Irina V. Perminova

Use of humic substances to remediate polluted environments : from theory to practice

Preface. Introduction. Contributors. Part 1. Remedial properties of humic substances: general considerations and problems in addressing needs of environmental remediation. 1. Remediation chemistry of humic substances: theory and implications for technology I.V. Perminova, K. Hatfield. 2. Soil organic matter and protective functions of humic substances in the biosphere D.S. Orlov and L.K. Sadovnikova. 3. Chemical stoichiometry and molecular level mechanisms as support for future predictive engineering calculations, D.S. Gamble et al. Part 2. Complexing interactions of humic substances with heavy metals and radionuclides and their remedial implementation. 4. Interactions of humic substances with trace metals and their stimulatory effects on plant growth A. Kaschl, Y. Chen. 5. Influence of UV-oxidation on the metal complexing properties of NOM F.H. Frimmel et al. 6. Role of humic substances in the complexation and detoxification of heavy metals: case study of the Dnieper reservoirs P.N. Linnik, T.A. Vasilchuk. 7. Complexation of radionuclides with humic substances V. Moulin. 8. Humic acids as barriers in actinide migration in the environment S.N. Kalmykov et al. 9. The use of humates for detoxification of soils contaminated with heavy metals O.S. Bezuglova, A.V. Shestopalov. Part 3. Sorptive-partitioning interactions of humic substances with organic ecotoxicants and their implementation for remediation technologies. 10. Utilization of immobilized humic organic matter for in-situ subsurface remediation G.U. Balcke et al. 11. The use of aqueous humic substances for in-situ remediation of contaminated aquifers D.R. Van Stempvoort et al. 12. Advantages of in situ remediation of polluted soil and practical problems encountered during its performance J.F. De Kreuk. 13. Wastewater treatment using modified natural zeolites P. Princz et al. Part 4. Impact on physiological functions of living organisms and on microbial transformations ofecotoxicants. 14. Mitigating activity of humic substances: direct influence on biota N.A. Kulikova et al. 15. Cytogenetic effects of humic substances and their use for remediation of polluted environments A. Gorova et al. 16. Influence of metal ions on the activity of soil humics-enzyme complexes S. Jorobekova et al. 17. Microbial redox reactions mediated by humus and structurally related quinines J. A. Field, F.J. Cervantes. 18. Enhanced humification of TNT H. Thomas, A. Gerth. 19. Commercial humates from coal and their influence on soil properties and initial plant development O.S. Iakimenko. 20. Impact of humic substances on plants in polluted environments: implications for phytoremediation technologies M.M. Kharitonov et al. Part 5. Quantifying structure and properties of humic substances and example studies on design of humic materials of the desired properties. 21. Molecular level structural analysis of natural organic matter and of humic substances by multinuclear and higher dimensional NMR spectroscopy N. Hertkorn, A. Kettrup. 22. Understanding capillary electrophoretic separation processes to characterize humic substances and their interactions with pollutants Ph. Schmitt-Kopplin, A. Kettrup. 23. Ozone application for modification of humates and lignins M.M. Ksenofontova et al. 24. Synthesis, metal-binding properties and detoxifying ability of sulfonated humic acids M.V. Yudov et al. Author Index. Subject Index.

Quantitative and qualitative precision improvements by effective mobility-scale data transformation in capillary electrophoresis analysis.

By transforming the time‐based x‐axis of electropherograms in capillary zone electrophoresis (CZE) into the corresponding effective mobility‐scale, we propose a simple and robust data representation for a better qualitative and quantitative capillary electrophoresis (CE) analysis. The time scale of the raw electrophoretic data (detection signal versus time) is transformed into an effective electrophoretic mobility scale (μeff‐scale) with account of the electroosmotic flow (EOF) peak or of an internal standard of known effective mobility. With the new scaling (detection signals versus effective mobility), the obtained electropherograms are more representative of the velocity‐based electrophoretic separation and the comparison of complete electropherograms is directly possible. This is of importance when tracking peaks in real samples where alteration in EOF stability can occur or when comparing electrophoretic runs from different experimental setups (independence in column length and voltage). Beside the qualitative possibilities, a quantitative improvement is achieved in the μeff‐scale with significant better peak area reproducibility and equal to more precision in quantitative analysis than with the primary time‐scale integration.*

REMEDIATION CHEMISTRY OF HUMIC SUBSTANCES: THEORY AND IMPLICATIONS FOR TECHNOLOGY

An overview is given of the interactions encountered between humic substances (HS), ecotoxicants, and living organisms in the context of environmental remediation. The most important interactions identified include: binding interactions affecting chemical speciation and bioavailability of contaminants; interfacial interactions altering physical speciation or interphase partitioning of ecotoxicants; abiotic-biotic redox interactions that influence metabolic pathways coupled to pollutants; and finally direct and indirect interactions coupled to various physiological functions of living organisms. Because humics are polyfunctional, they can operate as binding agents and detoxicants, sorbents and flushing agents, redox mediators of abiotic and biotic reactions, nutrient carriers, bioadaptogens, and growth-stimulators. It is shown that these functions possess significant utility in the remediation of contaminated environments and as such humic-based reactions pertinent to permeable reactive barriers, in situ flushing, bioremediation, and phytoremediation are examined in detail. Finally, this chapter introduces the novel concept of “designer humics” which are a special class of customized humics of the reduced structural heterogeneity and of the controlled size. They are developed and deployed to carry out one or more of the above in situ functions in an optimum manner and for the purpose of enhancing the efficacy of one or more remediation technologies. Designer humics possess specified reactive properties obtained by chemical modification and cross-linking of the humic backbone. This new class of reactive agents portend new opportunities for achieving enhanced remediation and for quantifying remediation performance. The latter is described in the context of the passive flux meter technology developed for direct measuring fluxes of contaminants and biomass.

