Phosphorus removal in constructed wetlands have received particular attention last decades by using specific materials promoting adsorption/precipitation mechanisms. Recent studies have shown interest in using apatite materials to promote P precipitation onto the particle surface. As previous trials were mainly done by lab experiments, this present study aims to evaluate the real potential of apatites to remove P from wastewater in pilots and a full-scale plant. Two different apatites have been studied in 1.5 m² pilots fed with wastewater from the outlet of a trickling filter. They were monitored to follow inlet/oulet flows, hydraulic gradient, meteorological conditions, pH, temperature, and redox potential. Treatment performances were evaluated by regular complete analysis (COD, BOD, SS, nitrogen and phosphorus forms, Ca) as well as PO4-P by a WTW online analyser. At the same time a full-scale experiment study have been done to point out P retention properties in real conditions over a 2 years period. P retention kinetics of two qualities of apatites are presented and discussed according to the temperature dependence. In this work apatite appears to have high retention capacity and is still an interesting way for P removal in constructed wetlands. However, other qualities of apatite must be studied for a better reliability of treatment.

The sorption of selenite, SeO32−, by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m2/g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, Kd, determined for the carbonated apatite in this work ranged from approximately 4200 to over 14,000 L/kg. A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. The results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.

Soil receiving discharges from Pb-acid batteries dismantling and restoring units (PBS) can have a high concentration of phytoavailable Pb. Reducing Pb phytoavailability in PBS can decline Pb uptake in food crops and minimize the risks to humans and the environment. This pot study aimed to reduce the concentration of phytoavailable Pb in PBS through Aspergillus niger (A. niger)−mediated release of PO₄³⁻ from fish bone [Apatite II (APII)] products. The PBS (Pb = 639 mg kg⁻¹ soil) was amended with APII powder (APII−P), APII char (APII−C), and A. niger inoculum as separate doses, and combining A. niger with APII−P (APII−P + A. niger) and APII−C (APII−C + A. niger). The effects of these treatments on reducing the phytoavailability of Pb in PBS and its uptake in fenugreek were examined. Additionally, enzymatic activities and microbial biomass carbon (MBC) in the PBS and the indices of plant physiology, nutrition, and antioxidant defense machinery were scoped. Results revealed that the APII−C + A. niger treatment was the most efficient one. Compared to the control, it significantly reduced the Pb phytoavailability (DTPA-extractable Pb fraction) in soil and its uptake in plant shoots, roots, and grain, up to 61%, 83%, 74%, and 92%. The grain produced under APII−C + A. niger were safe for human consumption as Pb concentration in grain was 4.01 mg kg⁻¹ DW, remaining within the permissible limit set by WHO/FAO (2007). The APII−C + A. niger treatment also improved soil pH, EC, CEC, MBC, available P content and enzymatic activities, and the fenugreek quality parameters. A. niger played a significant role in solubilizing PO₄³⁻ from APII−C, which reacted with Pb and formed insoluble Pb-phosphates, thereby reducing Pb phytoavailability in PBS and its uptake in plants. This study suggests APII−C + A. niger can remediate Pb-polluted soils via reducing Pb phytoavailability in them.

