Phosphorus fractions and speciation in an alkaline, manured soil amended with alum, gypsum, and Epsom salt.

Snowmelt runoff is a dominant pathway of phosphorus (P) losses from agricultural lands in cold climatic regions. Soil amendments effectively reduce P losses from soils by converting P to less soluble forms; however, changes in P speciation in cold climatic regions with fall-applied amendments have not been investigated. This study evaluated P composition in soils from a manured field with fall-amended alum (Al2(SO4)3·18H2O), gypsum (CaSO4·2H2O), or Epsom salt (MgSO4·7H2O) using three complementary methods: sequential P fractionation, scanning electron microscopy with energy-dispersive X-rays (SEM-EDX) spectroscopy, and P K-edge X-ray absorption near-edge structure spectroscopy (XANES). Plots were established in an annual crop field in southern Manitoba, Canada, with unamended and amended (2.5 Mg ha-1) treatments having four replicates in 2020 fall. Soil samples (0-10 cm) taken from each plot soon after spring snowmelt in 2021 were subjected to P fractionation. A composite soil sample for each treatment was analyzed using SEM-EDX and XANES. Alum- and Epsom salt-treated soils had significantly greater residual P fraction with a higher proportion of apatite-like P and a correspondingly lower proportion of P sorbed to calcite (CaCO3) than unamended and gypsum-amended soils. Backscattered electron imaging of SEM-EDX revealed that alum- and Epsom salt-amended treatments had P-enriched microsites frequently associated with aluminum (Al), iron (Fe), magnesium (Mg), and calcium (Ca), which was not observed in other treatments. Induced precipitation of apatite-like species may have been responsible for reduced P loss to snowmelt previously reported with fall application of amendments.

Staged purification of phosphogypsum using pH-dependent separation process.

Phosphogypsum (PG) is an industrial by-product of the transformation of phosphate rocks. For decades, PG has been a source of environmental concern due to the massive amount produced thus far, i.e., 7 billion tons, with a current production rate of 200-280 million tons per year. Phosphate minerals contain various impurities that precipitate and concentrate within PG. These impurities hinder PG usability in various sectors. This paper aims to purify PG using an innovative process based on staged valorization of PG. Initially, PG dissociation by ethylenediaminetetraacetic acid (EDTA) was optimized. After screening of different parameters and monitoring the ionic conductivity of solutions, it was disclosed that a pH-dependent solubilization process in the presence of EDTA resulted in high solubility of PG, up to 11.82 g/100 mL at pH > 11. Subsequently, a recovery of the purified PG by selective precipitation of calcium sulfate dihydrate (CSD) from obtained filtrate through pH adjustment to 3.5 were investigated. An abatement of 99.34% Cr, 97.15% Cd, 95.73% P2O5, 92.75% Cu, 92.38% Al2O3, 91.16% Ni, 74.58% Zn, 72.75% F, 61.43% MgO, 58.8% Fe2O3, 56.97% K2O, and 55.41% Ba was achieved. The process relied on the variation of EDTA chelation properties towards monovalent, divalent, and trivalent cations at different pHs. According to the findings of this study, a staged purification process in the presence of EDTA is an effective method for removing impurities from the industrial PG.

Enhancing dissolved inorganic phosphorous capture by gypsum-incorporated biochar: Synergic performance and mechanisms.

Excess nutrients, such as phosphorus (P), in watersheds jeopardize water quality and trigger harmful algal blooms. Using phosphorus sorption material (PSM) to capture P from wastewater and agricultural runoff can help recover nutrients and prevent their water pollution. In this study, a novel designer biochar was generated by pyrolyzing woody biomass pretreated with a flue gas desulfurization gypsum. The removal of dissolved inorganic phosphorus (DIP) by the gypsum-incorporated designer biochar was more efficient than the gypsum, suggesting the pretreatment of biomass with the gypsum results in a synergic effect on enhancing DIP capture. The maximum P adsorption capacity of the designer biochar was more than 200 mg g-1 , which is one order of magnitude greater than that of the gypsum. This result clearly showed that the designer biochar is a better PSM to capture DIP from nutrient-contaminated water compared to the gypsum. Post-sorption characterization indicated that the sorption of DIP by the gypsum-incorporated biochar involves multiple mechanisms. The precipitation reactions of calcium (Ca) cations and P anions to form CaHPO4 and Ca3 (PO4 )2 precipitates on the highly alkaline surface of the designer biochar were identified as a main mechanism. By contrast, CaHPO4 ·2H2 O is the only precipitated product for DIP sorption by the gypsum. In addition, the initial solution pH and the coexisting bicarbonate had less effects on the DIP removal by the designer biochar in comparison with the gypsum, which further confirms that the former is an excellent PSM to capture DIP from a variety of aquatic media.

