Antioxidant capacity sources of soils under different land uses.

Antioxidants (AOX) in soils originate mainly from secondary plant metabolites and are pivotal in many redox processes in environment, maintaining soil quality. Still, little is known about the influence of land uses on their accumulation in soil. The aim of the paper was to determine the content of these redox-active compounds in the extracts of A horizons of abandoned fallows, arable and woodland soils. Total antioxidant capacity (TAC) of soils under various uses and vegetation was evaluated in different soil extracts using Folin-Ciocâlteu method. The contribution of humic acids to TAC was determined and antioxidant profiles estimated using the chromatographic GC-MS method. Forest soils exhibited the highest TAC (15.5 mg g-1) and AOX contents (4.34 mg g-1), which were positively correlated with soil organic carbon content. It was estimated that humic acids contribute to over 50% of TAC in soils. The main phenolics in woodland A horizons were isovanillic and p-hydroxybenzoic acid (p-HA), while esculetin and p-HA predominated in the abandoned fallows due to the prevalence of herbaceous vegetation. Cultivated soils were the most abundant in p-HA (56.42%). In the studied topsoils, there were considerable amounts of aliphatic organic matter, which role in redox processes should be further evaluated.

Biochar and Organic Fertilizer Co-Application Enhances Soil Carbon Priming, Increasing CO2 Fluxes in Two Contrasting Arable Soils.

Biochar soil amendments, along with non-tillage agriculture, are often proposed as a strategy for carbon sequestration. It is still questionable how the quality of biochar might influence the priming effect on soil organic matter and whether the addition of unprocessed organic amendments will affect biochar stability. In the study, six different biochars and three exogenous organic matter sources were added to two distinct arable soils. CO2 emission was monitored for 100 days of incubation and CO2 flux was estimated. Results showed that biochar increased soil CO2 fluxes. The highest peaks, up to 162 µg C-CO2 h-1 100 g-1, were recorded in treatments with food waste biochars, suggesting that they serve as a source of easily available carbon to soil microbes. Co-application of raw organic materials (manure and fresh clover biomass) enhanced CO2 emission and carbon losses, especially in sandy soil, where 0.85-1.1% of total carbon was lost in the short-term experiment. Biochar properties and content of labile C can stimulate CO2 emission; however, in a long-term period, this contribution is negligible. The findings of our study showed that more attention should be paid to priming effects caused by the addition of exogenous organic matter when applied to biochar-amended soils.

The Interaction of Pesticides with Humin Fractions and Their Potential Impact on Non-Extractable Residue Formation.

The constant influx of pesticides into soils is a key environmental issue in terms of their potential retention in the soil, thus reducing their negative impact on the environment. Soil organic matter (SOM) is an important factor influencing the environmental fate of these substances. Therefore, the aim of this research was to assess the chemical behavior of pesticides (flufenacet, pendimethalin, α-cypermethrin, metazachlor, acetamiprid) toward stable soil humin fractions (HNs) as a main factor affecting the formation of non-extractable residues of agrochemicals in soil. This research was conducted as a batch experiment according to OECD Guideline 106. For this purpose, HNs were isolated from eight soils with different physicochemical properties (clay content = 16-47%, pHKCl = 5.6-7.7, TOC = 13.3-49.7 g·kg-1, TN = 1.06-2.90 g·kg-1, TOC/TN = 11.4-13.7) to reflect the various processes of their formation. The extraction was carried out through the sequential separation of humic acids with 0.1 M NaOH, and then the digestion of the remaining mineral fraction with 10% HF/HCl. The pesticide concentrations were detected using GC-MS/MS. The pesticides were characterized based on the different sorption rates to HNs, according to the overall trend: metazachlor (95% of absorbed compound) > acetamiprid (94% of absorbed compound) > cypermethrin (63% of partitioning compound) > flufenacet (39% of partitioning compound) > pendimethalin (28% of partitioning compound). Cypermethrin and metazachlor exhibited the highest saturation dynamic, while the other agrochemicals were much more slowly attracted by the HNs. The obtained sorption kinetic data were congruous to the pseudo-first-order and pseudo-second-order models related to the surface adsorption and interparticle diffusion isotherm. The conducted research showed that the processes of pesticide sorption, apart from physicochemical phenomena, are also affected by the properties of the pollutants themselves (polarity, KOC) and the soil properties (SOM content, clay content, and pHKCl).

