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PubMed1996

Spectroscopic and elemental investigation of microbial decomposition of aquatic fulvic acid in biological process of drinking water treatment.

As humic substances left in treated water tend to form trihalomethans during chlorination, their removal in water treatment processes is a significant concern for drinking water supplies. One of the removal technologies, the biofilm reactor is studied for the microbial decomposition of aquatic fulvic acid (AFA). The AFA is characterized by elemental analysis. UV-Vis, 13C-NMR, and IR spectroscopic methods. The spectroscopic and elemental investigation was capable of characterizing the microbial decomposition of AFA. Biologically treated fulvic acid was in a more oxidized state; its spectra displayed a higher degree of condensation of aromatic constituents than influent fulvic acid. Microbial degradation of AFA was more active in the low molecular weight fractions and intensively occurred in the aliphatic fraction.

Benzopyrans↗

PubMed1997

Microorganisms and enzymes involved in the degradation of plant fiber cell walls.

One of natures most important biological processes is the degradation of lignocellulosic materials to carbon dioxide, water and humic substances. This implies possibilities to use biotechnology in the pulp and paper industry and consequently, the use of microorganisms and their enzymes to replace or supplement chemical methods is gaining interest. This chapter describes the structure of wood and the main wood components, cellulose, hemicelluloses and lignins. The enzyme and enzyme mechanisms used by fungi and bacteria to modify and degrade these components are described in detail. Techniques for how to assay for these enzyme activities are also described. The possibilities for biotechnology in the pulp and paper industry and other fiber utilizing industries based on these enzymes are discussed.

Bacteria↗

PubMed2026

Plant-derived and microbial biostimulants in sustainable agriculture: mechanisms, applications, and challenges.

Plant biostimulants have emerged as transformative and sustainable tools for improving crop productivity, resource-use efficiency, and resilience under rapidly intensifying environmental stresses. Unlike conventional agrochemicals, biostimulants function by activating physiological, biochemical, and molecular processes that optimize plant performance without directly supplying nutrients or exerting pesticidal effects. This review comprehensively examines the integrated roles of plant-derived and microbial biostimulants in sustainable agriculture, with particular emphasis on microbial-mediated mechanisms underlying plant stress adaptation and rhizosphere functioning. Plant-derived biostimulants, including seaweed extracts, humic substances, protein hydrolysates, amino acids, and chitosan, enhance nutrient acquisition, root architecture, hormonal regulation, and antioxidant defense systems. More importantly, microbial biostimulants, such as plant growth-promoting rhizobacteria (PGPR), endophytic microorganisms, mycorrhizal fungi, actinomycetes, yeasts, and cyanobacteria, exert multifunctional effects through biological nitrogen fixation, mineral solubilization, phytohormone biosynthesis, volatile signaling, osmolyte accumulation, pathogen suppression, and modulation of stress-responsive genes. These beneficial microorganisms reshape rhizosphere microbial communities, improve nutrient cycling, and enhance plant tolerance to drought, salinity, heat, and heavy metal toxicity. Emerging evidence from genomics, transcriptomics, metabolomics, and microbiome-based investigations has further revealed the molecular networks and signaling pathways governing biostimulant-induced resilience and plant-microbe interactions. Despite their substantial promise, inconsistent field performance, formulation instability, regulatory limitations, and inadequate mechanistic understanding continue to restrict their large-scale adoption. This review highlights recent advances in microbial and plant-derived biostimulants while identifying critical knowledge gaps and future opportunities for precision biostimulant engineering, microbiome manipulation, and climate-resilient crop management. The integration of next generation biostimulant technologies into sustainable agricultural systems may significantly reduce dependence on agrochemicals while improving crop productivity, environmental sustainability, and global food security.

Agriculture↗

PubMed2003

Complexation as the most important factor in the fate and transport of heavy metals in the Dnieper water bodies.

The results of long-term investigations of the concentrations of dissolved forms of some heavy metals (Mn, Cu, Zn, Pb, Cr, Cd) and their species in the water of the Dnieper reservoirs and the Dnieper-Bug estuary are considered. Chemiluminescent methods, anodic stripping voltammetry, membrane filtration, ion-exchange, and gel-permeation chromatography were used for study of the speciation of the metals. It has been found that binding of heavy metals into complexes with dissolved organic matter (DOM) is the dominant factor of their stabilization in solution. The molecular weight distribution of organic metal complexes and their chemical nature, as well as the potential complexing ability of DOM were investigated. Humic substances, particularly fulvic acids, play a major role in the complexation. These ligands bind from 45 to 80% of metals in the form of organic complexes. Metal complex compounds of relatively low molecular weight (<5 kDa) predominated in the organic complexes.