Examination of the environmental behavior of phosphogypsum with the application of lab-scale experiment.

Phosphogypsum (PG) is a reject of the phosphoric acid production process in phosphate fertilizer industries. The process results in the production of relatively large quantities of PG that it might cause serious environmental and human health concerns. The data of a laboratory investigation of PG are presented here. Lab-scale experiments with lysimeters were conducted in order to simulate and examine the environmental characteristics and the temporal behavior of PG leachates in terms of physicochemical characteristics and chemical composition. Based on the results, leachates from already deposited for many years PG or its mixture with marble powder, seemed to have better pH and conductivity values and lower elemental concentrations compared to leachates from freshly disposed PG. However, the leachates characteristics improve and stabilize in both cases after four days of irrigation or of 1080-1240 mm of rain. Most major elements were found to have minimal leachability, and the material satisfied the environmental limits for its disposal at landfills for inert and non-hazardous wastes.

Enhancing bauxite residue properties for plant growth: Gypsum and organic amendment effects on chemical properties of soil and leachate.

Here, we assess the effects of gypsum and local organic waste as amendments to non-weathered, filter-pressed bauxite residue (BR) to improve its properties and support plant growth. In addition, we monitored the leachate quality of the amended BR under progressive leaching that simulated precipitation conditions in Northern Brazil. Free-draining column tests consisting of BR amended with gypsum and organic waste, at 5% and 10% w/w, respectively, were leached for 8 weeks to assess the effects on the chemical composition of BR and the leachates. Adding gypsum to BR reduced the exchangeable sodium (Na) percentage (ESP) from approximately 79%-48%, whereas adding only organic waste had smaller effects on ESP (from ∼79% to âˆ¼ 70%). The mean leachate pH ranged from 8.7 to 9.4 for the gypsum, and organic waste amended BR, while this was 10.3 in the leachate of the unamended BR. The treatments had similar trends of electrical conductivity throughout the experiments and were below 2 dS/cm after 8 weeks, when ∼1.700 mm simulated precipitation had leached. Aluminium (Al), Arsenic (As), and Vanadium (V) concentrations in leachates of BR with gypsum, either alone or in combination with organic waste, were significantly lowered than in leachate of non-amended BR. By contrast, metal concentrations increased if organic waste was added to BR. We conclude that amending BR with gypsum, in combination with organic waste, significantly improves the chemical properties of the solid phase and achieved rehabilitation goals for SAR and EC of the leachates after 8 weeks of leaching. However, despite high leaching rates, rehabilitation goals for pH and ESP were not achieved with gypsum either alone or combined with organic waste.

Effect of phosphate rock acid insoluble residue on hydration process and mechanical properties of α-hemihydrate gypsum.

