Concept: Humic acid
Knowledge of the structure-property-function relationship of humic substances (HSs) is key for understanding their role in soil. Despite progress, studies on this topic are still under discussion. We analyzed 37 humic fractions with respect to their isotopic composition, structural characteristics, and properties responsible for stimulating plant root parameters. We showed that regardless of the source of origin of the carbon (C3 or C4), soil-extracted HSs and humic acids (HAs) are structurally similar to each other. The more labile and functionalized HS fraction is responsible for root emission, whereas the more recalcitrant and less functionalized HA fraction is related to root growth. Labile structures promote root stimulation at lower concentrations, while recalcitrant structures require higher concentrations to promote a similar stimulus. These findings show that lability and recalcitrance, which are derived properties of humic fractions, are related to the type and intensity of their bioactivity. In summary, the comparison of humic fractions allowed a better understanding of the relationship between the source of origin of plant carbon and the structure, properties, and type and intensity of the bioactivity of HSs in plants. In this study, scientific concepts are unified and the basis for the agronomic use of HSs is established.
- Environmental science and pollution research international
- Published about 7 years ago
The aim of this study is to investigate how the presence of Cu influences tebuconazole (Teb) sorption onto contrasting soil types and two important constituents of the soil sorption complex: hydrated Fe oxide and humic substances. Tebuconazole was used in commercial form and as an analytical-grade chemical at different Teb/Cu molar ratios (1:4, 1:1, 4:1, and Teb alone). Increased Cu concentrations had a positive effect on tebuconazole sorption onto most soils and humic substances, probably as a result of Cu-Teb tertiary complexes on the soil surfaces. Tebuconazole sorption increased in the following order of different Teb/Cu ratios 1:4 > 1:1 > 4:1 > without Cu addition, with the only exception for the Leptosol and ferrihydrite. The highest K ( f ) value was observed for humic substances followed by ferrihydrite, the Cambisol, the Arenosol, and the Leptosol. The sorption of analytical-grade tebuconazole onto all matrices was lower, but the addition of Cu supported again tebuconazole sorption. The Teb/Cu ratio with the highest Cu addition (1:4) exhibited the highest K ( f ) values in all matrices with the exception of ferrihydrite. The differences in tebuconazole sorption can be attributed to the additives present in the commercial product. This work proved the importance of soil characteristics and composition of the commercially available pesticides together with the presence of Cu on the behavior of tebuconazole in soils.
Kinetics of humic acid (HA) adsorption onto soil minerals (kaolinite and hematite) has been investigated under various conditions. The influence of ionic strength, pH, and solution cations on the rate of adsorption has been studied. The rate and the amount of adsorbed humic acid onto soil minerals increased with increasing ionic strength, decreasing pH, and in the presence of Ca(2+) as background electrolyte. The adsorption equilibrium data showed that adsorption behavior of humic acid could be described more reasonably by Freundlich adsorption isotherm than Langmiur adsorption isotherm. Pseudo first order and pseudo second order kinetic models were used to evaluate the kinetic data and the rate constants. The results explained that humic acid adsorption on hematite and kaolinite was more conforming with pseudo second order kinetics.
The significance of natural organic matter (NOM, both humic acid and alginate) on the transport and deposition kinetics of ZnO nanoparticles (NPs) in irregular quartz sand was examined by direct comparison of both breakthrough curves and retained profiles with NOM present in NPs suspension versus those obtained without NOM. Packed column experiments were conducted in both NaCl and CaCl(2) solutions under a series of environmentally relevant ionic strengths. Under all examined conditions, breakthrough plateaus with NOM even at concentration as low as 1 mg L(-1) of total organic carbon (TOC) were higher than those without NOM, indicating that presence of NOM in NPs suspensions enhanced ZnO NPs transport. Although hyper-exponential retained profiles were observed both in the presence and absence of NOM, the amount of retained ZnO NPs acquired in the presence of NOM decreased slowly as the transport distance increased. Straining induced by concurrent aggregation is found to cause the hyper-exponential decrease. In the presence of NOM, electrosteric interaction effectively reduced the ZnO NPs deposition on collector surfaces and NPs-NPs aggregation. Subsequently, the amount of NPs that jammed in the column inlet in the absence of NOM were markedly decreased, which therefore exhibited as flatter retained profiles.
