basin with a use of three nonionic sorbents: Amberlite XAD-8 resin, PPL- and C18 - SPE cartridges, and one anion exchanging resin-diethylaminoethyl (DEAE) -cellulose. The structural studies were conducted with a use of electrospray ionization Fourier Transform Ion Cyclotron Resonance (ESI FT-ICR) mass spectrometry and liquid state (1)H NMR spectroscopy. The DOM isolates obtained with a use of PPL and C18 cartridges were characterized with higher content of aliphatic compounds as compared to XAD-8 and DEAE-isolates. In total, for all arctic DOM isolates we observed predominance of hydrogen saturated compounds with high H/C values of identified formulas from FT-ICR MS data. (1)H NMR spectroscopy studies have confirmed this trend and revealed high contribution of alkyl-chain protons into the spectral density of the arctic DOM reaching 43% for PPL isolates.

Enumeration of Labile Hydrogens in Natural Organic Matter by Use of Hydrogen/Deuterium Exchange Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

A method to enumerate labile hydrogens in all constituents of molecular ensemble of natural organic matter (NOM) based on our previously developed simple hydrogen/deuterium (H/D) exchange (electrospray ionization (ESI) ion source (Kostyukevich et al. Anal. Chem. 2013, 85, 5330) and ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry is presented. The method was applied for analysis of Suwannee River fulvic acid (SRFA), which is an International Humic Substances Society standard, as well as Siberian crude oil; and lignosulfonate. We found that SRFA and lignosulfonate molecules contain 2-5 labile hydrogens, and their number increases with the number of oxygens in the molecule. Also, we observed that compounds of Siberian crude oil ionizing in positive-ESI mode do not have labile hydrogens, while compounds ionizing in negative-ESI mode have one labile hydrogen that detaches during ESI ionization.

Structure of Humic Acids in Zonal Soils from 13 C NMR Data

The structure of humic acids (HAs) in zonal soil types—soddy-podzolic soils (two samples), gray forest soil (one sample), and chernozems (two samples)—was quantitatively studied by 13C NMR spectros-copy. In the series considered, the content of unsubstituted carbon in the aromatic fragments of HAs increased, and the fraction of unsubstituted aliphatic structures decreased. HAs of soddy-podzolic soils were found to be enriched with carbohydrate fragments compared to HAs of chernozems and gray forest soil. The carbon skeleton of HAs from typical rich chernozem contained significantly more aliphatic and carbohydrate fragments compared to typical chernozem, which probably reflected the lower degree of HA transformation in rich chernozem.

Structure of Humic Acids Isolated by Sequential Alkaline Extraction from a Typical Chernozem

It was shown with the isolation of a humic acid (HA) preparation from a typical chernozem by sequential alkaline extraction as an example that the preparative yield of HAs decreased at each sequential extraction stage by 3–4 times. On the basis of studying the obtained preparations using elemental analysis, gel-penetration chromatography, and 13C NMR spectroscopy, the tendencies of the changes in the structural-group and molecular-weight compositions of the HAs from one extraction stage to the next one were revealed. The conclusion was drawn that a single extraction is sufficient for obtaining a representative HA sample.

Nature-like solution for removal of direct brown 1 azo dye from aqueous phase using humics-modified silica gel

The objective was to estimate suitability of humics-modified silica gels for adsorptive removal of the Direct Brown 1 trisazo dye from aqueous phase. The major advantage of the proposed adsorbents is that of an ecologically sound procedure of immobilizing silanized humic derivatives onto silica gel in aquatic solutions. The silanized humic derivatives, in turn, are obtained without a use of organic solvent by reacting natural humic materials from peat and coal with 3-aminopropyltriethoxyorganosilane in water. These silanized derivatives are surface active and are capable of self assembling into humic adlayers at the water solid interface. A use of this approach allows for immobilization of up to 220 mg of humic materials per 1 g of SiO2. The adsorption capacity of humics-modified silica gels with respect to the Direct Brown 1 trisazo dye varied from 3.5 up to 8.8 mg per 1 g of SiO2. The maximum sorption obtained for the silanized derivative with 50% modification degree was comparable to adsorption capacity of activated coal to this dye (7.5 mg g(-1)). The results of this adsorption study, warrant further studies of azo dye removal from aqueous environments.

