Alteration of soil pH induced by submerging/drainage and application of peanut straw biochar and its impact on Cd(II) availability in an acidic soil to indica-japonica rice varieties.

The effects of soil pH variations induced by submergence/drainage and biochar application on soil cadmium (Cd) availability to different rice (Oryza sativa L.) varieties are not well understood. This study aims to investigate the possible reasons for available Cd(II) reduction in paddy soil as influenced by biochar and to determine Cd(II) absorption and translocation rates in different parts of various rice varieties. A pot experiment in a greenhouse using four japonica and four indica rice varieties was conducted in Cd(II) contaminated paddy soil with peanut straw biochar. The results indicated that the submerging led to an increase in soil pH due to the consumption of protons (H+) by the reduction reactions of iron/manganese (Fe/Mn) oxides and sulfate (SO42-) and thus the decrease in soil available Cd(II) contents. However, the drainage decreased soil pH due to the release of protons during the oxidation of Fe2+, Mn2+, and S2- and thus the increase in soil available Cd(II) contents. Application of the biochar increased soil pH during soil submerging and inhibited the decline in soil pH during soil drainage, and thus decreased soil available Cd(II) contents under both submerging and drainage conditions. The indica rice varieties absorbed more Cd(II) in their roots and accumulated higher amounts of Cd(II) in their shoots and grains than the japonica rice varieties. The Cd(II) sensitive varieties exhibited a greater absorption and translocation rate of Cd(II) compared to the tolerant varieties of both indica and japonica rice. Biochar inhibited the absorption and accumulation of Cd(II) in the rice varieties, which ultimately lowered the Cd(II) contents in rice grains below the national food safety limit (0.2 mg kg-1). Overall, planting japonica rice varieties in Cd(II) polluted paddy soils combined with the use of biochar can effectively reduce Cd(II) content in rice grains which protects human health against Cd(II) toxicity.

A new simple index for characterizing the labile heavy metal concentration in soil by diffusive gradients in thin films technique.

Diffusive gradients in thin films technique (DGT) is recognized as a more reliable method for determining labile heavy metal (HM) concentration in soil than traditional destructive methods. However, the current DGT measurement index, CDGT, theoretically underestimates the true labile concentration (Clabile) of HMs in soil and lacks direct comparability with the conventional soil HM content indices due to unit differences. Here, we proposed CDGT-W, a new simple index which is defined as the HM accumulation in the binding layer, normalized to the weight of soil (optimized water content = 100% of the maximum water holding capacity) filled in the open cavity-type DGT device over a specified deployment time (optimized time = 24 h). The procedure for measuring CDGT-W is analogous to that of CDGT but includes precise determination of water content (water/dry soil) and the mass of soil filled in the cavity. We conducted measurements of Cu, Pb, Cr(Ⅵ) and As(V) as CDGT-W, CDGT, solution concentration (Csoln), and CaCl2 extractable concentration (CCaCl2) on three soils with a diverse range of HM concentrations. CDGT-W showed significant linear correlations with all other tested indexes. The ratios of CDGT-W to CCaCl2 varied between 0.30 and 0.98 for all HM-soil combinations with only one exception, a range much greater than CDGT/Csoln (typically <0.1) but lower than 1. This suggested that CDGT-W may more accurately reflect Clabile than CDGT (theoretically underestimates Cliable) and CCaCl2(likely overestimates Cliable). Additionally, CDGT-W measurements for these four HMs exhibited a broad measure concentration range and a low detection limit (mg/kg level). Consequently, CDGT-W may offer a more reliable alternative to CDGT for characterizing Clabile in unsaturated soils.

Rapid assessment of soil accessible Cr(â ¥) in the field by a portable RGB color sensor.

