Phosphate solubilizing fungi (PSF) have been widely applied to dissolve insoluble phosphates (IPs). However, the PSF usually demonstrates a different phosphate solubilizing capacity for various IPs. This study explored the mechanisms of Aspergillus niger for the dissolution of ferric phosphate (FePO₄, Fe-P), and tricalcium phosphate (Ca₃[PO₄]₂, Ca-P) regarding the tricarboxylic acid (TCA) cycle. Aspergillus niger has higher phosphorus (P) content released from Ca-P, reached the maximum value of 861 mg/L after seven days of incubation, compared with the 169 mg/L from Fe-P. Oxalic acid promoted the release of P from Ca-P through the formation of calcium oxalate. The presence of Fe-P can stimulate A. niger to secrete large amounts of citric acid, confirmed by the enhancement of citrate synthase (CS) activity. However, citric acid only promotes 0.5% of P released from Fe-P. Meanwhile, although oxalic acid still dominates the release of P from Fe-P, its abundance was significantly declined. In contrast, oxalic acid also shows a higher P release ratio in Ca-P than citric acid, i.e., 36% vs. 22%. This study points to the future usage of A. niger to dissolve IPs in soil required to enhance oxalic acid secretion.

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.

Phosphogypsum (PG) is a by-product of the phosphorus (P) chemical industry, and usually contains ~2% residual phosphate. The P in PG would cause P pollution in the environment by the way of long-term stacking. Phosphate-solubilizing fungi (PSF) can effectively promote the release of P from insoluble phosphate. The aim of this study was to investigate the P release capacity between tricalcium phosphate (TCP) and PG by Aspergillus niger (ANG) via flask experiment. At the same time, the application of PG fertilizer (PGF) in soil was also performed. The dry biomass of ANG between TCP and PG treatment reached the maximum value of 0.71 and 0.38 g, respectively, after five days of incubation. The maximum P concentrations released from PG and TCP by ANG is five and seven days, i.e., 128 and 1103 mg/L, respectively. PG has a similar P release ratio compared with TCP by ANG, i.e., 52% vs. 55%. In the soil incubation experiment, PGF can significantly increase the soil available P content and continuously maintain the high concentration (17.2 mg/kg) after four weeks of incubation. The utilization of PG by ANG via the PGF is a feasible pathway to increase the soil P content, especially for the sustainable use of phosphate resources.