Chemical Transformation of Humic Acid Molecules under the Influence of Mineral, Fungal and Bacterial Fertilization in the Context of the Agricultural Use of Degraded Soils.

The main goal of this work was to study the structural transformation of humic acids (HAs) under the influence of selected strains of fungi (Aspergillus niger and Paecilomyces lilacinus) and bacteria (Bacillus sp., Paenibacillus polymyxa and Bacillus amyloliquefaciens) with/without the presence of NPK fertilizers. Two-year experiments were conducted on two different soils and HAs isolated from these soils were examined for structure, humification degree, and quantity using fluorescence and UV-Vis spectroscopy, elemental analysis, and extraction methods. Results showed that the applied additives contributed to the beneficial transformation of HAs, but effects differed for various soils. HAs from silty soil with higher organic carbon content showed simplification of their structure, and decreases in humification, molecular weight, and aromaticity under the influence of fungi and bacteria without NPK, and with NPK alone. With both fungi and NPK, increases in O/H and O/C atomic ratios indicated an increase in the number of O-containing functional groups. HAs from sandy soil did not show as many significant changes as did those from silty soil. Sandy soil exhibited a strong decline in HA content in the second year that was reduced/neutralized by the presence of fungi, bacteria, and NPK. Periodically observed fluorescence at ~300 nm/450 nm reflected formation of low-molecular HAs originating from the activity of microorganisms.

Comparison of Monovalent and Divalent Ions Removal from Aqueous Solutions Using Agricultural Waste Biochars Prepared at Different Temperatures-Experimental and Model Study.

Copper (Cu) and silver (Ag) occur naturally in the environment but have toxic effects on organisms at elevated concentrations. This paper discussed the removal of Cu and Ag from aqueous solutions using biochars obtained at different pyrolysis temperatures. Three biomass sources-sunflower husks (SH), a mixture of sunflower husks and rapeseed pomace (SR) and wood waste (WW)-were pyrolyzed at 300, 400 and 500 °C. Biochars produced at 500 °C exhibited a higher specific surface area, lower variable surface charge and lower contents of surface functional groups than those obtained at 400 or 300 °C. The pseudo-second-order model and intra-particle diffusion (IPD) model well-described the Cu and Ag adsorption kinetics. The Cu adsorption was about 1.48 times slower than the Ag adsorption on the biochars obtained at 500 °C. The model of Langmuir-Freundlich well-described the equilibrium adsorption. Agricultural biochars obtained at >500 °C had a surface with a higher affinity to attract Ag than Cu and were able to remove a larger amount of heavy metals from aqueous media than those prepared at lower pyrolysis temperatures.

Zinc Binding to Fulvic acids: Assessing the Impact of pH, Metal Concentrations and Chemical Properties of Fulvic Acids on the Mechanism and Stability of Formed Soluble Complexes.

The aim of the study was defined as a complementary analysis of molecular interactions between zinc (Zn) and fulvic acids (FAs) at a broad pH range (3-7), different metal concentrations (0-50 mg dm-3) and chemical properties of FAs and their impact on the Zn binding mechanism, stability, and efficiency. The results showed that the complexation reaction prevailed at pH 6 and 7, whereas protons exchange dominated interactions at pH 3. Stability constant of the complexes increased along with pH (logK increased from ~3.8 to 4.2). Complexation was preferred by less-humidified structures of lower molecular mass containing more oxygen groups. The number of fluorophores available for Zn(II) increased from pH 3 to 7 by ~44%. Depending on the pH, complexation involved a bidentate chelate, monodentate and bidentate bridging mode. Zn(II) binding was insufficiently modeled by the classic Stern-Volmer equation and well described by the double logarithmic equation (R > 0.94) as well as by a modified Stern-Volmer formula assuming the existence of available and unavailable fluorophore populations (R > 0.98). The fluorescence ratio of different fluorophores was proposed as an indicator of the binding affinity of various structures. A positive relationship was found between the fraction of accessible fluorophores and Zn(II) binding at pH 7 determined based on proton release (R = 0.91-0.97). The obtained results can find application in controlling the mobility and bioavailability of Zn in different conditions.

Purification of Aqueous Media by Biochars: Feedstock Type Effect on Silver Nanoparticles Removal.