The application of α-hemihydrate gypsum (α-HH) is limited by several factors, such as a rapid hydration rate, short setting time, poor water resistance, and high cost. Especially because of the high production cost, although α-HH has excellent mechanical strength, it is rarely used in the field of building materials. In this study, based on the composition characteristics of new industrial solid waste (phosphate-rock acid-insoluble residue, PAIR) and to meet the needs of resource utilization, gypsum matrix composites were prepared by adding PAIR to α-HH to solve the problems of short setting time and poor water resistance of gypsum matrix composites and improve the comprehensive properties of α-HH products. The results show that when the different types of pores formed during the hydration of α-HH were filled with inert substances, such as silicon dioxide, insoluble phosphate, and calcium fluoride from PAIR, the proportion of mesopores in the composite products increased, whereas that of harmful macropores decreased. The compressive and flexural softening coefficients of the PAIR/α-HH system with 23% PAIR were the highest at 57.25 and 60.125%, respectively, and the water resistance of the system was improved; when the content of PAIR reaches 35%, the strength of the composite products decreased from 58.125 to 43.8 MPa. The HPO42- in PAIR partially replaces the SO42- ion in the dihydrate gypsum (DH) lattice to form a Ca(SO4, HPO4)•2H2O double salt, leading to the production of eutectic phosphorus. Soluble F-, Al3+, Mg2+, and phosphorus-containing substances in PAIR form a variety of complex ions in PAIR/α-HH aqueous solution, which are adsorbed onto the surface of the new DH phase; the crystal morphology changed from thick, long columns to clusters, thin rods, and plates, inhibiting the nucleation and growth of DH and changing its crystal growth rate and crystallization behavior. Therefore, the setting time of gypsum is prolonged; when 35% PAIR was added, the induced nucleation period of the PAIR/α-HH system was prolonged from 40 to 265 min, and the final setting time was from 12 to 360 min. By mixing solid waste PAIR, while the setting time of α-HH is prolonged, its water resistance is improved, and its mechanical strength is not significantly reduced, reducing the cost. From the perspective of economy and environmental protection, this study is a way to α-HH is widely used in the field of building materials.

Geochemical and mineralogical characterization of phosphogypsum and leaching tests for the prediction of the mobility of trace elements.

Phosphoric acid manufacturing generates large amounts of phosphogypsum (PG); a by-product generally disposed in the surface or evacuated in the seawater without any pretreatment. Phosphogypsum may host non-negligible amounts of valuable elements such as rare earth elements (REEs), which are critical elements on the global market. Surface disposal of PG may be a sustainable option to allow further processing in order to recover valuable elements. However, surface disposal exposes PG to atmospheric conditions (e.g., water, oxygen) which may increase their reactivity and accelerate the release rate of chemical species. This study aims to evaluate the trace element release rate from PG at atmospheric conditions. The studied PG samples were collected from a Moroccan phosphate treatment plant. The samples were characterized for their (i) chemical composition using inductively coupled plasma optical emission spectrometry (ICP-OES) for major elements and inductively coupled plasma mass spectrometry (ICP-MS) for trace elements; (ii) mineralogical composition by X-ray diffraction (XRD), scanning electron microscope equipped with energy-dispersive spectrometer (SEM-EDS), laser-induced breakdown spectroscopy (LIBS), and the mineral chemical composition was analyzed by electron probe microanalyzer (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS); and (iii) chemical species release rate using leaching tests over 24 h at 25 and 60 °C. Chemically, the PG samples were mainly composed of Ca (23.03-23.35 wt.%), S (17.65-17.71 wt.%), and Si (0.75-0.82 wt.%), and non-negligible amounts of trace elements: REE (344-349 ppm), Cd (3.5-7.4 ppm), U (9.3-27.4 ppm). Mineralogically, the PGs are mainly formed by gypsum (94.2-95.9 wt.%) and quartz (1.67-1.76 wt.%). In terms of chemical species release, the PGs showed a higher reactivity at 60 °C compared to room temperature with a higher release rate at the beginning of the leaching tests. Quantitatively, the PG samples released 3.57-4.11 µg/L/day of REE, 3.18-17.29 µg/L/day of U, and 1.67-5.49 µg/L/day of Cd. Based on the leaching results, we concluded that the trace elements (e.g., U, Cd, REE) are incorporated in PG crystal lattice, which may explain their low concentrations in the leachates. Consequently, total digestion of PG matrix is required to solubilize REE.

A novel and sustainable approach for biotransformation of phosphogypsum to calcium carbonate using urease producing Lysinibacillus sphaericus strain GUMP2.