Field rapid determination of soil accessible Cr(Ⅵ) is of great significance for on-site assessment and decision-making about the health risks of contaminated sites. When the thickness of solutions with various concentrations of Cr(Ⅵ) is constant, there would be a quantitative relationship between the chromogenic difference of Cr(Ⅵ) solutions and the concentration of Cr(Ⅵ). The chromogenic difference could be described by Red (R), Green (G), Blue (B) values. Based on the chromogenic reaction between 1,5-diphenylcarbazide and Cr(Ⅵ), this study first established the calibration curve between the chromogenic difference and the concentration of Cr(Ⅵ) in standard solution with or without 0.01 M CaCl2, using an RGB color sensor. This is the subsequent determination basis of the method for rapidly assessing accessible Cr(Ⅵ) in the field (M-RGB). Then, the concentration of accessible Cr(Ⅵ) of contaminated soil with "hand-shaking + standing" field extraction method was compared with "end-over-end shaking" laboratory extraction method. Finally, the accessible Cr(Ⅵ) of contaminated soil extractants was determined via M-RGB integrating the field extraction method. Results indicated there was a highly significant linear relationship between colorimetric difference value (∆E) and Cr(Ⅵ) concentration in the range of 0.1-3 mg/L (R2 > 0.99, P < 0.01), based on the Euclidean formula for calculating ∆E. The "hand-shaking + standing" field extraction method was effective in obtaining accessible Cr(Ⅵ) extractants with or without 0.01 M CaCl2, with the high extraction efficiency within 100±1%. The concentrations of accessible Cr(Ⅵ) in various polluted soils determined by M-RGB were consistent with that determined by the ultraviolet-visible spectrophotometry, with the relative error within ±5%, and the relative standard deviation ≤ 20%. The spiked recovery experiments showed that the recovery of M-RGB was between 95% and 105%, which means M-RGB could realize the trace analysis for accessible Cr(Ⅵ) in the field.

Critical values of soil solution Al3+ activity and pH for canola and maize cultivation in two acidic soils.

BACKGROUND: Aluminum (Al) toxicity caused by soil acidification is the main constraint for crop growth in tropical and subtropical areas of southern China. The critical values of soil solution Al3+ activity and pH for crops in acidic soils can provide a useful reference for soil acidity amelioration. RESULTS: A pot experiment in a greenhouse was conducted to investigate the critical values of soil solution Al3+ activity and pH for canola and maize in an Ultisol and an Alfisol. The critical values of soil solution Al3+ activity in Ultisol and Alfisol for canola were 1.5 and 10.0 µmol L-1 , and 13.9 and 30.4 µmol L-1 for maize, respectively. The Al tolerance varied with soil type for the same variety of crop. There was more biomass of roots and shoots and higher plant height under the same Al3+ activity, and thus greater critical values of soil solution Al3+ activity for both crops in Alfisol than those in Ultisol, owing to higher Ca2+ /Al3+ , Mg2+ /Al3+ and K+ /Al3+ ratios in soil solution caused by higher cation exchange capacity and exchangeable base cations in Alfisol, when compared with those in Ultisol. The critical values of soil solution pH for canola and maize in Ultisol were 5.09 and 4.72, respectively; while those in Alfisol were 4.87 and 4.54, respectively. CONCLUSION: The critical values of Al3+ activity were higher for maize than for canola and the critical values for both crops were higher in Alfisol than in Ultisol. The critical soil pH for both crops showed opposite trends to soil Al3+ activity. © 2022 Society of Chemical Industry.

Effect of the interaction of fulvic acid with Pb(II) on the distribution of Pb(II) between solid and liquid phases of four minerals.

