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Chitosan is a biodegradable polymer with a vast range of applications. Along with its metal composites, chitosan has been applied in the remediation of polluted soils as well as a biofertilizer. However, little attention has been given to the degradation of chitosan composites in soil and how they affect soil respiration rate and other physicochemical parameters. In this study, the degradation of chitosan and its composites with gibbsite and hematite in an acidic Ultisol and the effect on urea (200 mg N kg−1) transformation were investigated in a 70-d incubation experiment. The results showed that the change trends of soil pH, N forms, and CO 2 emissions were similar for chitosan and its composites when applied at rates <5 g C kg−1. At a rate of 5 g C kg−1, the C and N mineralization trends suggested that the chitosan-gibbsite composite was more stable in soil and this stability was owed to the formation of a new chemical bond (CH–N–Al-Gibb) as observed in the Fourier-transform infrared spectrum at 1644 cm−1. The mineralization of the added materials significantly increased soil pH and decreased soil exchangeable acidity (P < 0.01). This played an important role in decreasing the amount of H+ produced during urea transformation in the soil. The soil's initial pH was an important factor influencing C and N mineralization trends. For instance, increasing the initial soil pH significantly increased the nitrification rate and chitosan decomposition trend (P < 0.01) and thus, the contribution of chitosan and its composites to increase soil pH and inhibit soil acidification during urea transformation was significantly decreased (P < 0.01). These findings suggest that to achieve long-term effects of chitosan in soils, applying it as a chitosan-gibbsite complex is a better option. [Display omitted] • Chitosan increased soil pH and inhibited the activation of soil exchangeable aluminum. • Chitosan-gibbsite complex was more stable in soil than chitosan-hematite complex. • Chitosan-gibbsite stability is owed to the formation of CH–N –Al -Gibb bond. • Chitosan and its composites reduced soil nitrification during urea transformation in soil. [ABSTRACT FROM AUTHOR]

To develop more green, practical and efficient biochar amendments for acidic soils, chitosan-modified biochar (CRB) and alginate-modified biochar (ARB) were prepared, and their effects on promoting soil pH buffering capacity (pHBC) and immobilizing cadmium (Cd) in the paddy soils were investigated through indoor incubation experiments. The results of Fourier transform infrared spectroscopy and Boehm titration indicated that the introduction of chitosan and sodium alginate effectively amplified the functional groups of the biochar, and improved acid buffering capacity of the biochar. Since there was a plateau region between pH 4.5 and 5.5 in acid-base titration curve of the CRB, adding this biochar to acidic paddy soils apparently improved the pHBC and enhanced the acidification resistance of the paddy soils. The addition of ARB enhanced the reduction reactions during submerging and weakened the oxidation reactions during draining, thus retarded the decline of paddy soil pH during drainage. Furthermore, the pH of the paddy soils with ARB addition was higher at the end of draining, which reduced the activity of soil Cd. Considering the environmental sustainability of chitosan and sodium alginate and convenience of preparation method, biochars modified with these two materials provided alternatives for acidic paddy soil amelioration and heavy metal immobilization. However, the additional experiments should be conducted under field conditions to confirm practical application effects in the future. [Display omitted] • Chitosan and alginate effectively amplified the functional groups on biochar. • The two modified biochars were environmentally sustainable. • The preparation methods of the two modified biochars were convenient. • Chitosan-modified biochar had potential in acidic paddy soil amelioration. • Alginate-modified biochar had advantages in heavy metal immobilization. [ABSTRACT FROM AUTHOR]

