DOC trend in Arctic lakes as a response to air pollution reduction by Kola North Smelter, Russia (1980-2018): possible mechanisms of transformation of organic substances

Author(s):  
Tatyana Moiseenko ◽  
Marina Dinu

<p>The phenomenon of increasing DOC levels in water systems over the last decades is confirmed by numerous studies (Driscoll et al., 2003; Stoddard et al., 1999; Skjelkvale et al., 2001a; Montein et al., 2007; Evans et al., 2008; Clark et al., 2013).  The increasing of organic matter content in lake waters is being also observed for the totality of lakes in the Kola North, more markedly in forest and water-logged subregions. This conforms to the data reported by Skjelkvale et al. (2001a) which demonstrates the significant increase of DOC. Montein et al. (2007) explain the increased DOC levels by reduction in strong acid flow and return of water chemistry to its natural parameters of specifying organic matter concentrations in water.</p><p>Clark et al. (2013) demonstrated that natural humus substances are capable of producing strong organic acids and increase water acidity. It is known that DOC level has a direct relationship with water color. In analyzing long-term study data with regard to the group of 75 lakes (obtained during 1990-2010) DOC is increased year-over-year, but the color decreased.</p><p>More evident dependence the increasing the content of DOC on reduced color from year to year (Fig.). The following chemical processes developing in water can explain this phenomenon.</p><p>Figure.  The correlation between the change of DOC (ΔDOC) and color (ΔColor) - file  </p><p><img src="data:;base64,%20" width="2296" height="3246"></p><p>The water color is predominantly determined by large molecules of humus acids which molecular weight >1000 Da. Macromolecular organic substances of humus type can be dissociated in water with formation of a free proton, as well as enter into reactions of decomposition (hydrolysis) and disproportionation with formation of low-molecular weight fragments. Its fragments also are dissociated of proton (see the diagram below). The above processes may be catalyzed by non-organic strong acids supplied from anthropogenic and natural sources. The diagram of the organic substances destruction of humus origin is given below, where R<sub>i  </sub>means non-symmetrical fragments of a natural polymer, Х<sub>i</sub>H - functional groups of organic substances of humus origin, and n - number of protons.</p><p>When strong acids get into a water environment humus acids are degraded into fractions.  It could be supposed that the organic matter structure undergoes changes in natural waters, as the fraction of high-molecular weight humus acids decrease. As a consequence of interaction between humus substances and protons the humic acids precipitate to form bottom sediments, whereas fulvic acids remain in water. Fulvic acids are characterized by lower molecular weights (from 500 to 2000 Da) and exert an insignificant effect on the water color. This phenomenon is well proved in a study published by Clark et al. (2013). However, to define more exactly this phenomenon, further experimental work is required.</p><p>Financing RSF 18-17-00184</p><p> </p><p> </p>

1996 ◽  
Vol 34 (9) ◽  
pp. 157-164 ◽  
Author(s):  
Kim C.-H. ◽  
M. Hosomi ◽  
A. Murakami ◽  
M. Okada

Effects of clay on fouling due to organic substances and clay were evaluated by model fouling materials and kaolin. Model fouling materials selected were protein, polysaccharide, fulvic acid, humic acid and algogenic matter (EOM:ectracellular organic matter, microbial decomposition products) and kaolin was selected as the clay material. Polysulfone membrane (MWCO(Molecular Weight Cut-Off) 10,000, 50,000 and 200,000) was used as an ultrafiltration membrane. In particular, the flux measurement of solutions containing algogenic matter used an ultrafiltration membrane of MWCO 50,000. The flux of protein and polysaccharide with coexistence of kaolin increased in the case of the ratio of MW/MWCO being greater than one, but did not increase in the case of the MW/MWCO ratio being below one. In contrast, the flux of fulvic acid and humic acid with coextence of kaolin decreased regardless of the ratio of MW/MWCO. The addition of dispersion agent and coagulant in the organic substances and kaolin mixture solution changed the size distribution of kaolin, and resulted in a change of the flux. EOM and microbial decomposition products decreased with the increase of the fraction of organic matter having molecular weight more than MWCO of membrane. The flux of the algogenic organic matter with coexistence of kaolin decreased with the increase of the amount of kaolin. It was suggested that the decline of the flux with coexistence of kaolin was due to the change of the resistance of the kaolin cake layer corresponding to the change in kaolin size distribution with charge.