Journal Article↗

PubMed2003

LC-MS analysis in the aquatic environment and in water treatment--a critical review. Part I: Instrumentation and general aspects of analysis and detection.

LC-MS has become an invaluable technique for trace analysis of polar compounds in aqueous samples of the environment and in water treatment. LC-MS is of particular importance due to the impetus it has provided for research into the occurrence and fate of polar contaminants, and of their even more polar transformation products. Mass spectrometric detection and identification is most widely used in combination with sample preconcentration, chromatographic separation and atmospheric pressure ionization (API). The focus of the first part of this review is directed particularly toward instruments and method development with respect to their applications for detecting emerging contaminants, microorganisms and humic substances (HS). The current status and future perspectives of 1) mass analyzers, 2) ionization techniques to interface liquid chromatography (LC) with mass spectrometry (MS), 3) methods for preconcentration and separation with respect to their application for water analysis are discussed and examples of applications are given. Quadrupole and ion trap mass analyzers with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) are already applied in routine analysis. Time-of-flight (TOF) mass spectrometers are of particular interest for accurate mass measurements for identification of unknowns. For non-polar compounds, different ionization approaches have been described, such as atmospheric pressure photoionization (APPI), electrochemistry with ESI, or electron capture ionization with APCI. In sample preconcentration and separation, solid phase extraction (SPE) with different non-selective sorbent materials and HPLC on reversed-phase materials (RP-HPLC) play the dominant role. In addition, various on-line and miniaturized approaches for sample extraction and sample introduction into the MS have been used. Ion chromatography (IC), size-exclusion chromatography (SEC), and capillary electrophoresis (CE) are alternative separation techniques. Furthermore, the issues of compound identification, matrix effects on quantitation, development of mass spectral libraries and the topic of connecting analysis and toxicity bioassays are addressed.

Journal Article↗

PubMed2006

O-Alkylation of a lignite humic acid by phase-transfer catalysis.

A mild phase-transfer catalytic reaction has been conducted to O-alkylate the acidic functions of a lignite humic acid (HA), using tetrabutylammonium hydroxide as the phase-transfer catalyst. The HA acidic functional groups were made to react, in tetrahydrofuran, by nucleophilic substitution with several alkyl halides-methyl iodide, and ethyl, propyl, and butyl, and benzyl bromide. The occurrence of the O-alkylation reaction was assessed by elemental analysis and 1H NMR, CPMAS 13C NMR, and FTIR spectroscopy. Bonding of alkyl groups increased the carbon and hydrogen content and the H/C ratios of all the humic reaction products. Increased nitrogen in the reaction products suggested incomplete removal of the phase-transfer catalyst after purification of the alkylated HA. 1H NMR and CPMAS 13C NMR spectra of alkylated products provided evidence of the successful occurrence of the alkylation reactions. Infrared spectra confirmed the NMR results, revealing the characteristic absorption of newly formed alkyl and aryl ethers and esters in the alkylated products and C-H stretching in the aromatic ring of the benzylated derivative. These findings indicate that humic matter can be successfully alkylated with several different alkylating groups by catalysed phase-transfer reaction. This O-alkylation reaction has the advantage of being mild, versatile, and high-yielding compared with traditional methylation reactions applied to HA. The possibility of introducing different alkyl groups into the HA by a mild phase-transfer reaction may become useful by enabling improved fractionation of humic supramolecular associations and further understanding of the molecular nature of humic substances.

Journal Article↗

PubMed2006

New analytical procedure based on a cellulose bag and ionic exchanger with p-aminobenzoic acid groups for differentiation of labile and inert metal species in aquatic systems.

A new procedure was developed for the in situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory to evaluate the influence of complexation time, mass of exchanger, pH, metal ions (Cu, Cd, Fe, Mn, and Ni), and concentration of organic matter on the relative lability of metal species. It was found that the pH and kinetics strongly influence the process of metal complexation by the DM-Cell-PAB system. At all pH levels, Cd, Mn, and Ni showed lower complexation with Cell-PAB resin than Cu and Fe metals. Note that relative lability of metals complexed to aquatic humic substances (AHS) in the presence of Cell-PAB resin showed the following order: Cu approximately or = Fe>>Ni>Mn=Cd. The results presented here also indicate that increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems.