Size Exclusion Chromatography Of Humic Substances: Complexities Of Data Interpretation Attributable To Non-size Exclusion Effects

The use of size exclusion chromatography (SEC) to support a theory of conformational changes in humic acids induced by organic acids is reviewed. Particular attention is given to an evaluation of the role of non-size exclusion effects in SEC experiments. In this review, results from SEC studies are interpreted in terms of electrostatic, salt, and specific sorption effects that influence the behavior of the HS on the gel. That interpretation has been proven by experimental results from SEC-fractionation of HS in the absence of organic acids, and this has revealed similar interactions between the HS and the gel. The preference here is for the theory of non-size exclusion effects based on considerations of HS as natural polyelectrolytes.

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.

Size-exclusion chromatographic descriptors of humic substances.

An approach to the generation of size exclusion chromatographic (SEC) descriptors of humic substances (HS) is proposed. It implies a calculation of initial, central and normalised statistical moments and some of their ratios from the raw SEC-data. The proposed descriptors extend the pool of common molecular weight (MW) characteristics (average MW’s and their ratios) up to 20 parameters, which is important for the purposes of classification and prognostic modelling. Original software was developed to facilitate the computation of molecular weight distribution (MWD) and SEC-descriptors of HS from raw chromatographic data. The developed approach was applied to two model compounds and three humic materials. The discriminatory power of the calculated descriptors was roughly estimated on the example of three humic materials of different origin with the use of a multivariate variance analysis. Weight average MW and a ratio of the z- to weight average distribution coefficients were found to be the best discriminators, whereas the significance level of discrimination provided by the second moment and Mz/Mw-ratio was lower than 95%. ©2000 Elsevier Science B.V. All rights reserved.

Towards a Quantitative Structure Activity Relationship (QSAR) of Dissolved Humic Substances as Detoxifying Agents in Freshwaters

In freshwater ecosystems, dissolved humic substances (HS) can sorb hydrophobic organic chemicals and thereby reduce their bioconcentration and toxicity. The extent of the sorption depends both on the concentration and on the origin of HS. This paper summarizes work that characterized HS from different origins by various spectroscopic and chemical properties, and related these properties to (1) the sorption of polycyclic aromatic hydrocarbons (PAHs) by HS (measured by a fluorescence quenching method), (2) effects of HS on the bioconcentration of PAHs and (3) effects of HS on the toxicity of PAHs. The most powerful predictor of the association between 26 different HS and the PAHs pyrene, fluoranthene, and anthracene was the content of aromatic carbons of the HS. The influence of HS on the bioconcentration of PAHs was investigated by measuring the effect of seven different humic and fulvic acids on the uptake of pyrene and benzo[a]pyrene into the nematode Caenorhabditis elegans. Again, parameters describing aromatic properties of the HS, such as the content of aromatic carbons, or the specific absorptivity at 254 nm gave the best prediction of HS effects on bioconcentration. Studies on the effect of HS on the toxicity of PAHs (impact on grazing activity of Daphnia magna) gave similar results: The detoxifying ability (= reduction of toxicity) of HS could be correlated to the quotient between aromatic carbons and aliphatic carbons in the HS. Taking these results together, we can describe the relationship between structure and effects of HS on bioavailability and toxicity of PAHs as follows: HS associate with PAHs, making the PAHs unavailable for uptake into organisms, and consequently reducing toxic effects of the PAHs. Aromatic properties of the HS can be used to predict the effect of HS in each of these steps.

Estimation of uptake of humic substances from different sources by Escherichia coli cells under optimum and salt stress conditions by use of tritium-labeled humic materials.

ABSTRACT The primary goal of this paper is to demonstrate potential strengths of the use of tritium-labeled humic substances (HS) to quantify their interaction with living cells under various conditions. A novel approach was taken to study the interaction between a model microorganism and the labeled humic material. The bacterium Escherichia coli was used as a model microorganism. Salt stress was used to study interactions of HS with living cells under nonoptimum conditions. Six tritium-labeled samples of HS originating from coal, peat, and soil were examined. To quantify their interaction with E. coli cells, bioconcentration factors (BCF) were calculated and the amount of HS that penetrated into the cell interior was determined, and the liquid scintillation counting technique was used as well. The BCF values under optimum conditions varied from 0.9 to 13.1 liters kg−1 of cell biomass, whereas under salt stress conditions the range of corresponding values increased substantially and accounted for 0.2 to 130 liters kg−1. The measured amounts of HS that penetrated into the cells were 23 to 167 mg and 25 to 465 mg HS per kg of cell biomass under optimum and salt stress conditions, respectively. This finding indicated increased penetration of HS into E. coli cells under salt stress.

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.