Lead (Pb) is one of the top metal pollutants worldwide, and its distribution between liquid and solid phases of soils is strongly controlled by its adsorption on minerals, organic matter, and their composites. This paper presented the effect of fulvic acid (FA) coexistence on the distribution of Pb(II) at the solid-liquid interface of four minerals, which provided reference for how to use humic substances to remove toxic Pb(II) in soils. The free Pb2+ of suspensions, measured by Pb ion selective electrode, was used to characterize the complexation of FA with Pb2+ at various pH. The adsorption isotherms of Pb(II) by montmorillonite, kaolinite, goethite, and gibbsite with and without FA were studied with batch experiments. Results indicated that the free Pb2+ decreased and complexed Pb(II) increased with the increase of FA concentration in Pb(II)-FA solutions, whether the initial concentration of Pb(II) was 0.1 or 1 mM. Pb2+ hydrolysis was low and the free Pb2+ concentration in pure lead solution without FA was generally unchanged with increasing solution pH at pH < 6.0. But free Pb2+ decreased with the increase of pH in the presence of FA, suggesting that the complexation ability of FA with Pb2+ increased with the increase of solution pH. The adsorption of Pb(II) by the minerals without FA followed the order: montmorillonite > kaolinite ≈ goethite > gibbsite at pH5.0. The Pb(II) adsorption by montmorillonite and kaolinite significantly enhanced with 1 g/L FA, while significantly inhibited with 3 g/L FA at low initial Pb(II) concentration. However, the effect of FA on Pb(II) adsorption by montmorillonite was greater than that of kaolinite, which was mainly related to the crystal layer structure, adsorption area, and cation exchange capacity of the minerals. The Pb(II) adsorption by goethite and gibbsite was significantly enhanced by the addition of both 1 g/L and 3 g/L FA, and the enhancement was more evident in goethite system. The effect of FA on the distribution of Pb(II) between solid and liquid phases of the minerals was determined by the factors such as the initial concentration ratio of FA to Pb(II), the adsorption capacity of minerals for FA, and the number of soluble complexes of FA with Pb2+. Therefore, the distribution of FA between solid and liquid of four minerals affected the distribution of Pb(II) between solid and liquid phases of the minerals greatly. The results can provide an important reference for understanding the distribution of Pb(II) and the dynamics and mobility of active components in polluted soils.

Effects of the increases in soil pH and pH buffering capacity induced by crop residue biochars on available Cd contents in acidic paddy soils.

To explore the effects of the increases in pH and pH buffering capacity (pHBC) induced by crop residue biochars on the changes in soil available Cd content, six acidic paddy soils developed from different parents were amended with seeded sunflower plate biochar (SSPBC), peanut straw biochar (PSBC) and corn straw biochar (CSBC). The pH, pHBC, and available Cd of the soils were measured after laboratory incubation. The results showed that the incorporation of crop residue biochars led to the increases in soil pH and pHBC, but a decrease in soil available Cd content. The decreasing order of available Cd content was SSPBC > PSBC > CSBC and was consistent with the changes in soil pH induced by the biochars. During submerging and draining, soil pH increased first and then declined, however the content of available Cd decreased first and then increased significantly. Soil pH in the treatments with biochars showed little change during draining, which was different from the control without the biochars added. This was attributed to the enhancing effect of the biochars on soil pHBC. Also, there was a significant negative correlation between the change in available Cd content and soil pHBC during submerging/draining alternation and suggested that higher pHBC corresponded to smaller soil available Cd content. Consequently, the amount of Cd absorbed by rice was reduced, thereby reducing the potential risk of soil Cd to humans. These results can provide useful references for the remediation of Cd-contaminated paddy soils.

Effects of pH variations caused by redox reactions and pH buffering capacity on Cd(II) speciation in paddy soils during submerging/draining alternation.