4-Aminobenzoic Acid↗

PubMed2000

A simplified HPTLC screening method for the estimation of the PAH content in soil samples.

Based on a highly significant correlation between the visual fluorescing fraction of PAH on the one hand and the total EPA-PAH16 content in mineral soils on the other hand, a deliberately incomplete RP-TLC separation of these compounds into a few fingerprint-like compressed bands within a determined "PAH window" has been achieved. The resulting band-pattern does not interfere normally with the more or less non-polar phenolic compounds which are associated with natural soil humic substances. The extraction step has been extremely simplified with regard to the quantity of the soil sample and of the extractant. The accuracy of this procedure has been ascertained by means of recovery experiments with an artificial soil enriched with PAH. A single spot application mode and an evaluation scheme allow the estimation of EPA-PAH16 contents of soil samples in relation to threshold values (1 or 5 or 10 mg/kg). This HPTLC screening method has been compared against standard HPLC methods. The simplified extraction step and the separation by HPTLC minimizes the actual costs and the time spent per sample.

Benzene↗

PubMed2000

Speciation of copper, lead and cadmium in aquatic systems by circulating dialysis combined with flame AAS.

The assessment of free Cu(II), Pb(II) and Cd(II) ions in the presence of complexed species was realised by a circulating dialysis with Cuprophan planar membranes and subsequent quantification by flame atomic absorption spectrometry. The effect of the flow rate, the time of equilibration, pH and the presence of various complexing agents in the donor solutions were studied. The determination of free Cu(II), Pb(II) and Cd(II) ions in the presence of soil humic substances resulted from the above studies.

Journal Article↗

PubMed2003

The combined effects of hardness, pH, and dissolved organic carbon on the chronic toxicity of Zn to D. magna: development of a surface response model.

The effect of changes in pH, hardness, and dissolved organic carbon (DOC) and the possible interactions among these parameters on the chronic toxicity of zinc to D. magna were investigated. Based on a Central Composite Design, models were developed that can explain the observed variation in EC(10) and EC(50) as a function of these toxicity modifying factors. All three parameters significantly altered the observed effect concentrations based on net reproductive rate. The largest differences in 21-day EC(10)s and EC(50)s caused by these factors were 10.1 and 4.9, respectively. An increase in pH and/or DOC decreased zinc toxicity. The significant interaction between pH and DOC on observed chronic Zn toxicity is in accordance with earlier reported increased sorption efficiency of Zn to humic substances at higher pH levels. Lowest Zn toxicity was observed in tests performed with moderately hard test media (between 200 and 300 mg/L as CaCO(3)). Lower or higher hardness of the test medium resulted in lower effect concentrations. Based on physico-chemical characteristics of the test media, developed models can be used to explain the variation between reported NOECs for Zn and may improve current environmental risk assessment procedures of metals.

Animals↗

PubMed1999

Degradation of Soil Humic Extract by Wood- and Soil-Associated Fungi, Bacteria, and Commercial Enzymes.

> Abstract An alkaline humic extract (HE) of a black calcareous forest mull was exposed to 36 fungal and 9 eubacterial isolates in liquid standing culture. At 21 d in fungi, and 4 d in bacteria, the groups of wood-degrading basidiomycetes, terricolous basidiomycetes, ectomycorrhizal fungi, soil-borne microfungi, and eubacteria had reduced the absorbance (A340) of HE media by 57, 28, 19, 26 and 5%, respectively. Gel permeation chromatography revealed that the large humic acid molecules were more readily degraded than the smaller fulvic acid molecules and served as a sole source of carbon and energy. The more active HE degraders reduced the overall molecular weight of humic and fulvic acids by 0.25 to 0.47 kDa. They also reduced the chemical reactivity of HE to tetrazotized o-dianisidine, indicating the degradation of hydroxylated aromatic molecules (which are responsible for this reaction). Decreases in absorbance, molecular weight, and reactivity were caused by fungal manganese peroxidase, horseradish peroxidase, beta-glucosidase, and abiotic oxidants such as H2O2 and Mn(III) acetate. It is concluded that fungi, some of which are propagated in contaminated soils to control xenobiotics, metabolize HE compounds enzymatically. They use enzymes which are also involved in the degradation of soil xenobiotics. Because of reductions in the molecular weight of HE, which is a potential carrier of heavy metal ions and xenobiotics, solubility and motility of humic substances in soil and surface waters are increased.

Journal Article↗

PubMed1999

Differential Dissolved Organic Nitrogen Availability and Bacterial Aminopeptidase Activity in Limnic and Marine Waters.