Topsoils near active and abandoned mining and smelting sites are highly polluted by metal(loid) contaminants, which are often bound to particulates emitted from ore processing facilities and/or windblown from waste disposal sites. To quantitatively determine the contaminant partitioning in the soil particulates, we tested an automated mineralogy approach on the heavy mineral fraction extracted from the mining- and smelting-polluted topsoils exhibiting up to 1920 mg/kg As, 5840 mg/kg Cu, 4880 mg/kg Pb and 3310 mg/kg Zn. A new generation of automated scanning electron microscopy (autoSEM) was combined and optimized with conventional mineralogical techniques (XRD, SEM/EDS, EPMA). Parallel digestions and bulk chemical analyses were used as an independent control of the autoSEM-calculated concentrations of the key elements. This method provides faster data acquisition, the full integration of the quantitative EDS data and better detection limits for the elements of interest. We found that As was mainly bound to the apatite group minerals, slag glass and metal arsenates. Copper was predominantly hosted by the sulfides/sulfosalts and the Cu-bearing secondary carbonates. The deportment of Pb is relatively complex: slag glass, Fe and Mn (oxyhydr)oxides, metal arsenates/vanadates and cerussite were the most important carriers for Pb. Zinc is mainly bound to the slag glass, Fe (oxyhydr)oxides, smithsonite and sphalerite. Limitations exist for the less abundant contaminants, which cannot be fully quantified by autoSEM due to spectral overlaps with some major elements (e.g., Sb vs. Ca, Cd vs. K and Ca in the studied soils). AutoSEM was found to be a useful tool for the determination of the modal phase distribution and element partitioning in the metal(loid)-bearing soil particulates and will definitely find more applications in environmental soil sciences in the future.

Several studies have shown Soluble Reactive Phosphorus (SRP) analyses provide a poor index of dissolved phosphorus (P) bioavailability in natural systems. We tested 21 inorganic and organic P containing compounds with series of nutrient uptake and bioavailability bioassay experiments and chemical characterizations. Our results show that in 81% of cases, these compounds did not fit the classic assumption that SRP approximately equals Bioavailable P (BAP). Many organic compounds were classified as non-reactive, but had very rapid uptake kinetics and were nearly entirely bioavailable (e.g., several nucleic acids, ATP, RNA, DNA and phosphatidylcholine). Several inorganic compounds also classified as non-reactive but had high bioavailability (i.e., sodium tripolyphosphate and phosphorus pentoxide). Conversely, apatite was operationally classified as reactive, but had low bioavailability. Due to their tendency to alias as SRP, but recalcitrance and very low bioavailability, humic-(Al/Fe)-phosphorus complexes may play an especially important role in the dissolved phosphorus dynamics of natural systems.

Phosphorus (P) in surface sediments of the Laizhou Bay (LB) and the coastal waters around the Zhangzi Island (ZI) was analyzed. Six forms of P were separated — exchangeable or loosely sorbed P (Ads–P), aluminum-bound P (Al–P), iron-bound P (Fe–P), authigenic apatite plus CaCO3-bound P plus biogenic apatite (Ca–P), detrital apatite plus other inorganic P (De–P) and organic P (OP). The average contents of P in the LB were in the order: De–P>OP>Ca–P>Fe–P>Ads–P>Al–P; in the ZI, the corresponding order was De–P>OP>Fe–P>Ca–P>Ads–P>Al–P. Due to the high nutrient loadings from the surrounding rivers, TP contents in sediments of the LB were higher than in those of the ZI. The potential bio-available P (Ads–P and OP) accounted for 14.7% and 24.2% of TP in sediments of the LB and the ZI, respectively.

In this research, the influence of application mode (capping and amendment) on the control of cadmium (Cd) liberation from sediment by apatite/calcite mixture and its phosphorus release risk were investigated. The results showed that calcite addition had a limited effect on the speciation of Cd in sediment, but apatite addition had a significant impact on the fractionation of Cd in sediment. Apatite amendment could effectively immobilize the most readily mobilized Cd by transferring the acid-soluble fraction to the reducible and residual fractions. Apatite addition also could effectively reduce the concentration of toxicity characteristic leaching procedure (TCLP)-leachable Cd in sediment, and apatite had a much higher reduction efficiency of TCLP-leachable Cd than calcite. Apatite/calcite mixture capping could reduce the risk of Cd liberation from sediment into the overlying water, and the controlling efficiency of apatite/calcite mixture capping was higher than that of apatite/calcite mixture amendment. The effect of apatite/calcite mixture addition on the concentration of reactive soluble phosphorus (SRP) in the overlying water was limited. The introduction of calcite into the apatite capping layer could lower the risk of phosphorus release from apatite to the overlying water as compared to single apatite capping. However, the apatite/calcite mixture capping layer still had a relatively high risk of phosphorus liberation into the overlying water. Results of this work suggest that apatite/calcite mixture has a high potential to be used as a capping material to control Cd release from sediment from the perspective of controlling efficiency and application convenience.