Due to the harmful effects of nanoparticles in the environment, their effective removal from aqueous media is of great importance. This paper described the research on the silver nanoparticles (Ag-NPs) sorption on biochars obtained from different feedstock types. The sorbents were produced through pyrolysis (double-barrel method) of the vineyard (BV), paulownia tree (BP), and tobacco (BT). BV exhibited the highest specific surface area, porosity, value of variable surface charge, and content of surface acidic functional groups among the used biochars. The pseudo-second order model best described the obtained adsorption kinetics, whereas the Freundlich model accounted for the registered adsorption data. The Ag-NPs removal was highly efficient in the case of BV, especially in the nanoparticle concentration range 50-500 mg/L. Thus, this biochar can be considered as an ecofriendly, effective, low-cost organic adsorbent, potentially used in the aqueous media purification.

Insight into the interaction mechanism of iron ions with soil humic acids. The effect of the pH and chemical properties of humic acids.

The main aim of this work was to study the mechanisms of interaction between iron(II) ions and humic acids as a function of pH, iron concentration and various humic acids chemical properties, including the degree of humification, elemental composition, aromaticity and content of acidic functional groups. The results indicated that iron was bound by humic acids at pH 7 in amounts ∼2 times higher than at pH 5 (averaged capacities: 117 and 57 cmol/kg, respectively). Iron binding at pH 7 increased with increasing the total carboxylic and phenolic groups content and the degree of humification of humic acids (R-coefficients: 0.99 and 0.95, respectively). The stability of humic acid-iron complexes at pH 7 were only slightly lower than at pH 5 due to iron hydroxides formed at pH > 5 (averaged stability constants: 5.18 and 5.26, respectively). Iron coordination mode varied depending on pH: at pH 5, the bidentate (chelate) mode dominated, whereas at pH 7 the bridging mode appeared prevalent. The total amount of bound iron was much smaller than the content of the carboxylic and phenolic groups in humic acids, on average by ∼80 (pH 7) and ∼90.1% (pH 5) indicating the occurrence of steric effects in humic acid structure i.e. the reduction of the complexation capacity of free functional groups by adjacent groups occupied by iron and/or the formation of intramolecular aggregates with iron hindering the access of further metal ions. At pH 5 the complexes were soluble in the iron concentration range positively correlated to carboxylic and phenolic groups content, showing the protective nature of negatively charged functional groups on the stability of the solution. At this pH, the destabilization of the system was governed by the neutralization of humic acid charged structures by metal cations and the compression of the double electric layer. At pH 7 the stability of the humic acid-iron solution was largely determined by the form of iron, mainly by the precipitation of metal hydroxides acting as a flocculant destabilizing the solution by co-precipitation of humic acid-iron complexes.

A Comparative Study of the Application of Fluorescence Excitation-Emission Matrices Combined with Parallel Factor Analysis and Nonnegative Matrix Factorization in the Analysis of Zn Complexation by Humic Acids.

The main aim of this study was the application of excitation-emission fluorescence matrices (EEMs) combined with two decomposition methods: parallel factor analysis (PARAFAC) and nonnegative matrix factorization (NMF) to study the interaction mechanisms between humic acids (HAs) and Zn(II) over a wide concentration range (0-50 mg·dm-3). The influence of HA properties on Zn(II) complexation was also investigated. Stability constants, quenching degree and complexation capacity were estimated for binding sites found in raw EEM, EEM-PARAFAC and EEM-NMF data using mathematical models. A combination of EEM fluorescence analysis with one of the proposed decomposition methods enabled separation of overlapping binding sites and yielded more accurate calculations of the binding parameters. PARAFAC and NMF processing allowed finding binding sites invisible in a few raw EEM datasets as well as finding totally new maxima attributed to structures of the lowest humification. Decomposed data showed an increase in Zn complexation with an increase in humification, aromaticity and molecular weight of HAs. EEM-PARAFAC analysis also revealed that the most stable compounds were formed by structures containing the highest amounts of nitrogen. The content of oxygen-functional groups did not influence the binding parameters, mainly due to fact of higher competition of metal cation with protons. EEM spectra coupled with NMF and especially PARAFAC processing gave more adequate assessments of interactions as compared to raw EEM data and should be especially recommended for modeling of complexation processes where the fluorescence intensities (FI) changes are weak or where the processes are interfered with by the presence of other fluorophores.

The influence of biochar on the content of carbon and the chemical transformations of fallow and grassland humic acids.