Soil Organic Matter Composition and pH as Factors Affecting Retention of Carbaryl, Carbofuran and Metolachlor in Soil.

The majority of studies concerning the environmental behavior of hydrophobic pollutants in soil consider soil organic matter (SOM) content as a main factor influencing chemical retention, whereas the composition of SOM and its individual fraction share are often neglected. In the present paper, carbaryl, carbofuran and metolachlor retention by loamy sand and loam topsoil materials is compared and referred to humic acids (CHA) and the residual carbon (CR) content of SOM. Additionally, the sorption-desorption behavior of agrochemicals in soils was tested at a pH of three to seven. Calculated isothermal parameters point to favorable, spontaneous and physical pesticide sorption. Groundwater ubiquity score (GUS) indexes confirmed the low leaching ability of metolachlor on soils and moderate of carbofuran. The high affinity of carbaryl to CR may explain its pronounced sorption in loam soil and the lowest percolation potential. Carbofuran retention in soils was associated with montmorillonite (Mt) and CR fractions. Meanwhile, metolachlor uptake was related to humic acid and Mt content of the soils. Lower pH enhanced retention of the agrochemicals, except for carbaryl sorption in sandy loam soil. Results of this study highlight that SOM composition and mutual share of individual organic carbon fractions alongside pH may play a crucial role in predicting non-ionic pesticide behavior in soil.

Aging of biodegradable-mulch-derived microplastics reduces their sorption capacity of atrazine.

Degradable plastics are gradually regarded as alternatives of conventional, synthetic organic polymers to reduce the plastics or microplastics (MPs) pollution; however, the reports upon environmental risk of degradable plastics are still limited. In order to evaluate the potential vector effect of biodegradable MPs on coexisting contaminants, sorption of atrazine onto pristine and ultraviolet-aged (UV) polybutylene adipate co-terephthalate (PBAT) MPs and polybutylene succinate co-terephthalate (PBST) MPs were investigated. The results showed that, UV aging led to more wrinkles and cracks on the surface, increased homogeneous chains proportion, enhanced hydrophobicity, and enlarged crystallinity of both MPs. The sorption kinetics of atrazine to MPs fitted well into pseudo-first-order (R2 = 0.809-0.996) and pseudo-second-order (R2 = 0.889-0.994) models. In the concentration range of 0.5-25 mg L-1, the sorption isotherm fitted into linear (R2 = 0.967-0.996) and Freundlich model (R2 = 0.972-0.997), indicating that the absorption partitioning was the dominant sorption mechanism. The partition coefficient (Kd) of atrazine to PBAT- MPs (40.11-66.01 L kg-1) was higher than that of PBST- MPs (34.34-57.96 L kg-1), and the Kd values of both MPs declined for aged MPs. The specific surface area, hydrophobicity, polarity and crystallinity of MPs jointly interpreted the changing sorption capacity of the MPs. In the present study, both aged PBAT- and aged PBST- MPs exhibited lower vector potential to atrazine than pristine MPs, suggesting reduced risk of being a pollutant carrier, which is of great significance for the development of biodegradable plastics.

Deashed Wheat-Straw Biochar as a Potential Superabsorbent for Pesticides.