Incubation experiments were conducted to investigate the influencing factors of pH variation in different paddy soils during submerging/draining alternation and the relationship between pH buffering capacity (pHBC) and Cd speciation in ten paddy soils developed from different parent materials (including 8 acid paddy soils and 2 alkaline paddy soils). The soil pHBC and the changes in soil pH, Eh, Fe2+, Mn2+, SO42- and Cd speciation were determined. The results showed that there was a significant positive correlation between cation exchange capacity (CEC) and pHBC of these paddy soils, indicating that soil CEC is a key factor affecting the pHBC of paddy soils. The contribution of Fe(III) oxide reduction to H+ consumption is far greater than the reduction of Mn(IV)/Mn(III) oxides and SO42- during the submerging. For example, the contribution of the reduction of manganese oxides, SO42- and iron oxides to H+ consumption in the paddy soils from Anthrosol at 15 d submerging was 1.2%, 11.6% and 87.2%, respectively. This confirms that the reduction of Fe(III) oxides plays a leading role in increasing soil pH. Importantly, we noticed that during submerging, soil pH was increased and resulted in the content of available Cd in soils being reduced. This was due to the transformation of Cd to less active forms. Also, there was a significant positive correlation between the change rate of available Cd, the percentage of acid extractable Cd and pH variation. This suggests that the variation in soil pH was responsible for the transformation of Cd speciation. In addition, the change rate of available Cd and the percentage of acid extractable Cd concentration were significantly negatively correlated with soil pHBC. The soil with higher pHBC experienced less pH change, and thus the change rate of available Cd and the percentage of acid extractable Cd concentration were less for the soil. The results of this study can provide a basis for the remediation of Cd-contaminated acidic paddy soils.

The effects of H2O2- and HNO3/H2SO4-modified biochars on the resistance of acid paddy soil to acidification.

Biochar was prepared from rice straw and modified with 15% H2O2 and 1:1 HNO3/H2SO4, respectively. The unmodified biochars and HCl treated biochars for carbonate removal were used as control. The biochars were added to the acid paddy soil collected from Langxi, Anhui Province, China at the rate of 30 g/kg. The paddy soil was flooded and then air-dried, and soil pH and Eh were measured in situ with pH electrode and platinum electrode during wet-dry alternation. Soil pH buffering capacity (pHBC) was determined by acid-base titration after the wet-dry treatment. Then, the simulated acidification experiments were carried out to study the changing trends of soil pH, base cations and exchangeable acidity. The results showed that soil pHBC was effectively increased and the resistance of the paddy soil to acidification was apparently enhanced with the incorporation of H2O2- and HNO3/H2SO4-modified biochars. Surface functional groups on biochars were mainly responsible for enhanced soil resistance to acidification. During soil acidification, the protonation of organic anions generated by dissociation of these functional groups effectively retarded the decline of soil pH. The modification of HNO3/H2SO4 led to greater increase in carboxyl functional groups on the biochars than H2O2 modification and thus HNO3/H2SO4-modified biochars showed more enhancement in soil resistance to acidification than H2O2-modified biochars. After a wet-dry cycle, the pH of the paddy soil incorporated with HNO3/H2SO4-modified biochar increased apparently. Consequently, the addition of HNO3/H2SO4-modified biochar can be regarded as a new method to alleviate soil acidification. In short, the meaning of this paper is to provide a new method for the amelioration of acid paddy soils.

Inhibition of phosphate sorptions on four soil colloids by two bacteria.

Ion sorption on soil and sediment has been reported to be potentially affected by bacteria which may interact both physically and chemically with solid surfaces. However, whether and how bacteria affect the sorption of inorganic phosphate (P) on soil colloids remains poorly known. Here, we comparably investigated the P sorption on four soil colloids (three highly weathered soils including two Oxisols and one Ultisol and one weakly weathered soil Alfisol) and their complexes with Bacillus subtilis and Pseudomonas fluorescens. Batch experiments showed a notable reduction in P sorption on the colloids of highly weathered soils by the two bacteria at varying P concentrations and pHs; whereas that on the colloids of Alfisol appeared to be unaffected by the bacteria. The inhibitory effect was confirmed by both greater decline in P sorption at higher bacteria dosages and the ability of the bacteria to desorb P pre-adsorbed on the colloids. Further evidence was given by isothermal titration calorimetric experiments which revealed an alteration in enthalpy change caused by the bacteria for P sorption on Oxisol but not for that on Alfisol. The B. subtilis was more efficient in suppressing P sorption than the P. fluorescens, indicating a dependence of the inhibition on bacterium type. After association with bacteria, zeta potentials of the soil colloids decreased considerably. The decrease positively correlated with the decline in P sorption, regardless of soil and bacterium types, demonstrating that the increment in negative charges of soil colloids by bacteria probably contributed to the inhibition. In addition, scanning electron microscopic observation and the Derjaguin-Landau-Verwey-Overbeek theory prediction suggested appreciable physical and chemical interactions between the bacteria and the highly weathered soil colloids, which might be another contributor to the inhibition. These findings expand our understandings on how bacteria mobilize legacy P in soils and sediments.