There is limited information regarding the effect of biochar (BioC) on the fertility of fallow and grassland soils, as well as on the properties of their humic acids (HAs). The objective of this study was to evaluate with a 3-year field experiment the influence of BioC on the organic matter (OM) in Haplic Luvisol. BioC (obtained via wood waste pyrolysis at 650 °C) was applied to the soil of subplots under fallow and grassland at doses of 0, 1, 2 and 3 kg m-2. The soil samples were collected eight times. The physicochemical properties were determined for the soil and BioC by analysing the density, pH, surface charge, ash, and organic carbon content. Based on the changes in the structure of the HAs and their quantity in the soils, the chemical properties of the HAs were determined. The maximum BioC dose caused an increase in the content of Corg and HAs. BioC did not influence the humification degree coefficients of the HAs originated from fallow, whereas in the grassland, there were significant changes observed in these coefficient values, indicating that BioC may stimulate and accelerate the humification process of soil HAs. Increasing the BioC doses caused an increase in the soil's HA content, suggesting an increase in soil sorption capacity. The fluorescence data showed BioC addition to the soil caused an increase in the number of structures characterised by low molecular weight and a low degree of humification.

Carboxin and Diuron Adsorption Mechanism on Sunflower Husks Biochar and Goethite in the Single/Mixed Pesticide Solutions.

The study focused on the adsorption mechanism of two selected pesticides: carboxin and diuron, on goethite and biochar, which were treated as potential compounds of mixed adsorbent. The authors also prepared a simple mixture of goethite and biochar and performed adsorption measurements on this material. The adsorbents were characterized by several methods, inter alia, nitrogen adsorption/desorption, Boehm titration, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The adsorption study included kinetics and equilibrium measurements, in the solution containing one or two pesticides simultaneously. The adsorption data were fitted to selected theoretical models (e.g., Langmuir, Freudlich, Redlich-Peterson, pseudo first-order and pseudo second-order equations). Based on the obtained results, it was stated that, among all tested adsorbents, biochar had the highest adsorption capacity relative to both carboxin and diuron. It equaled 0.64 and 0.52 mg/g, respectively. Experimental data were best fitted to the pseudo second-order and Redlich-Peterson models. In the mixed systems, the adsorption levels observed on biochar, goethite and their mixture were higher for diuron and lower for carboxin, compared to those noted in the single solutions. The presented results may enable the development of new mixed adsorbent for remediation of soils polluted with pesticides.

The effect of application of digestate and agro-food industry sludges on Dystric Cambisol porosity.

The spatial arrangement and pore size distribution play an important role in accumulation and protection of exogenous organic matter (EOM) in the soil, but how different organic materials contribute to modify pore structure is poorly understood. We aimed at exploring possible changes in the complexity of the soil phase during fertilization with different doses of digestate and sludges sourced from the agro-food industry. For this purpose, the short-term effects-one year, of soil fertilization, were investigated in several sampling periods and within two depths (0-25 cm and 25-40 cm). Changes in the specific surface area (SSA), total pore volume (VMIP), total pore area (SMIP), average pore radius (RMIP) and pore size distribution (PSD) were monitored using N2 adsorption/desorption (NAD) and mercury porosimetry (MIP) methods. Our results showed that the intensity of observed changes depended on the type and dose of organic material, soil depth and sampling date. Accumulation of EOM increased with soil depth, masking a large proportion of SSA. Deeper soil layer was more susceptible to changes in the pore size distributions due to the formation of new elongated pores. We concluded that this specific structural porosity was related to the decomposition of organic matter during the formation of soil aggregates.

Study on Adsorption and Aggregation in the Mixed System of Polyacrylamide, Cu(II) Ions and Innovative Carbon-Silica Composite.

The paper presents an original study on adsorption and aggregation phenomena in a mixed system consisting of a macromolecular compound, heavy metal ions and an innovative adsorbent. The authors used ionic polyacrylamides (PAM), Cu(II) ions and carbon-silica composite (C-SiO2) in the experiments. Such a system has not yet been described in the literature and therefore, the article is of significant novelty and great importance. The composite was prepared by mixing phenol-formaldehyde resin with silica and pyrolysis at 800 °C. The adsorbed amounts of Cu(II) ions and PAM were determined spectrophotometrically. C-SiO2 was characterized using potentiometric titration, microelecrophoresis and Fourier Transform Infrared Spectroscopy (FTIR) analysis. In turn, the C-SiO2 aggregation was established turbidimetrically as well as using a particle size analyzer. The obtained results indicated that both Cu(II) ions and ionic polyacrylamide were adsorbed on the composite surface at pH 6. The highest noted adsorbed amounts were 9.8 mg/g for Cu(II) and 35.72 mg/g for CT PAM-25%. Cu(II) ions increased the anionic PAM adsorbed and reduced the cationic PAM one. The adsorption of anionic PAM (50 ppm) stimulated the solid aggregation significantly. What is more, Cu(II) ions enhanced this process. The size of particles/aggregates formed without additives equaled 0.44 µm, whereas in the mixed Cu(II)/AN PAM system, they were even at 1.04 µm.