The phosphorus-sulfur two-step production process was developed in the wet-process phosphoric acid industry to solve phosphogypsum pollution. However, phosphate rock acid-insoluble residue is produced during this process as a new type of solid waste, which had a high potential for recycling. For process reasons, this type of residue still contains a certain amount of fluorine and phosphorus, which has a massive impact on the potential uses of phosphate rock acid-insoluble residue. Therefore, X-ray photoelectron spectroscopy, Raman, electron probe spectroscopy, and scanning electron microscopy were used to examine the existing form and distribution of fluorine and phosphorus in phosphate rock acid-insoluble residue. The mass fraction of F and P₂O₅ were 9.407% and 11.862%, respectively. Fluorine existed mainly in the form of fluorite, fluorapatite and metal fluoride. Phosphorus existed mainly in the form of fluoroapatite, phosphate, hydrogen phosphate, and dihydrogen phosphate. The total phosphate, hydrogen phosphate and dihydrogen phosphate contents were much higher than that of fluoroapatite, whereas the fluoroapatite content was higher than that of fluorite and metal fluoride. Fluorine and phosphorus were distributed in the form of agglomerates in the phosphate rock acid-insoluble residue. Fluorine and phosphorus were partially correlated, showing a weak relationship in the high phosphorus area.

The recovery and recycling of nutrients (N&P) from wastewater are one of the major topics to save primary energy and resources, to raise the efficiency of wastewater treatment plants, and to foster a future circular economy. In the present study, the removal of ammonium (NH₄⁺) and phosphate (PO₄³⁻) using natural and Ca-treated zeolite is investigated in detail. Special emphasis is put on the simultaneous removal of both species from model solutions followed by elaborate mineralogical analyses (XRD, EPMA, FEG-SEM) for zeolite characterization and in order to determine the type, structure, and crystal sizes of CaP-phases precipitating on the zeolites surface. The effectivity of the phosphate segregation and chemical composition and the crystalline structure of the CaP-phase precipitating on the surface of the zeolite depend on the physico chemical conditions in particular on pH, molar ratio of Ca and P (due to zeolite modification), and the presence of NH₄⁺. Results of simultaneous removal experiments of N&P revealed that Ca pretreatment enhances P segregation and increases the obtainable P-loadings of Ca–zeolites. Maximum P-loadings of 25 mg g⁻¹ Ca–zeolite in binary solutions containing both ammonium and phosphate were obtained. Simultaneous phosphate removal by surface precipitation of CaP-phases does not significantly influence ammonium ion exchange and the type of CaP-precipitates formed on the zeolite surface is assumed to be mainly brushite and apatite.

Fluorapatite (FAp) is the largest phosphorous (P) reservoir on Earth. However, due to its low solubility, dissolved P is severely deficient in the pedosphere. Fungi play a significant role in P dissolution via excretion of organic acids, and in this regard, it is important to understand their impact on P cycling. The object of this study was to elucidate the balance between P release and F toxicity during FAp dissolution. The bioweathering of FAp was assisted by a typical phosphate-solubilizing fungus, Aspergillus niger. The release of elements and microbial activities were monitored during 5-day incubation. We found that the release of fluorine (F) was activated after day 1 (~90 mg/L), which significantly lowered the phosphate-solubilizing process by day 2. Despite P release from FAp being enhanced over the following 3 days, decreases in both the amount of biomass (52% decline) and the respiration rate (81% decline) suggest the strong inhibitory effect of F on the fungus. We thus concluded that F toxicity outweighs P supply, which in turn inhibits fungi growth and prevents further dissolution of FAp. This mechanism might reflect an underappreciated cause for P deficiency in soils.