Enhancement of Cd(II) adsorption by rice straw biochar through oxidant and acid modifications.

To develop high-efficient biochar adsorbents, the effects and mechanisms of oxidant modification and acid modification on Cd(II) adsorption by rice straw biochar were investigated. Three rice straws from Langxi in Anhui Province, Yingtan in Jiangxi Province, and Lianyungang in Jiangsu Province were collected to prepare biochars by anaerobic pyrolysis in a muffle furnace. Rice straw biochars were modified by 15% H2O2 and 1:1 HNO3/H2SO4 mixed acid, respectively, to obtain modified biochars. The untreated rice straw biochar and HCl-treated rice straw biochar with carbonate removed were used as controls. The functional groups on the surfaces of the biochars were qualitatively and quantitatively determined by Fourier transform infrared spectra and Boehm titration, respectively. The adsorption and desorption of Cd(II) onto and from the biochars and modified biochars were measured under various pH conditions. The results showed that oxidant modification with 15% H2O2 and acid modification with 1:1 HNO3/H2SO4 significantly increased the number of carboxyl functional groups on the surfaces of the biochars, and acid modification was more effective than oxidant modification in amplifying carboxyl functional groups on the surfaces of the biochars. The increase of surface functional groups effectively enhanced the specific adsorption of Cd(II) on the modified biochars. Therefore, both oxidant modification and acid modification enhanced the adsorption of Cd(II) on the biochars through increasing functional groups on the surfaces of the biochars.

Effects of crop straw biochars on aluminum species in soil solution as related with the growth and yield of canola (Brassica napus L.) in an acidic Ultisol under field condition.

The toxicity of aluminum (Al) to plants in acidic soils depends on the Al species in soil solution. The effects of crop straw biochars on Al species in the soil solution, and canola growth and yield were investigated in this study. In a long-term field experiment, there were four treatments, which were a control, rice straw biochar (RSB), canola straw biochar (CSB), and peanut straw biochar (PSB). The soil solution was collected in situ, the Al species were identified, and the relationships between the concentration of phytotoxic Al and canola growth and yield were evaluated. The results showed that applying the three biochars resulted in significant decreases in the concentrations of total Al, monomeric Al, and monomeric inorganic Al (P < 0.05). The Al3+, Al-OH, and Al-SO4 proportions of the total Al also decreased. The abilities of the different biochars to reduce dissolved Al followed the order PSB > CSB > RSB, which was consistent with the alkalinity of these biochars. Application of the biochars significantly decreased the concentration of phytotoxic Al (Al3+ + Al-OH), which improved canola growth and increased the canola seed and straw yields. Plant height, leaf number per plant, area per leaf, chlorophyll content, and canola yield were negatively correlated with the Al3+ + Al-OH concentrations. Therefore, the results showed that crop straw biochars can be used to ameliorate soil acidity and alleviate Al toxicity in acidic soils, and that peanut straw biochar is the best amendment for acidic soils.

Phytotoxicity of Cu2+ and Cd2+ to the roots of four different wheat cultivars as related to charge properties and chemical forms of the metals on whole plant roots.