Hay-based activated biochars obtained using two different heating methods as effective low-cost sorbents: Solid surface characteristics, adsorptive properties and aggregation in the mixed Cu(II)/PAM system.

The main aim of the study was to compare the sorption capacity of hay-based activated biochars, obtained using conventional and microwave furnance, relative to copper(II) ions and ionic polyacrylamides (PAM). Surface properties of the solids were characterized by, inter alia, N2 adsorption/desorption isotherm method, whereas their tendency to aggregation was established turbidimetrically. Adsorption capacity of biochars were performed in the simple and mixed Cu(II)/PAM systems, i.e. the examined suspensions contained one or two adsorbates at the same time. The results indicated that biochar prepared in microwave furnance was characterized by larger micropore area and, as a result, it had higher adsorption capacity relative to Cu(II) ions. At pH 6, when the initial Cu(II) concentration equaled 100 mg/L, the biochar obtained by microwave heating adsorbed 81.5% of Cu(II) ions, whereas the one obtained by conventional heating - 51.6%. Due to high molecular weight, the PAM macromolecules could not penetrate the biochar micropores and thus the polymer adsorbed amounts were similar for both materials. For initial polymer concentration equal to 100 mg/L, the solids adsorbed 65-66.2% of cationic PAM containing 25% of quaternary amine groups. In the mixed system of anionic polyacrylamide and Cu(II) ions, the formation of Cu(II)-PAM complexes occurred, which favored both heavy metal and polymer adsorption on the solid surface. On the other hand, cationic polyacrylamide and heavy metal ions made the contact with the solid difficult for each other. What is more, ionic polyacrylamide and copper(II) ions stimulated the biochar aggregation due to surface charge neutralization and flocculation.

Solvation force between surfaces modified by tethered chains: a density functional approach.

The behavior of Lennard-Jones fluid in slitlike pores with walls modified by tethered chain molecules is studied using density functional theory. The effects of confinement and chemical modification of pore walls on the solvation force are investigated. Two models of the pore walls are considered. According to the first model, the chain molecules are chemically bonded by their end segments to opposite walls of the pore, forming flexible pillars. In the second model the chains build up a brush at each wall due to bonding of the first segment at one wall. The nonbonded terminating segment of a molecule is strongly attracted via a short-range potential to any wall of the pore. Then a pillarlike or looplike structure of chains can be formed. In the first model the solvation force at the wall-to-wall is repulsive for narrow pores and strongly attractive for wider pores of the order of the nominal chain length. Oscillations of the solvation force are induced by adsorbed fluid structure and by ordered structure of segments on the fragment of entirely attractive force curve. In the second model, however, the solvation force decays to zero as the pore width increases. Attractive force can be induced at intermediate separation between walls due to modification of the pore walls.

Use of thermal analysis coupled with differential scanning calorimetry, quadrupole mass spectrometry and infrared spectroscopy (TG-DSC-QMS-FTIR) to monitor chemical properties and thermal stability of fulvic and humic acids.

Thermogravimetry-coupled with differential scanning calorimetry, quadrupole mass spectrometry, and Fourier-transform infrared spectroscopy (TG-DSC-QMS-FTIR)-was applied to monitor the thermal stability (in an N2 pyrolytic atmosphere) and chemical properties of natural polymers, fulvic (FA) and humic acids (HA), isolated from chemically different soils. Three temperature ranges, R1, 40-220°C; R2, 220-430°C; and R3, 430-650°C, were distinguished from the DSC data, related to the main thermal processes of different structures (including transformations without weight loss). Weight loss (ΔM) estimated from TG curves at the above temperature intervals revealed distinct differences within the samples in the content of physically adsorbed water (at R1), volatile and labile functional groups (at R2) as well as recalcitrant and refractory structures (at R3). QMS and FTIR modules enabled the chemical identification (by masses and by functional groups, respectively) of gaseous species evolved during thermal decomposition at R1, R2 and R3. Variability in shape, area and temperature of TG, DSC, QMS and FTIR peaks revealed differences in thermal stability and chemical structure of the samples between the FAs and HAs fractions of different origin. The statistical analysis showed that the parameters calculated from QMS (areas of m/z = 16, 17, 18, 44), DSC (MaxDSC) and TG (ΔM) at R1, R2 and R3 correlated with selected chemical properties of the samples, such as N, O and COOH content as well as E2/E6 and E2/E4 indexes. This indicated a high potential for the coupled method to monitor the chemical changes of humic substances. A new humification parameter, HTD, based on simple calculations of weight loss at specific temperature intervals proved to be a good alternative to indexes obtained from other methods. The above findings showed that the TG-DSC-QMS-FTIR coupled technique can represent a useful tool for the comprehensive assessment of FAs and HAs properties related to their various origin.