Abstract Nitrogen often limits primary production in marine ecosystems and its loading from terrestrial sources is the major cause of enhanced coastal eutrophication worldwide. About 70% of nitrogen transported by rivers globally is dissolved organic nitrogen (DON). Therefore, terrestrial DON is potentially an important component of the N dynamics in aquatic ecosystems, but the bioavailability of this organic nitrogen is poorly known. Bacterial extracellular hydrolysis of polymers is a bottleneck in the utilization of natural dissolved organic matter, mostly consisting of high molecular weight compounds. To study the bacterial utilization and extracellular enzymatic hydrolysis of DON, we developed a bioassay employing natural DON as the only N source, and N as the limiting nutrient. Bacterial cell density and activity of an unspecific aminopeptidase (AMPase) were followed in the cultures. Natural DON stimulated the cell-specific AMPase activity. Furthermore, refractory and humus-rich DOM caused a stronger stimulation than labile DOM. We propose that the previously reported inhibitory effect of humic substances on enzyme activity was outweighed by the induction of enzyme synthesis caused by refractory substrates. AMPase activity and the estimated DON bioavailability were more than twofold higher in seawater than in freshwater with identical substrate additions. This indicates that hydrolysis and turnover of land-derived DON is enhanced when it enters coastal marine waters, enabling it to support elevated bacterioplankton and phytoplankton growth.http://link.springer-ny.com/link/service/journals/00248/bibs/38n3p264.html</hea

Journal Article↗

PubMed2003

Termite symbiotic systems: efficient bio-recycling of lignocellulose.

Termites thrive in great abundance in terrestrial ecosystems and play important roles in biorecycling of lignocellulose. Together with their microbial symbionts, they efficiently decompose lignocellulose. In so-called lower termites, a dual decomposing system, consisting of the termite's own cellulases and those of its gut protists, was elucidated at the molecular level. Higher termites degrade cellulose apparently using only their own enzymes, because of the absence of symbiotic protists. Termite gut prokaryotes efficiently support lignocellulose degradation. However, culture-independent molecular studies have revealed that the majority of these gut symbionts have not yet been cultivated, and that the gut symbiotic community shows a highly structured spatial organization. In situ localization of individual populations and their functional interactions are important to understand the nature of symbioses in the gut. In contrast to cellulose, lignin degradation does not appear to be important in the gut of wood-feeding termites. Soil-feeding termites decompose humic substances in soil at least partly, but little is known about the decomposition. Fungus-growing termites are successful in the almost complete decomposition of lignocellulose in a sophisticated cooperation with basidiomycete fungi cultivated in their nest. A detailed understanding of efficient biorecycling systems, such as that for lignocellulose, and the symbioses that provide this efficiency will benefit applied microbiology and biotechnology.

Animals↗

PubMed2004

Anaerobic degradation of monoaromatic hydrocarbons.

Over the last two decades significant advances have been made in our understanding of the anaerobic biodegradability of monoaromatic hydrocarbons. It is now known that compounds such as benzene, toluene, ethylbenzene, and all three xylene isomers can be biodegraded in the absence of oxygen by a broad diversity of organisms. These compounds have been shown to serve as carbon and energy sources for bacteria growing phototrophically, or respiratorily with nitrate, manganese, ferric iron, sulfate, or carbon dioxide as the sole electron acceptor. In addition, it has also been recently shown that complete degradation of monoaromatic hydrocarbons can also be coupled to the respiration of oxyanions of chlorine such as perchlorate or chlorate, or to the reduction of the quinone moieties of humic substances. Many pure cultures of hydrocarbon-degrading anaerobes now exist and some novel biochemical and genetic pathways have been identified. In general, a fumarate addition reaction is used as the initial activation step of the catabolic process of the corresponding monoaromatic hydrocarbon compounds. However, other reactions may alternatively be involved depending on the electron acceptor utilized or the compound being degraded. In the case of toluene, fumarate addition to the methyl group mediated by benzylsuccinate synthase appears to be the universal mechanism of activation and is now known to be utilized by anoxygenic phototrophs, nitrate-reducing, Fe(III)-reducing, sulfate-reducing, and methanogenic cultures. Many of these biochemical pathways produce unique extracellular intermediates that can be utilized as biomarkers for the monitoring of hydrocarbon degradation in anaerobic natural environments.

Anaerobiosis↗

PubMed2001

Biodegradation of radiolabelled synthetic lignin (14C-DHP) and mechanical pulp in a compost environment.