The relationship between the chemical forms of Cu2+ and Cd2+ adsorbed on the roots of different wheat cultivars and their phytotoxic effects on the plants were investigated. The wheat varieties Dunmaiwang (DMW), Tekang 6 (TK6), Zhongmai895 (ZM895), and Chaojixiaomai (AK68) were used. The zeta potentials of wheat roots, measured by the streaming potential method, were used to characterize root charge properties. Results indicated that the changes in zeta potential at pH 4.01-6.61 were 14.7, 15.53, 13.01, and 12.06 mV for ZM895, AK68, DMW, and TK6, respectively. The negative charge and functional groups on ZM895 and AK68 roots were greater than on DMW and TK6 roots, which led to more exchangeable and complexed Cu2+ and Cd2+ on ZM895 and AK68 roots and increased Cu2+ and Cd2+ toxicity compared to DMW and TK6. Coexisting cations, such as Ca2+, Mg2+, K+, and NH4+, alleviated Cu2+ and Cd2+ toxicity to wheat roots through competition for adsorption sites on the roots, which decreased exchangeable and complexed Cu2+ and Cd2+ on wheat roots. The Ca2+ and Mg2+ were most effective in alleviating heavy metal toxicity and they decreased exchangeable Cu2+ on AK68 roots by 39.14% and 47.82%, and exchangeable Cd2+ by 8.51% and 28.23%, respectively.

The mechanism for inhibiting acidification of variable charge soils by adhered Pseudomonas fluorescens.

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.

An electrokinetic perspective into the mechanism of divalent and trivalent cation sorption by extracellular polymeric substances of Pseudomonas fluorescens.

Extracellular polymeric substances (EPS) contain a vast number of functional groups which can provide sorption sites for heavy metal cations in solution, however, the mechanisms for the interaction of EPS with various metal cations were not well understood. In this study, the sorption potential of EPS from Pseudomonas fluorescens for different cations was investigated. The changes of electrokinetic properties that occurred on the surface of EPS once they adsorbed these cations were also studied using zeta potential measurements as a function of pH and cation concentration. The adsorption data fitted Freundlich isotherm better than Langmuir and D-R isotherms. The interactions of the cations with EPS were favourable with the separation factor Kr < 1. Under different pH conditions, the zeta potential of EPS in the different cation solution followed the order: Fe(III) (at pH ≤ 5.0) > Al(III) > Cu(II) > Mn(II) > Ni(II)≈Cd(II) > Ca(II) > EPS, while with respect to the initial cation concentration, the zeta potential of EPS was in the order: Fe(III) > Al(III) > Cu(II) > Cd(II) > Ni(II)≈Mn(II)≈Ca(II). The effect of cation sorption on the surface charge of EPS increased with pH as well as cation concentration. The thermodynamic analysis demonstrated that besides the sorption of Fe which was exothermic, all the other cations were adsorbed through an endothermic process. The ΔSads revealed that most of the cations interacted with EPS through the formation of inner-sphere complexes. The ATR-FTIR analyses confirmed that complexation occurred between the cations and functional groups on the surface of EPS. The zeta potential of EPS shifted to positive value direction due to sorption of cations on EPS, indicating that the specific interactions were involved in the sorption process. This study enhances our understanding of EPS aggregation and heavy metal bio-sorption through the electrokinetic mechanism. The results will provide useful references for immobilization of heavy metals and alleviation of Al toxicity in acidic soils.

Adhesion mediated transport of bacterial pathogens in saturated sands coated by phyllosilicates and Al-oxides.