Transformation of humic substances of highly oxidized brown coal by basidiomycetes Trametes hirsuta and Trametes maxima

The ability of white rot basidiomycetes Trametes hirsuta and Trametes maxima to transform coal humic substances (HS’s) under the conditions of solid phase cultivation in the presence or absence of an easily available source of carbon (glucose) has been studied. It was shown that during the growth of the fungal strains used in media containing HS’s, destructive and condensation processes of HS transformation proceeded simultaneously. Based on a comparative physicochemical analysis of the initial HS’s and HS’s trans-formed by the fungi, it was established that, despite the introduction of glucose may favor a deeper transformation of HS’s by basidiomycetes, the general direction of their modification is dominant reduction or oxidation and is determined by the physiological biochemical peculiarities of the strain used.

The carbon distribution among the functional groups of humic acids isolated by sequential alkaline extraction from gray forest soil

Preparations of humic acids (HAs) were isolated from a gray forest soil by sequential alkaline extraction. From a sample of 500 g, HA preparations of 2.24, 0.23, and 0.20 g were obtained from the first, second, and third alkaline extracts, respectively. The structure of the preparations was determined by 13C NMR spectroscopy. At each next extraction step, the portion of aliphatic fragments in the HA preparations increased and the content of aromatic structures decreased. The conclusion was drawn that a single extraction is sufficient for obtaining a representative HA sample.

Enumeration of carboxyl groups carried on individual components of humic systems using deuteromethylation and Fourier transform mass spectrometry

AbstractHere, we report a novel approach to enumeration of carboxylic groups carried by individual molecules of humic substances using selective chemical modification and isotopic labeling (deuteromethylation) and high-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS). Esterification was conducted with a use of thionyl chloride–deuteromethanol reagent under mild conditions to avoid transesterification. The deuteromethylated products were subjected to solid phase extraction using PPL Bond Elute cartridges prior to FTICR MS analysis. An amount of carboxyl groups in the individual molecular component was estimated from the length of identified deuteromethylation series. The method allowed for discerning between compounds with close elemental compositions possessing different protolytic properties. We found that different carboxylic moieties occupy distinct regions in molecular space of humic substances (HS) projected onto Van Krevelen diagram. These locations do not depend on the source of the humic material and can be assigned to carboxyl-rich alicyclic molecules (5 to 6 COOH), hydrolyzable tannins (3-4 COOH), lignins (1 to 2 COOH), condensed tannins and lignans (0 to 1 COOH), and carbohydrates (0 COOH). At the same time, the alignment pattern of these carboxylated species along the structural evolution lines in Van Krevelen diagrams was characteristic to the specific transformation processes undergone by the humic materials in the different environments. The obtained data enable mapping of molecular ensemble of HS with regards to their specific acidic compartments and might be used for directed fractionation of HS. Graphical abstractSelective isotopic labeling followed by FTICR MS enables discerning between humic molecules with close elemental compositions carrying different numbers of carboxylic groups.

Preparation of Methoxysilyl Humic Acid Derivatives with the Use of 3-Isocyanatopropyltrimethoxysilane

A new method for modifying (methoxysilylating) coal humic acids by reacting them with 3-isocyanatopropyltrimethoxysilane is described. The modification products structurally characterized by FTIR and NMR spectroscopy. The sorption ability of methoxysilated humic acids on silica gel is studied in the batch mode to illustrate their affinity to silicon minerals.

Extraction of Humic Substances from Fresh Waters on Solid-Phase Cartridges and Their Study by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Humic substances (HS) have been extracted from fresh waters on macroporous adsorbents of different types, Amberlite XAD-8 resin and Bond Elute PPL solid-phase cartridge. Comparative analysis of the extracted samples by ultra-high resolution mass spectrometry demonstrated selectivity of the selected adsorbents to the components of the molecular assembly of HS: the XAD-8 resin has affinity to the higher oxidized aromatic compounds and PPL has affinity to substances of stronger aliphatic character and nitrogen-containing compounds. Because of this fact, a comparison of the molecular composition of HS isolated from various sources must be performed taking into account selective adsorption; therefore, it is necessary to compare the products extracted by the same adsorbent for correct interpretation.