Co-pyrolysis of sewage sludge and phosphate tailings: Synergistically enhancing heavy metal immobilization and phosphorus availability.

Phosphate tailings (PT) was used to reduce the release of heavy metals (HMs) during pyrolysis and the leachable rate of residual HMs, and simultaneously improve the bioavailability of phosphorus in the sludge-based biochar. The concentration of heavy metals and the fractions determined by BCR method was used to investigate the release and the transformation of Zn, Pb, Mn, Ni and Cu during pyrolysis involved with the effects of temperature and the addition of PT. The respective pyrolysis experiments shows that the release of Zn and Pb increases with temperature for both sewage sludge (SS) and PT, and the bioavailable fractions (F1 + F2) of Mn, Ni, and Cu increases with temperature for PT. During co-pyrolysis, blended samples released lower quantities of Zn and Pb and presented lower bioavailability of HMs than the individual SS or PT. A synergistic effect of co-pyrolysis was evident for volatile Zn and Pb. The decomposition of CaMg (CO3)2 from PT produced CaO, by which the volatile ZnCl2 and PbCl2 were transformed into ZnO and PbO with less volatility and higher reactivity with SiO2 and Al2O3 than the chlorides. Then SiO2 and Al2O3 from SS acted as the final stabilizer to immobilize the oxides. The final product combined with SiO2 and Al2O3, such as ZnSiO4 and ZnAl2O4, were detected. The addition of PT also introduced more Ca and P into sludge to produce biochar with higher concentration of apatite phosphorus with higher bioavailability.

Speciation of La3+-Cl- Complexes in Hydrothermal Fluids from Deep Potential Molecular Dynamics.

The stability of rare earth element (REE) complexes plays a crucial role in quantitatively assessing their hydrothermal migration and transformation. However, reliable data are lacking under high-temperature hydrothermal conditions, which hampers our understanding of the association behavior of REE. Here a deep learning potential model for the LaCl3-H2O system in hydrothermal fluids is developed based on the first-principles density functional theory calculations. The model accurately predicts the radial distribution functions compared to ab initio molecular dynamics (AIMD) simulations. Furthermore, species of La-Cl complexes, the dissociation pathway of the La-Cl complexes dissociation process, and the potential of mean forces and corresponding association constants (logK) for LaCln3-n (n = 1-4) are extensively investigated under a wide range of temperatures and pressures. Empirical density models for logK calculation are fitted with these data and can accurately predict logK data from both experimental results and AIMD simulations. The distribution of La-Cl species is also evaluated across a wide range of temperatures, pressures, and initial chloride concentration conditions. The results show that La-Cl complexes are prone to forming in a low-density solution, and the number of bonded Cl- ions increases with rising temperature. In contrast, in a high-density solution, La3+ dominates and becomes the more prevalent species.

Utilizing CaCl2 to promote the enrichment and bioavailability of phosphorus in incinerated sludge ash.

Recovering phosphorus from incineration sludge sewage ash (ISSA) is a well-established technology, with a greater recovery potential than that of supernatant or sludge. ISSA can be utilized as a secondary raw material in the fertilizer industry, or as a fertilizer if heavy metal concentrations do not exceed permissible limits, thus reducing the cost of phosphorus recovery. Increasing the temperature to produce ISSA with higher solubility and plant availability of phosphorus is advantageous for both pathways. But a decrease in the extraction of phosphorus is also observed at high temperatures, thereby diminishing the overall economic benefits. In this study, CaCl2 was utilized to mitigate the decrease in the extraction rate and also to promote the bioavailability of phosphorus. The addition of CaCl2 (80 g/kg of dry sludge) effectively promoted the conversion of non-apatite inorganic phosphorus to apatite inorganic phosphorus at a rate of 87.73% at 750 °C. Furthermore, the decrease in the extraction rate of phosphorus at 1,050 °C was comparatively smaller in the presence of CaCl2. If iron flocculants are used to capture P in wastewater management, it may be necessary to pay special attention to the amount of addition and incineration temperature to maximize the economic potential of recycling.

Effect of Corn Straw Blending on Phosphorus Specification and Bioavailability of Incinerated Sludge Ash.

Phosphorus is a depletable resource, and the consumption of phosphorus fertilizer increases with the growing population size. Phosphorus recycled from incinerated sludge ash can be a complement to phosphatic fertilizers in districts suffering from phosphorus resource shortages (e.g., Germany, Japan, and Sweden). The apatite inorganic phosphorus (AP) content in incinerated sludge ash is a key factor influencing the recoverability and bioavailability. Biomass straw is rich in calcium and magnesium minerals and can be used as an additive to be blended with sludge to increase the AP content. However, most of the current studies added excessive amounts of calcium-based or biomass additives, and the bioavailability of various Ca-Mg-P minerals generated after the addition of biomass has not been systematically discussed. In this study, the changes of the phosphorus form in the mixed sludge and biomass with Ca/P in the range of 1.0-2.5 are studied, and the influence of temperature and additives on the phosphorus form and the bioavailability of phosphorus in the ash samples are discussed by combining X-ray diffraction and citric acid (CA) leaching experiments. The AP content is very low in the residue of the sludge or corn straw (CS) that has been burned individually. The sludge and the blended sludge and CS were incinerated at various temperatures. As the incineration temperature increased, the conversion of non-apatite inorganic phosphorus (NAIP) to AP was promoted, but the bioavailability did not change until 1050 °C for samples with a Ca/P of 2.5. In the range from 750 to 950 °C, higher temperature promotes the formation of Ca2P2O7 and CaP2O6. CaP2O6 is insoluble in CA; thus, the bioavailability changes little from 750 to 950 °C, although the AP content increases. With the increase of Ca/P, the conversion of NAIP to AP and the bioavailability of phosphorus were promoted. For the blended sludge and CS ash, Ca7Mg2P6O24 appears at 950 and 1050 °C and the bioavailability also increases.