Biochar activation methods have attracted extensive attention due to their great role in improving sorptive properties of carbon-based materials. As a result, chemically modified biochars gained application potential in the purification of soil and water from xenobiotics. This paper describes changes in selected physicochemical properties of high-temperature wheat-straw biochar (BC) upon its deashing. On the pristine and chemically activated biochar (BCd) retention of five pesticides of endocrine disrupting activity (carbaryl, carbofuran, 2,4-D, MCPA and metolachlor) was studied. Deashing resulted in increased sorbent aromaticity and abundance in surface hydroxyl groups. BCd exhibited more developed meso- and microporosity and nearly triple the surface area of BC. Hydrophobic pesticides (metolachlor and carbamates) displayed comparably high (88-98%) and irreversible adsorption on both BCs, due to the pore filling, whereas the hydrophilic and ionic phenoxyacetic acids were weakly and reversibly sorbed on BC (7.3 and 39% of 2,4-D and MCPA dose introduced). Their removal from solution and hence retention on the deashed biochar was nearly total, due to the increased sorbent surface area and interactions of the agrochemicals with unclogged OH groups. The modified biochar has the potential to serve as a superabsorbent, immobilizing organic pollutant of diverse hydrophobicity from water and soil solution.

Optimized isolation method of humin fraction from mineral soil material.

Humic substances, including humin fraction, play a key role in the fate of organic and inorganic xenobiotics contaminating the environment. Humin is an important fraction of humic substances, which has been the least studied to date. This is due to the difficulties connected with its isolation that pose a number of methodological problems. Methods of humin fraction isolation can be divided into following main groups: (1) digestion of mineral soil components with HF/HCl followed by alkali extraction of HA and FA; (2) alkali extraction of HA and FA followed by extraction of humin by different organic solvents; and (3) alkali extraction of HA and FA followed by HF/HCl digestion of mineral soil components. Nevertheless, each of these methods has different limitations. We described in detail a useful procedure of humin isolation, in which this fraction was not extracted, but isolated from the soil by removing its soluble organic and mineral components. A modified method of HA and FA extraction with 0.1 M NaOH, according to the International Humic Substances Society, was used in the first step. Then, the mineral components in the residue were digested with the 10% HF/HCl. Unlike the procedures oriented to increase the concentration of organic matter, samples were treated several times with the HF/HCl mixture until the mineral fraction was almost completely digested. The main assumption of the method modification was to obtain the highest yield with the lowest possible ash content, but without affecting humin chemical structure. The results showed that the proposed procedure is characterized by a high efficiency and recovery and, therefore, it can be used to isolate high amounts of humin from soil.

The contribution of water extractable forms of plant nutrients to evaluate MSW compost maturity: a case study.

The object of the experiment was to evaluate municipal solid waste (MSW) compost. Composting was carried out in a pile under aerobic conditions. Total content as well as water-extractable forms of macro and microelements were analysed during composting. Nutrient solubility indices were calculated for samples taken at various stages of maturity. The soluble forms of C, P, K, Ca and Mg decreased relatively to their total forms following maturation phases. For all micronutrients tested, a significant reduction in the proportion of soluble forms in relation to their total content was observed with an increase in composting time. In mature compost, low solubility were found for nitrogen, potassium, sodium and magnesium, which may indicate that the final product is a good source of these nutrients. The solubility index (percentage share of water-extractable forms of macro- and micronutrients in the total content) for iron indicates that the composting process does not affect its degree of solubility. Solubility index instead of the content of water-extractable forms of chosen macro- and microelements could be taken into account in determining the degree of MSW compost maturity.

Wheat Straw Biochar as a Specific Sorbent of Cobalt in Soil.

There is an urgent need to search for new sorbents of pollutants presently delivered to the environment. Recently biochar has received much attention as a low-cost, highly effective heavy metal adsorbent. Biochar has been identified as an efficient material for cobalt (Co) immobilization from waters; however, little is known about the role of Co immobilization in soil. Hence, in this study, a batch experiment and a long-term incubation experiment with biochar application to multi-contaminated soil with distinct properties (sand, loam) were conducted to provide a brief explanation of the potential mechanisms of Co (II) sorption on wheat straw biochar and to describe additional processes that modify material efficiency for metal sorption in soil. The soil treatments with 5% (v/w) wheat straw biochar proved to be efficient in reducing Co mobility and bioavailability. The mechanism of these processes could be related to direct and indirect effects of biochar incorporation into soil. The FT-IR analysis confirmed that hydroxyl and carboxyl groups present on the biochar surface played a dominant role in Co (II) surface complexation. The combined effect of pH, metal complexation capacity, and the presence of Fe and Mn oxides added to wheat straw biochar resulted in an effective reduction of soluble Co (II), showing high efficiency of this material for cobalt sorption in contaminated soils.