Agronomy ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 1067
Author(s):  
Aleksandra Ukalska-Jaruga ◽  
Romualda Bejger ◽  
Guillaume Debaene ◽  
Bożena Smreczak

The objective of this paper was to investigate the molecular characterization of soil organic matter fractions (humic substances (HS): fulvic acids-FAs, humic acids-HAs, and humins-HNs), which are the most reactive soil components. A wide spectrum of spectroscopic (UV–VIS and VIS–nearIR), as well as electrochemical (zeta potential, particle size diameter, and polydispersity index), methods were applied to find the relevant differences in the behavior, formation, composition, and sorption properties of HS fractions derived from various soils. Soil material (n = 30) used for the study were sampled from the surface layer (0–30 cm) of agricultural soils. FAs and HAs were isolated by sequential extraction in alkaline and acidic solutions, according to the International Humic Substances Society method, while HNs was determined in the soil residue (after FAs and HAs extraction) by mineral fraction digestion using a 0.1M HCL/0.3M HF mixture and DMSO. Our study showed that significant differences in the molecular structures of FAs, Has, and HNs occurred. Optical analysis confirmed the lower molecular weight of FAs with high amount of lignin-like compounds and the higher weighted aliphatic–aromatic structure of HAs. The HNs were characterized by a very pronounced and strong condensed structure associated with the highest molecular weight. HAs and HNs molecules exhibited an abundance of acidic, phenolic, and amine functional groups at the aromatic ring and aliphatic chains, while FAs mainly showed the presence of methyl, methylene, ethenyl, and carboxyl reactive groups. HS was characterized by high polydispersity related with their structure. FAs were characterized by ellipsoidal shape as being associated to the long aliphatic chains, while HAs and HNs revealed a smaller particle diameter and a more spherical shape caused by the higher intermolecular forcing between the particles. The observed trends directly indicate that individual HS fractions differ in behavior, formation, composition, and sorption properties, which reflects their binding potential to other molecules depending on soil properties resulting from their type. The determined properties of individual HS fractions are presented as averaged characteristics over the examined soils with different physico-chemical properties.


1967 ◽  
Vol 47 (3) ◽  
pp. 245-250 ◽  
Author(s):  
M. Schnitzer

Twenty organic-soil samples of widely differing degrees of decomposition were extracted with 0.5 N NaOH solution under N2. Amounts of humic and of fulvic acids in the acidified extracts did not correlate significantly with pyrophosphate solubilities. This was thought to be due to interference in the separation scheme by relatively large amounts of ash constituents in the extracts. Since the "classical" fractionation of soil organic matter appears to involve essentially the "salting out" of higher molecular-weight humic from lower molecular-weight fulvic acids, an excessively high salt concentration during the separation should be avoided.To lower the concentration of inorganic constituents in the extracts, the samples were first pretreated with dilute HCl–HF solution and then extracted with 0.1 N NaOH rather than with 0.5 N NaOH. Under these conditions, amounts of fulvic acids in the acidified extracts showed a significant positive correlation (r = 0.52) with pyrophosphate solubilities of untreated extracts, whereas amounts of humic acids in the extracts exhibited a highly negative correlation (r = −0.57) with pyrophosphate solubilities. In the soils examined, increased humification was associated with increases in fulvic-acid but decreases in humic-acid concentrations.From the results of this and of earlier investigations done in this laboratory it appeared that the main mechanism governing humification in these soils was oxidative degradation, resulting ultimately in the formation of fulvic from humic acid.


2008 ◽  
Vol 58 (8) ◽  
pp. 1535-1539 ◽  
Author(s):  
L. Sabina ◽  
B. Kus ◽  
H.-K. Shon ◽  
J. Kandasamy

Organic characterisation in rainwater was investigated in terms of dissolved organic carbon (DOC) and molecular weight distribution (MWD) after powdered activated carbon (PAC) adsorption. PAC adsorption was used as pretreatment to membrane filtration to reduce membrane fouling. The MW of organic matter in rainwater used in this study was in the range of 43,000 Da to 30 Da. Each peak of organic matter consisted of biopolymers (polysaccharides and proteins), humic and fulvic acids, building blocks, low MW acids (hydrolysates of humic substances), low MW neutrals and amphiphilics. Rainwater contained the majority of hydrophilic compounds up to 72%. PAC adsorption removed 33% of total DOC. The removal efficiencies of the hydrophobic and hydrophilic fractions after PAC adsorption were 50% and 27%, respectively. PAC adsorption was found to preferentially remove the hydrophobic fraction. The majority of the smaller MW of 1,100 Da, 820 Da, 550 Da, 90 Da and 30 Da was removed after PAC adsorption. The MFI values decreased from 1,436 s/L2 to 147 s/L2 after PAC adsorption. It was concluded that PAC adsorption can be used as a pretreatment to membrane filtration with rainwater.


Soil Research ◽  
2005 ◽  
Vol 43 (2) ◽  
pp. 189 ◽  
Author(s):  
C. N. Guppy ◽  
N. W. Menzies ◽  
P. W. Moody ◽  
F. P. C. Blamey

The incorporation of organic matter (OM) in soils that are able to rapidly sorb applied phosphorus (P) fertiliser reportedly increases P availability to plants. This effect has commonly been ascribed to competition between the decomposition products of OM and P for soil sorption sites resulting in increased soil solution P concentrations. The evidence for competitive inhibition of P sorption by dissolved organic carbon compounds, derived from the breakdown of OM, includes studies on the competition between P and (i) low molecular weight organic acids (LOAs), (ii) humic and fulvic acids, and (iii) OM leachates in soils with a high P sorption capacity. These studies, however, have often used LOAs at 1–100 mm, concentrations much higher than those in soils (generally <0.05 mm). The transience of LOAs in biologically active soils further suggests that neither their concentration nor their persistence would have a practical benefit in increasing P phytoavailability. Higher molecular weight compounds such as humic and fulvic acids also competitively inhibit P sorption; however, little consideration has been given to the potential of these compounds to increase the amount of P sorbed through metal–chelate linkages. We suggest that the magnitude of the inhibition of P sorption by the decomposition products of OM leachate is negligible at rates equivalent to those of OM applied in the field. Incubation of OM in soil has also commonly been reported as reducing P sorption in soil. However, we consider that the reported decreases in P sorption (as measured by P in the soil solution) are not related to competition from the decomposition products of OM breakdown, but are the result of P release from the OM that was not accounted for when calculating the reduction in P sorption.