Mineralization of radioactive synthetic lignin (14C-DHP) was studied in a compost environment at 35, 50 and 58 degrees C. Compost samples were successively extracted with water, dioxane and alkali, and the molecular weight distribution of some extracts was determined by gel permeation chromatography (GPC). Biodegradation of lignin-containing spruce groundwood (SGW) and pine sawdust was concurrently determined in controlled composting tests by measuring evolved CO2. The temperatures were the same as in the 14C-DHP mineralization experiment and bleached kraft paper, with a lignin content of 0.2%, was used as a reference. The mineralization of 14C-DHP was relatively high (23-24%) at 35 degrees C and 50 degrees C, although the mixed population of compost obviously lacks the most effective lignin degraders. At 58 degrees C the mineralization of 14C-DHP, as well as the biodegradation of SGW and sawdust, was very low, indicating that the lignin-degrading organisms of compost were inactivated at this temperature. SGW was poorly biodegradable (<40%) in controlled composting tests compared with kraft paper (77-86%) at all temperatures, which means that lignin inhibits the degradation of carbohydrates. During the incubation, water-soluble degradation products, mainly monomers and dimers, and the original 14C-DHP were either mineralized or bound to humic substances. A substantial fraction of 14C-DHP was incorporated into humin or other insolubles.

Biodegradation, Environmental↗

PubMed2006

When quinones meet amino acids: chemical, physical and biological consequences.

Quinones and amino acids are usually compartmentally separated in living systems, however there are several junctions in which they meet, react and influence. It occurs mainly in wounded, cut or crushed plant material during harvest, ensiling or disintegrating cells. Diffusing polyphenols are oxidized by polyphenol oxidases (PPOs) to quinonic compounds, which associate reversibly or irreversibly with amino acids and proteins. The reaction takes place with the free nucleophilic functional groups such as sulfhydryl, amine, amide, indole and imidazole substituents. It results in imine formation, in 1,4-Michael addition via nitrogen or sulphur and in Strecker degradation forming aldehydes. The formation and activity of quinone-amino acids conjugates influences the colour, taste, and aroma of foods. Physical and physiological phenomena such as browning of foods, discoloration of plants during processing, alteration of solubility and digestibility, formation of humic substances, germicidal activity, cytotoxicity and more occur when quinones from disintegrating cells meet amino acids. The mechanisms of toxicity and the pathways by which PCBs may be activated and act as a cancer initiator include oxidation to the corresponding quinones and reaction with amino acids or peptides. Sclerotization of insect cuticle is a biochemical process involving also the reaction between quinones and amino acid derivatives.

Amino Acids↗

PubMed1987

Influence of aquatic humus and pH on the uptake and depuration of cadmium by the Atlantic salmon (Salmo salar L.).

Uptake and release of cadmium by Atlantic salmon at the concentrations near the background values for fresh water have been studied using cadmium labelled with Cd-109. Cumulation constant and biological half-time of release were established for different concentrations of humus and values of pH. The uptake is strongly dependent on the concentration of humus, showing a pronounced maximum at a DOC concentration of 2.7 mg/l. Release of cadmium is relatively slow, the biological half-time exceeds one year in the water without humic substances. Calculated bioconcentration factors range from 130 to several thousands, which may explain the wide differences of bioconcentration factor reported for natural systems. A general equation enabling calculation of bioconcentration factors for various conditions has been derived. An attempt is done to discuss the results from the point of view of physico-chemical forms of cadmium in respective waters. The amount of cadmium adsorbed on the surface of the fish was proved to be insignificant when compared with total concentration of cadmium bioaccumulated in the fish.

Adsorption↗

PubMed1991

Mutagenicity of ozonation and chlorination products from p-hydroxybenzaldehyde.

p-Hydroxybenzaldehyde, a component of soil humic substances, was ozonated and chlorinated. The ether extract and the residue were subjected to the Ames assay; mutagenic activities were identified. The non-ionic resin CSP800 and the anion exchange resin CHPA25 were used for separation of mutagenic compounds. The compounds in the water layer were not adsorbed on CSP800 or CHPA25 and exhibited strong mutagenic activity. Mutagenic activity was reduced as the added chlorine was increased. Ether extracts were analyzed by gas chromatography-mass spectrometry (GC-MS) and chloral, 1,3-dichloro-2-propanone, 1,2,3-trichloro-1-propene, tetrachloroethylene and 1,1,1,3,3-pentachloro-2-propanone were identified as mutagenic compounds.

Animals↗