Acidification in variable charge soils is on the rise due to increased acid deposition and use of nitrogenous fertilizers. The associated low pH and cation exchange capacity make the soils prone to depleted base cations and increased levels of Al3+. Consequently, Al toxicity to plants and soil infertility decrease crop yield. This study was designed to investigate the effect of Pseudomonas fluorescens on the acidification of two Ultisols. The simulated acidification experiment demonstrated that the pH of bacteria-treated soil was higher than that of control under similar conditions, suggesting that the adhered bacteria inhibited soil acidification. This observation was attributed to the association of organic anions (RCOO− or RO−) on bacteria with H+ to form neutral molecules (RCOOH or ROH) and reducing the activity of H+ in solution. The bacteria also inhibited the increase in soil soluble Al and exchangeable Al during soil acidification. The adhesion of bacteria on the soils increased soil effective cation exchange capacity (ECEC) and exchangeable base cations at each pH compared to control. The release of exchangeable base cations from bacteria-treated soil, and the decrease in soil ECEC and exchangeable base cations with decreasing pH confirmed that protonation of organic anions on adhered bacteria was mainly responsible for the inhibition of soil acidification. The change of zeta potential of the bacteria with pH and the ART-FTIR analysis at various pH provided more evidence for this mechanism. Therefore, the bacteria in variable charge soils played an important role in retarding soil acidification. Image 1 • Pseudomonas fluorescens inhibited the acidification of variable charge soils. • P. fluorescens inhibited the production of soil soluble Al and exchangeable Al. • Protonation of bacteria organic anions is responsible for inhibiting acidification. • Association of organic anions with H+ formed neutral acid functional groups. • Protonation of organic anions decreased soil exchangeable base cations and ECEC. [ABSTRACT FROM AUTHOR]

The dual role of biochar for inhibiting soil acidification induced by nitrification was determined through two-step incubation experiments in this study. Ca(OH) 2 or biochar was added respectively to adjust soil pH to the same values (pH 5.15 and 5.85), and then the amended soils were incubated in the presence of urea for 70 days. The results showed that compared with Ca(OH) 2 treatment, both rice straw biochar and peanut straw biochar inhibited the decrease in soil pH and the increase in exchangeable acidity during the incubation. The application of biochars suppressed soil nitrification during the incubation, and thus reduced 7.5 mmol kg−1 and 1.4 mmol kg−1 protons released from nitrification compared to Ca(OH) 2 treatments. Compared with Ca(OH) 2 treatment, the ammonia-oxidizing bacteria population size was decreased by 8% and 12% in rice straw biochar and peanut straw biochar treatments respectively, which was the main responsibility for the inhibited nitrification after biochar application. In addition, the application of rice straw biochar and peanut straw biochar increased soil pH buffering capacity (pHBC) respectively by 22% and 32%. The increased pHBC played the main role (75%) in inhibiting the acidification of the soil amended with peanut straw biochar, while the rice straw biochar inhibited soil acidification mainly through suppressing nitrification during the incubation. Overall, compared with lime application, biochars can inhibit soil acidification caused by urea application through suppressing the nitrification process and improving the resistance of soils to acidification. The crop residue biochars presented a longer-lasting effect on ameliorating acidic soils than mineral lime. Image 1 • Biochar played a dual role in inhibiting soil acidification from nitrification. • Biochar decreased proton release through suppressing soil nitrification. • Biochar increased soil pH buffering capacity and the resistance to acidification. • Biochar would be a better option to ameliorate acidic soils than liming. [ABSTRACT FROM AUTHOR]

Phyllosilicate minerals are the important components in soils and an important source of activated aluminum (Al) during soil acidification. However, the mechanisms for Al activation in phyllosilicate minerals were not understood well. In this paper, the effect of phyllosilicate surface hydroxyl groups on Al activation during acidification was studied after the minerals were modified with inorganic and organic materials. After modification of kaolinite, montmorillonite, and illite with fulvic acid (FA-), iron oxide (Fe-), Fe combined with FA (Fe-FA-), and siloxane (Si–O-), the interlayer spaces were altered. For instance, when modified with Fe, Fe entered the interlayer spaces of kaolinite and montmorillonite and changed the interlayer spaces of both minerals but did not affect that of illite. Also, the other modification methods had significant effects on the interlayer space of montmorillonite but not on kaolinite and illite. It was observed that all the modification strategies inhibited Al activation during acidification by reducing the number of hydroxyl groups on the mineral surfaces and inhibiting protonation reactions between H+ and hydroxyl groups. Nevertheless, the inhibition effect varies with the type of phyllosilicate mineral. For kaolinite (Kao), the inhibition effect of the different modification methods on Al activation during acidification followed: Fe-FA-Kao > Fe-Kao > Si–O-Kao > FA-Kao. Additionally, for montmorillonite (Mon), the inhibition effect was in the order: Si–O-Mon > Fe-Mon > Fe-FA-Mon > FA-Mon, while for illite, it was: Fe-illite > Si–O-illite ≈ Fe-FA-illite > FA-illite. Thus, the hydroxyl groups on the surfaces and edges of phyllosilicate minerals play an important role in the activation of Al from the mineral structure. Also, the protonation of hydroxyl groups may be the first step during Al activation in these minerals. The results of this study can serve as a reference for the development of new technologies to inhibit soil acidification and Al activation. [Display omitted] • Surface –OH of phyllosilicate minerals plays an important role in Al mobilization. • Surface modification reduced active hydroxyl groups on phyllosilicate minerals. • Surface modification inhibited Al activation in minerals induced by acidification. [ABSTRACT FROM AUTHOR]