2019 ◽  
Vol 4 (2) ◽  
pp. 10-16
Author(s):  
Boris Klenov ◽  
Mikhail Yakutin

The paper analyzes the issue of environmental sustainability (ES) of the system of humus substances. The main problem in studies of ES consists in determination of its most informative criteria. Besides the bioclimatic indices, the characteristics of humus such as its content, type of humus and degree of humification of organic matter were ascertained to be included into the number of obligatory criteria of ES. Additional study of humic acids as more chemically and biologically sustainable soil organic substances showed that the fraction of calcium humates (combined with exchangeable calcium) proved to be the most informative criteria of ES. The most representative data on ES are obtained at simultaneous study of virgin and arable soil samples.


2018 ◽  
Vol 18 (8) ◽  
pp. 2823-2832 ◽  
Author(s):  
Lidia Oktaba ◽  
Diana Odrobińska ◽  
Łukasz Uzarowicz

Abstract Purpose In urban areas, humus quantity and quality depend less on natural environmental factors than on anthropogenic ones. The aim of the study was to assess the impact of different land use types of urban soils on the properties of soil organic matter (SOM). Materials and methods Thirty-five sites involving four ways of soil use were examined: lawns, allotment gardens, fallows, and arable lands. The study was conducted in Pruszków Town in the Warsaw Agglomeration, Central Poland. Lawns and allotment gardens were located in the central part of the town, whereas fallows and arable lands were in the peripheral zones. Humus horizons, to a depth of 0–20 cm, were analyzed. Using Na-pyrophosphate extraction, we determined the soluble SOM compounds (PY), and the organic matter in the extraction residue, considered as humins (HM). In a separate extraction (with 0.05 M H2SO4), low molecular weight (LMW) humus compounds were determined. The quantity of humic acids (HA) precipitated during Na-pyrophosphate extraction was determined as well. A spectroscopic method (UV-Vis) was used to characterize HA properties. The absorption coefficients E4/E6 were calculated based on the results of absorbance measurements involving 465- and 665-nm wavelengths of UV-Vis light. Statistical analyses were performed to find similarities and differences between soils differently used in Pruszków. Results and discussion The dominant part of the humus in the studied soils were humins HMs. There were two times more HM in the central part of the town than that in the peripheral zones. The same observation was made for soluble humus compounds (PY). The amount of LMW fractions was similar in soils of all uses. The degree of humification was small and averaged about 30% for all soils. Fulvic acid (FA) concentrations predominated over HA concentrations in all soils. The least condensed HA occurred in the allotment gardens with an E4/E6 ratio of 5.7, whereas the most condensed HAs were present in soil on arable lands (E4/E6 ratio of 4.7). Conclusions The studies have shown that the type of land use affects humus properties. The main differences were found to be in the quantity of humus compounds. Soils from the central part of the town contained more stable (HM) and soluble (PY) compounds than soils in the outskirts of town. PY compounds were characterized by a simple structure. Fulvic acids (FA) dominated in all of the studied soils (low HA/FA ratio). A high E4/E6 ratio indicates low maturity of humic fractions with low molecular weight compounds.


2020 ◽  
pp. 1-5
Author(s):  
Giorgi Makharadze ◽  
Tamar Makharadze

Natural macromolecular organic substances-fulvic acids take an active part in complex formation processes and stipulate migration forms of heavy metals in natural waters The calculation of the migration forms of heavy metals is one of the problematic issue of the contemporary chemistry, which couldn’t be solved without using the conditional stability constants of fulvate complexes. In spite of researches, experimental data on stability constants of complex compounds of fulvic acids with heavy metals ( among them copper) are heterogeneous and they differ in several lines from each other. One of the reason of such condition is ignoring an average molecular weight of the associates of fulvic acids, which finally causes the wrong results. Complex formation process between copper (II) and fulvic acids was studied by the solubility method at pH=9.0. Cu(OH)2 suspension was used as a solid phase. Fulvic acids were isolated from Paravani lake by the adsorption –chromatographic method. In this article is shown that, during complex formation process every 1/4 part of an associate of fulvic acids(Mw=7610), inculcates into copper's inner coordination sphere as an integral ligand, so it may assume, that the average molecular weight of the associate of fulvic acids which takes part in complex formation process equals to 1903. This part of the associate of fulvic acids was conventionally called an“active associate".The average molecular weight of the“active associate”was used for determination the composition of copper fulvate complex, the concentration of free ligand and stability constant, which equals to 2,25x107   


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