Biochar is a pyrogenous, organic material synthesized through pyrolysis of different biomass (plant or animal waste). The potential biochar applications include: (1) pollution remediation due to high CEC and specific surface area; (2) soil fertility improvement on the way of liming effect, enrichment in volatile matter and increase of pore volume, (3) carbon sequestration due to carbon and ash content, etc. Biochar properties are affected by several technological parameters, mainly pyrolysis temperature and feedstock kind, which differentiation can lead to products with a wide range of values of pH, specific surface area, pore volume, CEC, volatile matter, ash and carbon content. High pyrolysis temperature promotes the production of biochar with a strongly developed specific surface area, high porosity, pH as well as content of ash and carbon, but with low values of CEC and content of volatile matter. This is most likely due to significant degree of organic matter decomposition. Biochars produced from animal litter and solid waste feedstocks exhibit lower surface areas, carbon content, volatile matter and high CEC compared to biochars produced from crop residue and wood biomass, even at higher pyrolysis temperatures. The reason for this difference is considerable variation in lignin and cellulose content as well as in moisture content of biomass. The physicochemical properties of biochar determine application of this biomaterial as an additive to improve soil quality. This review succinctly presents the impact of pyrolysis temperature and the type of biomass on the physicochemical characteristics of biochar and its impact on soil fertility.

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 β-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 β-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 β-sites; stability increased with humification decrease for γ-structures. The stability of complexes at α and β-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.

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The main aim of the study was to examine the biochar efficiency in copper (Cu) ion removal from Haplic (Luvisol, Podzol) soils. In other words, the most effective biochar dose and the most favorable environment pH value were proposed. The copper removal was carried out based on the adsorption process. The results of kinetics measurements were modeled using Richie equation, whereas the adsorption isotherms using Langmuir-Freundlich and Dubinin-Radushkevich equations. The copper removal is a strongly pH-dependent process which is associated with variability of chemical Cu forms and various reactivities of organic molecules. The Cu adsorption amount was higher on silty Haplic Luvisol than on sandy Haplic Podzol mainly due to higher content of organic carbon, functional groups, clay and silt fractions as well as larger surface area. Moreover, the biochar addition increased linearly the soil surface charge and contributed to higher copper adsorption in the whole range of investigated ion concentrations. The higher the biochar dose added, the more Cu ions were adsorbed.

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.

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.