An accurate and fast method for simultaneous determination of small organic acids and much larger humic acids was developed using high performance size exclusion chromatography. Two small organic acids, i.e. salicylic acid and 2,3-dihydroxybenzoic acid, and one purified humic acid material were used in this study. Under the experimental conditions, the UV peaks of salicylic acid and 2,3-dihydroxybenzoic acid were well separated from the peaks of humic acid in the chromatogram. Concentrations of the two small organic acids could be accurately determined from their peak areas. The concentration of humic acid in the mixture could then be derived from mass balance calculations. The measured results agreed well with the nominal concentrations. The detection limits are 0.05 mg/L and 0.01 mg/L for salicylic acid and 2,3-dihydroxybenzoic acid, respectively. Applicability of the method to natural samples was tested using groundwater, glacier, and river water samples (both original and spiked with salicylic acid and 2,3-dihydroxybenzoic acid) with a total organic carbon concentration ranging from 2.1 to 179.5 mg C/L. The results obtained are promising, especially for groundwater samples and river water samples with a total organic carbon concentration below 9 mg C/L.
The inner filter effects in synchronous fluorescence spectra (Δλ=60nm) of sedimentary humic substances from a salt marsh were studied. Accordingly to their type and the influence of plant colonization, these humic substances have different spectral features and the inner filter effects act in a different manner. The fluorescence spectra of the humic substances from sediments with colonizing plants have a protein like band (λexc=280nm) which is strongly affected by primary and secondary inner filter effects. These effects were also observed for the bands situated at longer wavelengths, i.e., at λexc=350nm and λex=454nm for the fulvic acids (FA) and humic acids (HA), respectively. However, they are more important for the band at 280nm, causing spectral distortions which can be clearly seen when the spectra of solutions 40mgL(-1) of different samples (Dissolved Organic Carbon - DOC∼20mgL(-1)) are compared with and without correction of the inner filter effects. The importance of the spectral distortions caused by inner filter effects has been demonstrated in solutions containing a mixture of model compounds which represent the fluorophores detected in the spectra of sedimentary humic samples. The effectiveness of the mathematical correction of the inner filter effects in the spectra of those solutions and of solutions of sedimentary humic substances was studied. It was observed that inner filter effects in the sedimentary humic substances spectra can be mathematically corrected, allowing to obtain a linear relationship between the fluorescence intensity and humic substances concentration and preventing distortions at concentrations as high as 50mgL(-1) which otherwise would obscure the protein like band.
Humic substances (HS), an important fraction of soil organic carbon, are distributed widely throughout cold environments. A total of cold-adapted 122 bacterial strains were isolated from 66 Alaska grassland soil samples based on their ability to grow on humic acids (HA), a main fraction of HS, as a carbon and energy source. These isolates were identified based on 16S rRNA gene sequencing, with class Bacilli (79.5%) and γ-Proteobacteria (17.1%) comprising the largest groups. Among them, 45 strains, mainly Paenibacillus (27 strains) and Pseudomonas (15 strains), were selected for further screening. Two strains (Pseudomonas sp. PAMC 26793 and Paenibacillus sp. PAMC 26794) most efficiently degraded HA, but showed significant differences in their ability to grow on various monocyclic aromatics, which are putative degradative metabolites of HS. Fourier transform infrared spectra also showed substantial but different changes in HA chemical structure after incubation with each strain. Gel permeation chromatography demonstrated that depolymerization and polymerization of HA occurred during HS degradation by these newly isolated microbes.