The current knowledge of bacterial migration is mainly derived from work using bare or Fe-coated quartz sands as porous media. However, mineral coatings on quartz by phyllosilicates and Al-oxides prevail in natural soils, and their effect on bacterial transport remains unknown. Herein, we systematically explored the transport of two bacterial pathogens (Escherichia coli and Staphylococcus aureus) through saturated bare quartz and those coated by kaolinite (KaoQuartz), montmorillonite (MontQuartz) or Al-oxides (AlQuartz) under various solution ionic strength (IS) and pH levels. Elevating IS or decreasing pH discouraged bacterial mobility in all cases, with one exception for the migration of S. aureus through AlQuartz at various IS levels. E. coli showed a higher mobility than S. aureus in all cases. All the three coatings, especially the Al-oxides inhibited bacterial transport through quartz. Overall, the two phyllosilicates-coated sands showed transport behaviors (mobility trends with IS, pH, and cell type) similar to those for the bare quartz which could be explained by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Nevertheless, for transport within AlQuartz, there were deviations between the observations and the DLVO predictions, probably because of the existence of non-DLVO forces such as hydrophobic and chemical interactions. More importantly, the bacterial retention was found to correlate well with the adhesion regardless of the solution condition and the bacteria and media type, thereby revealing a central role of adhesion in mediating migration through mineral-coated sands. These findings highlight the significance of mineral coating and adhesion in pathogen dissemination in natural soils.

Preferential adhesion of surface groups of Bacillus subtilis on gibbsite at different ionic strengths and pHs revealed by ATR-FTIR spectroscopy.

Adhesion of bacteria onto minerals is a ubiquitous process that plays a central role in many biogeochemical, microbiology and environmental processes in soil and sediment. Although bacterial adhesion onto soil minerals such as phyllosilicates and Fe-oxides have been investigated extensively, little is known about the mechanisms for bacterial attachment onto Al-oxides. Here, we explored the adhesion of Bacillus subtilis onto gibbsite (γ-AlOOH) under various ionic strengths (1, 10, 50, and 100 mM NaCl) and pHs (pH 4, 7, and 9) by in-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The time evolution of the peak intensities of the attached bacteria suggested that the adhesion underwent an initial rapid reaction followed by a slow pseudo-first-order kinetic stage. Spectral comparison between the attached and free cells, together with the interaction energy calculated with the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory and the micro-morphology of bacteria-gibbsite complexes, indicated that both electrostatic and chemical (bacterial groups such as phosphate and carboxyl covalently bind to gibbsite) interactions participated in the adhesion processes. Both solution ionic strength (IS) and pH impacted the spectra of attached bacteria, but the peak intensity of different bands changed differently with these two factors, showing a preferential adhesion of surface groups (phosphate, carboxyl, and amide groups) on gibbsite at different conditions. The diverse responses to IS and pH alteration of the forces (chemical bonds, electrostatic attractions, and the hydrophobic interactions) that essentially govern the adhesion might be responsible for the preferential adhesion. These results may help to better understand how bacteria adhere onto soil oxides at molecular scales.

Adsorption mechanism of extracellular polymeric substances from two bacteria on Ultisol and Alfisol.

The primary objective of this study was to identify the capacity and mechanism of extracellular polymeric substance (EPS) adsorption on soil colloids of Alfisol and Ultisol at different pH and ionic strengths. Two kinds of EPS were extracted from Bacillus subtilis and Pseudomonas fluorescens by centrifugation, and their adsorption on Ultisol and Alfisol was investigated using a batch adsorption experiment and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The average diameter of EPS from B. subtilis and P. fluorescens was 1825 and 1288 nm, respectively, and both the EPS were negatively charged. The zeta potentials of the two EPS became more negative with increasing solution pH from 3 to 8 and less negative with increasing ionic strength from 0 to 80 mM. The maximum adsorption capacity of EPS-C and EPS-N on Alfisol was higher than that on Ultisol, whereas the maximum adsorption capacity of EPS-P on Alfisol was lower than that on Ultisol. The adsorption of EPS-C, EPS-N, and EPS-P of both the EPS on Ultisol and Alfisol decreased with increasing solution pH from 3 to 8. Adsorption of EPS-C, EPS-N, and EPS-P of both the EPS on Alfisol significantly increased with increasing ionic strength from 0 to 10 mM, whereas it remained constant, slightly increased, or reduced, when the ionic strength was increased from 10 to 80 mM. The adsorption of EPS-C, EPS-N, and EPS-P on Ultisol slightly increased with increasing ionic strength from 0 to 80 mM. Saturation coverage determined by ATR-FTIR showed that adsorption of whole EPS on Ultisol was higher than that on Alfisol at pH 6 after 60 min. Thus, electrostatic force between EPS and soil colloids played an important role in EPS adsorption. Besides, proteins and phosphate groups in EPS also contributed to EPS adsorption on soil colloids.