[Display omitted] • More exchangeable Al was observed on montmorillonite than on kaolinite at pH < 5.1. • Exchangeable Al in Alfisol was larger than that in Ultisols under acidic conditions. • Soil CEC and organic matter play an important role in acid buffering performance. • Soil organic matter inhibited the production of exchangeable and soluble Al. Soil acidification is an increasing challenge to food security due to the production of free aluminum ion (Al3+) that is toxic to crops. The production of exchangeable Al3+ in soils during acidification is a complex process and its specific mechanism is not clear. In this study, kaolinite, montmorillonite, and three acidic soils (two Ultisols and one Alfisol) were used to investigate the changes in exchangeable and soluble Al with pH using a constant pH automatic potentiometric titrator. The effect of soil organic matter (SOM) on soil pH and Al change was also investigated. The results showed that montmorillonite consumed more acid than kaolinite under the same conditions, which were consistent with the larger cation exchange capacity (CEC) of montmorillonite than kaolinite. When the pH was adjusted from 4.8 to 4.3, the exchangeable Al of montmorillonite was significantly higher than that of kaolinite. This was consistent with their CEC and indicated that montmorillonite adsorbed more H+ than kaolinite at the same pH, resulting in more exchangeable Al on its surface. Besides CEC, SOM shows a significant effect on acid buffering capacity and Al activation of acid soils. When acidified to the same pH, the content of exchangeable Al in Alfisol was larger than that in Ultisols. This observation was consistent with the larger CEC and smaller organic matter content of Alfisol. The presence of more organic matter in the Ultisols not only improved their acid buffering performance, but also inhibited the production of exchangeable and soluble Al. In conclusion, CEC of soils and minerals play an important role in soil acid buffering performance. While, SOM not only improves soil acid buffering performance, but also inhibits the mobilization of soil Al. [ABSTRACT FROM AUTHOR]

Forest soil acidification caused by acid deposition is a serious threat to the forest ecosystem. To investigate the liming effects of biomass ash (BA) and alkaline slag (AS) on the acidic topsoil and subsoil, a three-year field experiment under artificial Masson pine was conducted at Langxi, Anhui province in Southern China. The surface application of BA and AS significantly increased the soil pH, and thus decreased exchangeable acidity and active Al in the topsoil. Soil exchangeable Ca2+ and Mg2+ in topsoil were significantly increased by the surface application of BA and AS, while an increase in soil exchangeable K+ was only observed in BA treatments. The soil acidity and active Al in subsoil were decreased by the surface application of AS. Compared with the control, soluble monomeric and exchangeable Al in the subsoil was decreased by 38.0% and 29.4% after 3 years of AS surface application. There was a minimal effect on soluble monomeric and exchangeable Al after the application of BA. The soil exchangeable Ca2+ and Mg2+ in the subsoil increased respectively by 54% and 141% after surface application of 10 t ha−1 AS. The decrease of soil active Al and increase of base cations in subsoil were mainly attributed to the high migration capacity of base cations in AS. In conclusion, the effect of surface application of AS was superior to BA in ameliorating soil acidity and alleviating soil Al toxicity in the subsoil of this Ultisol. [Display omitted] • Biomass ash (BA) and alkaline slag (AS) effectively amended the topsoil acidity. • BA surface application increased soil exchangeable K+ in both topsoil and subsoil. • The acidity and active Al in subsoil were reduced by surface application of AS. • High mobility of Ca and Mg in AS contributed to the reduced active Al in subsoil. [ABSTRACT FROM AUTHOR]