Interactions of Zn(II) Ions with Humic Acids Isolated from Various Type of Soils. Effect of pH, Zn Concentrations and Humic Acids Chemical Properties.

The main aim of this study was the analysis of the interaction between humic acids (HAs) from different soils and Zn(II) ions at wide concentration ranges and at two different pHs, 5 and 7, by using fluorescence and FTIR spectroscopy, as well as potentiometric measurements. The presence of a few areas of HAs structures responsible for Zn(II) complexing was revealed. Complexation at α-sites (low humified structures of low-molecular weight and aromatic polycondensation) and ß-sites (weakly humified structures) was stronger at pH 7 than 5. This trend was not observed for γ-sites (structures with linearly-condensed aromatic rings, unsaturated bonds and large molecular weight). The amount of metal complexed at pH5 and 7 by α and γ-structures increased with a decrease in humification and aromaticity of HAs, contrary to ß-areas where complexation increased with increasing content of carboxylic groups. The stability of complexes was higher at pH 7 and was the highest for γ-structures. At pH 5, stability decreased with C/N increase for α-areas and -COOH content increase for ß-sites; stability increased with humification decrease for γ-structures. The stability of complexes at α and ß-areas at pH 7 decreased with a drop in HAs humification. FTIR spectra at pH 5 revealed that the most-humified HAs tended to cause bidentate bridging coordination, while in the case of the least-humified HAs, Zn caused bidentate bridging coordination at low Zn additions and bidentate chelation at the highest Zn concentrations. Low Zn doses at pH 7 caused formation of unidentate complexes while higher Zn doses caused bidentate bridging. Such processes were noticed for HAs characterized by high oxidation degree and high oxygen functional group content; where these were low, HAs displayed bidentate bridging or even bidentate chelation. To summarize, the above studies have showed significant impact of Zn concentration, pH and some properties of HAs on complexation reactions of humic acids with zinc.

Phase behavior of a binary symmetric mixture in slitlike pores with opposing walls: application of density functional approach.

We study adsorption of a symmetric binary Lennard-Jones mixture, which exhibits partial mixing in a bulk phase, in slitlike pores formed by the walls having antisymmetric properties with respect to the components. The calculations are carried out by means of a density functional approach. We show that under suitable conditions the pore filling may occur as a sequence of two first-order transitions. The capillary condensation may lead to an "antisymmetric" liquidlike film, the symmetry of which follows the symmetry of the adsorbing potential, or to a "demixed" film, the symmetry of which is only weakly associated with the symmetry of the adsorption potential. The additional first-order antisymmetric-demixed film transition begins at the triple point temperature and ends at the critical end point temperature.

Photosensitizing properties of water-extractable organic matter from soils.

Water-extractable organic matter (WEOM) was extracted using pure water from two black soils and from the Elliott reference soil of the International Humic Substances Society (IHSS). WEOMs were characterized by chemical and spectroscopic methods. The apparent quantum yields of singlet oxygen, triplet excited states and hydroxyl radicals formation upon irradiation within the wavelength range 290-450 nm were determined using chemical probes and compared to those of standard Elliott humic substances. In general, the aromatic content, as measured by the SUVA value, was close in WEOMs and humic substances, while the E2/E3 was higher and the humification index lower in the former. Quantum yield values measured for WEOMs fell within the range of those found for basic medium extracted humic substances or were even higher in one case. Thus, water soluble aromatic moiety of the soil organic matter, especially those with low humification degree, is important for the photosensitizing properties. We also found that WEOMs sensitized the bisphenol A phototransformation with rates of the same order of magnitude for all the samples.

Capillary Condensation in Pores with Energetically Heterogeneous Walls: Density Functional versus Monte Carlo Calculations.

We investigate adsorption of a Lennard-Jones fluid in slit-like pores with energetically heterogeneous walls by using Grand Canonical Monte Carlo simulations and a density functional approach. The model of a fluid-wall potential is qualitatively similar to that invoked by Röcken et al. (J. Chem. Phys. 108, 8089, (1999); i.e., it consists of a homogeneous part that varies in the direction perpendicular to the wall and a periodic part, varying also in one direction parallel to the wall, but in contrast to the above mentioned work, both parts of the fluid-wall potential are modeled by Lennard-Jones (9, 3) type functions. The structure of the adsorbed film is characterized by local densities. We evaluate the phase diagrams for several systems characterized by different corrugation of the adsorbing potential and discuss the discrepancies between theoretical predictions and computer simulations. Copyright 2001 Academic Press.