Rice straw can adsorb Cd(II) from wastewater, and modification of rice straw may improve its adsorption efficiency. The rice straw powder (Sp) from the direct pulverization of rice straw was used as the control, the rice straw ash (Sa), biochar (Sa), and modified rice straw (Ms) were prepared by ashing, pyrolysis and citric acid modification, respectively, and all of them were examined as adsorbents for Cd(II) in this study. Batch adsorption experiments were adopted to systematically compare the adsorption capacities of rice straw materials prepared with different modification methods for Cd(II) from aqueous solution under different levels of initial Cd(II) concentration (0–800 mg·L⁻¹), temperature (298, 308, and 318 K), contact time (0–1440 min), pH value (2–10), and ionic strength (0–0.6 mol·L⁻¹). The results indicated that the modification method affected the adsorption of Cd(II) by changing the specific surface area (SSA), Si content, surface morphology, and O-containing functional group of rice straw. Compared with Sp, Ms held more surface O–H, aliphatic and aromatic groups, while Sa had more phenolic, C–O (or C–O–C), and Si–O groups, and Sb held more C–O (or C–O–C) and Si–O groups; besides, Sa, Sb, and Ms had larger SSA than Sp. Adsorption capacity of the four adsorbents for Cd(II) increased and gradually became saturated with the increase in the initial Cd(II) concentration (0–800 mg·L⁻¹). The adsorption capacity of Cd(II) was significantly higher at 318 K than 298 K and 308 K, regardless of the adsorbent type. Sa had the largest SSA (192.38 m²·g⁻¹) and the largest adsorption capacity for Cd(II). When the initial Cd²⁺ concentration was at 800 mg·L⁻¹, the Cd(II) adsorption amount reached as high as 68.7 mg·g⁻¹ with Sa at 318 K. However, the SSA of Sp was only 1.83 m²·g⁻¹, and it had the least adsorption capacity for Cd(II). Only the adsorption of Cd(II) upon Sb at 298 K was spontaneous, and surprisingly, all other adsorptions were nonspontaneous. These adsorptions were all chemical, and were favorable, exothermic and order-increasing processes. The pseudo-second-order model showed a strong fit to the kinetics of Cd(II) adsorption by the four adsorbents. The adsorption capacities of Cd(II) by the adsorbents were less at low pH, and all were enhanced with the increase of initial pH value (2–10) in the solution. The inhibiting effect on Cd(II) adsorption due to the increase in ionic strength was greater with Sa, Sb, and Ms than that under Sp. The rice straw ash prepared by ashing unexpectedly had greater adsorption capacity for Cd(II) than the biochar and citric acid modified rice straw. The optimum condition for Cd(II) adsorption was established as the temperature of 318 K, initial Cd(II) concentration of 800 mg·L⁻¹, contact time of 240 min, and no Na(I) interference regardless of absorbent. In conclusion, rice straw ash shows the greatest potential of being applied to paddy fields for the remediation of Cd(II) pollution so as to reduce the risk of Cd(II) enrichment in rice grains and straws.

Rice straw is a kind of low-cost biosorbent. Through mechanical crushing, pyrolysis, incineration, and citric acid (CA) modification, it could be converted to rice straw powder (Sp), biochar (Sb), ash (Sa), and modified rice straw (Ms) accordingly. Using rice straw as an adsorbent, the influence of pH value (2, 4, and 9), initial Cd(II) concentration (0, 200, and 800 mg/L), and ionic strength (0, 0.2, to 0.6 mg/L) on the adsorption capacity for Cd(II) were examined with three replicates, and the relevant mechanisms were explored using Fourier transform infrared (FTIR) technology. Results showed that the modifications could improve the adsorption capacity of Cd(II) by changing their chemical structures. The products (Sb and Sa) of the pyrolysis and incineration of rice straw contained fewer hydroxyl and alkyl groups, but more Si–O groups. Citric acid modification removed a portion of silica in rice straw, increased its carboxylic content, and made more –OH groups exposed. Compared with Sp, Sb, Sa, and Ms were more likely to act as π donors in the Cd(II) sorption process and exhibited more carboxyl binding. The bands of C = C, –O–CH₃, and the O–H, carboxyl, Si–O–Si or Si–O groups were involved in the Cd(II) sorption process. The adsorption amount of Cd(II) by the four adsorbents increased with the increase in the pH value of the solution and the initial Cd(II) concentration. Affected by pH in a solution, ion exchange, surface complexation, and precipitation were the major adsorption mechanisms. Further, under the influence of the initial Cd(II) concentration, electrostatic attraction played a leading role. With no interference by ionic strength, all the adsorbents had the greatest adsorption amount of Cd(II), and the intensity of O–H vibration was also the weakest; ion exchange was the most important mechanism in this process. Regardless of the influencing factors, Sa, with the greatest specific surface area, had an absolute advantage in the adsorption capacity of Cd(II) over Sp, Sb, and Ms.

The contribution of microbial residues formed on lignin and cellulose to the formation of humus (HS) was investigated. The microbial residues formed by Aspergillus niger (A. niger) in the cultures of cellulose and lignin in a fluid medium were structurally characterized by elemental analysis, differential thermal analysis (DTA), FTIR spectroscopy and CP/MAS ¹³C NMR spectroscopy. Compared to cellulose itself, the microbial residue from cellulose contains more aromatic compounds and N-containing compounds and fewer carbohydrates and carboxylic compounds. A. niger improved the thermal stability and aromaticity of the cellulose. However, compared with that on lignin, more N-containing compounds, carbohydrates and carboxylic acid derivatives and less aromatic material were found in the microbial residue from lignin. Regardless of whether the carbon source was cellulose or lignin, A. niger utilized the N in the fluid medium to synthesize its own cells, and eventually, they could transfer the N into the microbial residue; in addition, the O-alkyl species dominated over the alkyl and aromatic compounds in the microbial residue. Although the molecular structures of the components of the microbial residue from lignin tended to be simpler, they were more alkylated, more hydrophobic and less aliphatic than those from cellulose. During culture with A. niger, the cellulose underwent degradation and then a polymerization, which led to an increased degree of condensation but a lower degree of oxidation, providing essential precursor substances for HSs formation. However, lignin underwent oxidative degradation. The microbial residue from lignin had a lower degree of condensation and a higher degree of oxidation.