In this work, fouling, scaling and cleaning of the capacitive deionisation (CDI) with activated carbon electrodes were systematically investigated for the first time. Electrode fouling caused by dissolved organic matter using sodium salt of humic acid as a model foulant (measured by total organic carbon concentration, TOC) and inorganic salt (NaCl, MgCl(2), CaCl(2) and FeCl(3)) in the CDI feed solutions was investigated in a series of controlled fouling experiments. After each CDI experiment, a series of cleaning steps was performed to understand the reversibility of fouling accumulated on the electrode surface by analysing the cleaning solutions. The higher the TOC concentration in the CDI feed solution, the more the reduction of salt removal efficiency, declination in the production rate and energy consumption. Dissolved organic matter is the main cause of electrode fouling, as it blocks the activated carbon pores and reduces their electrosorption capacitance. Ca and Mg have no noticeable effect on the CDI treatment performance. However, Fe seemed to have a greater effect on CDI electrode fouling. Alkaline and acid cleaning solutions were able to restore the recovery of the CDI performance from fouling. Pre-treatment to reduce the dissolved organic matter levels is recommended to achieve sustainable treatment performance.
Humic acids (HAs) of four representative forest soils profiles from Central Spain (two with different vegetation - pine and oak - but same parent material - granitie, and two with same vegetation - holm oak - but different parent material - granite and limestone) were investigated by solid-state cross polarization with magic angle spinning (13)C nuclear magnetic resonance (NMR) spectroscopy. The objectives included the investigation of the impact of different forest properties on HA composition, assessing how the structural characteristics of the HA vary with soil depth, and evaluating the role of HA as surrogates for mapping the different forest soils signatures using structural data derived from (13)C NMR spectroscopy. On average, alkyl C is the dominant C constituent (38-48% of the total NMR peak area) in all HA samples, followed by aromatic (12-22%) and O-alkyl C (12-19%), and finally carboxyl C (7.0-10%). The NMR data also indicated that HA composition is likely to be differently affected by the soil physico-chemical properties and type of forest vegetation. The structural characteristics of the HA from soil under oak did not differ broadly downward in the profile, whereas soil HA under pine forest exhibits a somewhat higher recalcitrant nature as a consequence of a higher degree of decomposition. The soil HA from holm oak forests differed from the other two forest soils, exhibiting a progressive decomposition of the alkyl C structures with increasing depth, while the carbohydrate-like indicator (O-alkyl C) is apparently being protected from mineralization in the horizons below the ground level. Overall, these differences in soil HA NMR signatures are an important diagnostic tool for understanding the role of different soil environmental factors on the structural composition of HA from Mediterranean forest soils.
Soil contamination with PCBs and PAHs in adjacent forest plots, characterized by a distinct composition in tree species (spruce only, mixed and beech only), was analyzed to investigate the influence of ecosystem type on contaminant mobility in soil under very similar climate and exposure conditions. Physical-chemical properties and contaminant concentrations in litter (L), organic (F, H) and mineral (A, B) soil horizons were analyzed. Contaminant distribution in the soil core varied both in relation to forest type and contaminant group/properties. Contaminant mobility in soil was assessed by examining the ratios of total organic carbon (TOC)-standardized concentrations across soil horizons (Enrichment factors, EFTOC) and the relationship between EFTOC and the octanol-water equilibrium partitioning coefficient (KOW). Contaminant distribution appeared to be highly unsteady, with pedogenic/biogeochemical drivers controlling contaminant mobility in organic layers and leaching controlling accumulation in mineral layers. Lighter PCBs displayed higher mobility in all forest types primarily controlled by leaching and, to a minor extent, diffusion. Pedogenic processes controlling the formation of soil horizons were found to be crucial drivers of PAHs and heavier PCBs distribution. All contaminants appeared to be more mobile in the soil of the broadleaved plot, followed by mixed canopy and spruce forest. Increasing proportion of deciduous broadleaf species in the forest can thus lead to faster degradation or the faster leaching of PAHs and PCBs. The composition of humic substances was found to be a better descriptor of contaminant concentration than TOC.