1,2,3-propanetriol radicals formed during oxidative stress.

The presented results attempt to approximate the proper structure of the radical formed as a result of the oxidation of 1,2,3-propanetriol. To fulfil the aim unstable radical originated in 1,2,3-propanetriol was trapped by PBN. Resulted spin adduct was measured using EPR spectroscopy and the isotropic hyperfine coupling constants aiso (14 N) and aiso (1 H) were obtained by simulation of the EPR spectrum. The next step consisted of conducting a comparative analysis of EPR parameters, based on the calculations conducted at the DFT and MP2 methods level in open-shell formalism including solvent effects. For comparison, calculations were also carried out at the level of combined methods (UB3LYP/QCISD and UMP2/QCISD) in terms of the ONIOM formalism. Comparison of the experimental EPR data of the isotropic hyperfine coupling constants aiso (14 N) and aiso (1 H) with the calculated parameters indicate that oxidation of 1,2,3-propanetriol leads to a carbon centred radical where unpaired electron is situated on the second (middle) carbon of 1,2,3-propanetriol. What is important, this conclusion could be made regardless of the chosen calculation method. However, it could be stated that for calculation of the isotropic hyperfine coupling constants aiso (14 N) and aiso (1 H) of PBN/gly• adducts, UMP2 polarisable conductor calculation model with two ethanol molecules is explicitly defined.

Can Carbamates Undergo Radical Oxidation in the Soil Environment? A Case Study on Carbaryl and Carbofuran.

Radical oxidation of carbamate insecticides, namely carbaryl and carbofuran, was investigated with spectroscopic (electron paramagnetic resonance [EPR] and UV-vis) and theoretical (density functional theory [DFT] and ab initio orbital-optimized spin-component scaled MP2 [OO-SCS-MP2]) methods. The two carbamates were subjected to reaction with •OH, persistent DPPH• and galvinoxyl radical, as well as indigenous radicals of humic acids. The influence of fulvic acids on carbamate oxidation was also tested. The results obtained with EPR and UV-vis spectroscopy indicate that carbamates can undergo direct reactions with various radical species, oxidizing themselves into radicals in the process. Hence, they are prone to participate in the prolongation step of the radical chain reactions occurring in the soil environment. Theoretical calculations revealed that from the thermodynamic point of view hydrogen atom transfer is the preferred mechanism in the reactions of the two carbamates with the radicals. The activity of carbofuran was determined experimentally (using pseudo-first-order kinetics) and theoretically to be noticeably higher in comparison with carbaryl and comparable with gallic acid. The findings of this study suggest that the radicals present in soil can play an important role in natural remediation mechanisms of carbamates.

Pro- and Antioxidative Effect of α-Tocopherol on Edible Oils, Triglycerides and Fatty Acids.

Using advanced electron paramagnetic resonance techniques (EPR), oxidation of crude vegetable oils and their components (fatty acids and triglycerides) by radicals generated from hydrogen peroxide was investigated. The correlation rotational times were determined allowing us to characterize radicals formed during edible oils oxidation. Additionally 1H- and 14N-hyperfine coupling constants differentiate the fatty acids dependently on their unsaturation. The acids with a higher number of unsaturated bonds exhibit higher AN values of PBN/·lipid adduct. The waste oil with high free fatty acids content underwent the oxidation reaction more efficiently, however due to saturation and the high content of the fatty acids the carbon-centered radicals formed (upon hydrogen peroxide radicals) and their PBN (N-tert-butyl-α-phenylnitrone) adducts were less stable. The antioxidant effect was dependent on the amount of α-tocopherol added. In small amounts of up to 0.35 mg/1 g of fatty acid or triglyceride, it inhibited the creation of PBN/·lipid adducts while with higher amounts it intensified adduct formation. The α-tocopherol (AT) addition influence was also studied as spin scavenging dependence and indicated that any addition of the antioxidant in the investigated samples led to free radical scavenging and the effect increased with the increase in AT content.