This paper analyzed the compositional and structural changes of humic acid (HA) after combined with phosphate fertilizer (PHA), and investigated its effects on the growth of maize seedlings with four humic acid concentrations. The results showed that the atomic ratios of O/C and (O + N)/N of PHA were significantly lower than those of HA, which indicated that PHA had poor hydrophilicity compared with HA. The spectra of FTIR and NMR results suggested that the relative content of carboxyl group in PHA was higher than that in HA. X-ray photoelectron spectroscopy technology showed that the relative amount of C–C in PHA was lower than that in HA, while C–H was the opposite. The above changes were attributed to the crack of HA structure during the preparation of humic acid enhanced phosphate fertilizer, which was verified by the results from the determination of gel permeation chromatography that there were more low molecular weight components in PHA than that in HA. However, compared with HA, PHA showed a worse effect in promoting growth and the uptake of nitrogen, phosphorus and potassium by maize seedlings. This worse effect might be attributed to the poor hydrophilicity and unsuitable addition amount of PHA.

No abstract

No abstract

No abstract

BACKGROUND: Humic acid (HA)-enhanced urea (HAU) is the top-selling efficiency-enhanced urea in China. Comprehensive investigation into the structure and efficacy of HA complex formation with urea (HACU)the main reaction product during HAU's productionis required to clarify the reaction mechanism between HA and urea, and to provide guidance for the development of high-efficiency HAU.RESULTS: HACU showed discrepant structural and compositional features from raw HA. Nitrogen (N) content in HACU was 7.3 times greater than that of HA. Several high-resolution analytical methods showed a sharp increase of ammonia in the gaseous product during HACU pyrolysis, suggesting that urea contributed N to HACU. HACU was characterized with significantly fewer carboxyl groups than in raw HA, implying that the carboxyl group was the main group in HA to participate in the reaction between HA and urea. The presence of amide-N in HACU verified the structure of the reaction product. Furthermore, both HACU and HA could enhance the biomass in hydroponically grown maize seedlings, but the highest stimulation for HACU came about when its carbon concentrations were 50-100 mg L −1 , higher than the optimal carbon concentration for HA (25 mg L −1 ), attributed to the lower carboxyl group content for HACU to some extent. CONCLUSION: During HAU's production, reaction with N derived from urea to form amide-N decreased the carboxyl groups in HA, leading to higher concentrations for HACU required to achieve the similar bioefficacy of HA.

In the process of phosphate fertilizer production, adding humic acid to produce humic-acid-value-added phosphate fertilizer can improve fertilizer efficiency and promote crop growth. Although studies have primarily focused on investigating the impact of humic acid’s structure and function on phosphorus availability in humic-acid-added phosphate fertilizers, there is limited research on the regulatory effects of phosphorus fertilizer structure and the synergistic mechanisms involving microorganisms. Therefore, this study aimed to examine the chemical and biological mechanisms underlying the increased efficiency of humic-acid-added phosphate fertilizers by implementing various treatment processes. These processes included physically blending humic acid with phosphate fertilizer (HA+P), chemically synthesizing humic acid phosphate fertilizer (HAP), using commercially available humic acid phosphate fertilizer (SHAP), employing ordinary potassium phosphate fertilizer (P), and implementing a control treatment with no phosphate fertilizer (CK). Investigating the synergistic mechanism of humic-acid-added phosphate fertilizers holds significant importance. The results showed that during the preparation of HAP at high temperature, a new absorption peak appeared at 1101 cm−1, and a new chemical bond -O- was formed. The hydroxyl fracture in humic acid combined with phosphoric acid to form a phosphate ester (P-O-C=O) structure. HAP residues were concentrated on the surface and loaded with more soil minerals. The content of highly active oxygen-containing functional groups—such as aromatic C-O, carboxyl/amide carbon and carbonyl carbon—increased significantly, while the content of alkyl carbon, oxyalkyl carbon, and aromatic carbon decreased. Upon combining humic acid with potassium phosphate, the carboxyl group and calcium ions formed the HA-m-P complex, increasing the content of soluble phosphate (H2PO4−) in the soil by 1.71%. Compared to HA+P treatment, HAP treatment significantly increased the soil’s available P content by 13.8–47.7% (P < 0.05). The plant height, stem diameter, and above-ground biomass of HAP treatment were increased by 21.3%, 15.31%, and 61.02%, respectively, and the total accumulations of N, P, and K nutrient elements were increased by 6.71%, 31.13%, and 41.40%, respectively, compared to the control treatment. The results of high-throughput sequencing showed that the rhizosphere soil of HA+P and HAP treatment was rich in bacterial groups, the soil microbial structure was changed, and the bacterial community diversity was increased under HAP treatment. The number of genes encoding phytase and alkaline phosphatase associated with organophosphorus dissolution increased by 3.23% and 2.90%, respectively, in HAP treatment. Humic acid phosphate fertilizer forms phosphate esters in the process of chemical preparation. After application, the soil’s microbial community structure is changed, and soil enzyme activity related to phosphorus transformation is improved to promote tomatoes’ absorption of soil nutrients, thus promoting tomato plant growth and nutrient accumulation.