Peanut straw biochar increases the resistance of two Ultisols derived from different parent materials to acidification: A mechanism study.

The mechanisms for increasing soil pH buffering capacity (pHBC) and soil resistance to acidification by peanut straw biochar were investigated by undertaking indoor incubation and simulated acidification experiments using two Ultisols derived from tertiary red sandstone and quaternary red earth. The biochar increased the pHBC and resistance of the two Ultisols to acidification. The addition of 3% biochar increased the pHBC of the two Ultisols by 76% and 25%, respectively. The increased resistance of the soils to acidification led to the inhibition to decrease in soil pH and the activation of soil Al during acidification. The protonation of carboxyl groups on the biochar surface was the main mechanism responsible for resisting acidification of the Ultisols when the pH was between 4.5 and 7.0. The higher soil pH (>6.0) after biochar application and the large number of carboxyl groups on the biochar surface were essential if biochar was to significantly increase the resistance of soils to acidification.

ATR-FTIR investigation of mechanisms of Bacillus subtilis adhesion onto variable- and constant-charge soil colloids.

The primary objective of this study was to determine the capacity and the mechanisms of adhesion of Bacillus subtilis onto variable- and constant-charge soil colloids. The adhesion process was investigated using in situ attenuated total reflectance (ATR)-Fourier transform infrared spectroscopy (FTIR), zeta potential, and batch adhesion experiments. The maximum adhesion capacity of B. subtilis on the colloids of Oxisol, Ultisol, and Alfisol reached 699.17, 462.56, and 258.82mgg-1, respectively. B. subtilis adhesion to all three soil colloids decreased as the suspension pH increased from 3 to 8. Saturation coverage and adhesion rate constant values were calculated with the pseudo-first-order kinetics equation using the absorbance at 1548cm-1. Both values were highest for Oxisol, followed by Ultisol, and lowest for Alfisol. These observations are consistent with the surface charges of these soil colloids. A larger positive charge on variable-charge soils (Oxisol and Ultisol) increased B. subtilis adhesion relative to that of constant-charge soil (Alfisol). This is in agreement with the interaction energy between B. subtilis and soil colloids, which was calculated using the Derjaguin-Landau-Verwey-Overbeek theory. As revealed by ATR-FTIR spectroscopy, chemical bonds formed by protein, phosphate, and COOH groups on B. subtilis, as well as iron and aluminum hydroxyl groups in soil, contributed to B. subtilis adhesion to soil colloids. Therefore, chemical bond formation and electrostatic interaction are two major mechanisms of B. subtilis adhesion onto soil colloids.

Effects of Surface Charge and Functional Groups on the Adsorption and Binding Forms of Cu and Cd on Roots of indica and japonica Rice Cultivars.

This work was designed to understand the mechanisms of adsorption of copper (Cu) and cadmium (Cd) on roots of indica and japonica varieties of rice. Six varieties each of indica and japonica rice were grown in hydroponics and the chemical properties of the root surface were analyzed, including surface charges and functional groups (-COO- groups) as measured by the streaming potential and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). Binding forms of heavy metals adsorbed on rice roots were identified using sequential extraction methods. In rice roots exposed to Cu and Cd solutions, Cu existed mainly in both exchangeable and complexed forms, whereas Cd existed mainly in the exchangeable form. The amounts of exchangeable Cu and Cd and total adsorbed metal cations on the roots of indica varieties were significantly greater than those on the roots of japonica varieties, and the higher negative charges and the larger number of functional groups on the roots of indica varieties were responsible for their higher adsorption capacity and greater binding strength for Cu and Cd. Surface charge and functional groups on roots play an important role in the adsorption of Cu and Cd on the rice roots.