Incorporating humic acid (HA) into phosphate fertilizers to produce HA-enhanced phosphate fertilizers (HAPs) can improve the migration and availability of fertilizer-derived phosphorus (P) in soil. However, the optimal proportion of HA remains inconsistent. Here, we investigated the effects of HAPs with different HA proportions (0.1–10% w/w) on water-soluble P fixation rate, P migration, P transformation, and soil microorganisms, and analyzed the main P forms in HAP using Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The results showed that incorporating 0.1% HA had no impact on P migration and transformation, whereas incorporating 0.5–10% HA increased the migration distance and cumulative migration of fertilizer-derived P by 0–5 mm and 17.1–30.3%, respectively, compared with conventional phosphate fertilizer (CP). Meanwhile, HAPs with 0.5–10% HA significantly reduced the water-soluble P fixation rate by 18.3–25.6%, and significantly increased the soil average available P (AP) content in 0–40 mm soil layer around the P application site by 6.2–12.9% relative to CP, partly due to the phosphate monoesters in HAPs. Clustering analysis revealed that 0.5% HA had similar effects relative to higher HA proportions (1% and 5%), and the inhibition of HAP with 0.5% HA on bacteria and fungi was also greater than that of CP due to the high concentration of soil P. Overall, 0.5% was determined to be the optimal amount of HA for HAP production, which provided a theoretical basis for the development of high-efficiency phosphate fertilizer.

Cellulose, a kind of polymer containing abundant functional groups, has widespread use in the adsorptive removal of environmental pollutants. An efficient and environmental friendly polypyrrole (PPy) coating approach is employed to modify the agricultural by-product straw derived cellulose nanocrystal (CNC) into excellent property adsorbents for removing the heavy metal ion of Hg(II). The FT-IR and SEM-EDS results demonstrated that PPy is formed on the surface of CNC. Consequently, the adsorption measurements proved that the obtained PPy-modified CNC (CNC@PPy) possesses a remarkably enhanced Hg(II) adsorption capacity of 1095 mg g−1, owing to a plentiful functional group of doped Cl element on the surface of CNC@PPy by forming Hg2Cl2 precipitate. The results of the study suggest that the Freundlich model is more effective than the Langmuir model at describing the isotherms, while the pseudo-second order kinetic model is better suited to correlating with the experimental data compared to the pseudo-first order model. Further, the CNC@PPy exhibits an outstanding reusability, capable of maintaining 82.3% of its original Hg(II) adsorption capacity after five successive adsorption cycles. The findings of this work reveal a method to convert the agricultural by-product into high performance environmental remediation materials.