Phosphogypsum (CaSO4) is produced as a waste by-product during phosphoric acid production in the fertilizer industry. Only 15% of worldwide phosphogypsum production is recycled, while 85% is stored in the vicinity of factories as huge piles resulting in environmental and health hazards. An extensively studied biotransformation of phosphogypsum to calcium carbonate or calcite (CaCO3) using sulfate reducing bacteria (SRBs) is a prolonged process and results in the formation of extremely hazardous H2S gas. Here we report for the first time a novel approach for biotransformation of phosphogypsum to CaCO3 using urease producing Lysinibacillus sphaericus strain GUMP2. The strain could effectively transform phosphogypsum to crystalline, bead-shaped CaCO3 precipitates. In a batch reactor with the PG loading rate of 60 g/L, 100% biotransformation was observed within seven days. After calcite recovery, the ammonium sulfate formed in the supernatant was recovered by precipitation. Urease-producing L. sphaericus strain GUMP2 could be used to remove the hazardous phosphogypsum from the environment by converting it to the industrially useful CaCO3 and ammonium sulfate, a valuable agricultural fertilizer. This novel and sustainable approach could be a promising solution for the hazardous phosphogypsum in the phosphoric acid industries.

An assessment of physical properties and the viability of osteoblast-like cells of cefazolin-impregnated calcium sulfate bone-void filler.

Calcium sulfate, an injectable and biodegradable bone-void filler, is widely used in orthopedic surgery. Based on clinical experience, bone-defect substitutes can also serve as vehicles for the delivery of drugs, for example, antibiotics, to prevent or to treat infections such as osteomyelitis. However, antibiotic additions change the characteristics of calcium sulfate cement. Moreover, high-dose antibiotics may also be toxic to bony tissues. Accordingly, cefazolin at varying weight ratios was added to calcium sulfate samples and characterized in vitro. The results revealed that cefazolin changed the hydration reaction and prolonged the initial setting times of calcium sulfate bone cement. For the crystalline structure identification, X-ray diffractometer revealed that cefazolin additive resulted in the decrease of peak intensity corresponding to calcium sulfate dihydrate which implying incomplete phase conversion of calcium sulfate hemihydrate. In addition, scanning electron microscope inspection exhibited cefazolin changed the morphology and size of the crystals greatly. A relatively higher amount of cefazolin additive caused a faster degradation and a lower compressive strength of calcium sulfate compared with those of uploaded samples. Furthermore, the extract of cefazolin-impregnated calcium sulfate impaired cell viability, and caused the death of osteoblast-like cells. The results of this study revealed that the cefazolin additives prolonged setting time, impaired mechanical strength, accelerated degradation, and caused cytotoxicity of the calcium sulfate bone-void filler. The aforementioned concerns should be considered during intra-operative applications.

Continuous and simultaneous conversion of phosphogypsum waste to sodium sulfate and potassium sulfate using quaternary phase diagram.

In this present work, the transformation of the Moroccan phosphogypsum (PG) waste, considered a potential source of sulfate, into potassium sulfate compound could help reduce environmental impact and create a new value chain for the phosphate industry. Generally, solid-liquid equilibria are frequently applied in chemical industries. They are a valuable aid in visualizing the precipitation, separation, and purification of a solid phase and the pathways by which crystallization can occur. This process aims to produce potassium sulfate (K2SO4), a high-value fertilizer, from sulfate solutions obtained after dissolving PG in a NaOH medium. The quaternary phase diagram Na+, K+//Cl-, SO42--H2O at 25 °C was especially used to determine the operating conditions and the design of a crystallization process during the PG conversion into K2SO4. The Jänecke representation of this system enables the determination of the optimal trajectory in the phase diagram for the double decomposition reaction. X-ray fluorescent (XRF) and X-ray diffraction (XRD) techniques were conducted to identify the crystalline phases formed during our process. In summary, the results of this study could contribute to the development of a sustainable valorization PG. Furthermore, K2SO4 represents a good alternative to potassium chloride for chloride-sensitive crops.

Characteristic pollutant purification analysis of modified phosphogypsum comprehensive utilization.

The waste product phosphogypsum (PG) is produced in phosphoric acid production processes. Its storage requires large amounts of land resources and poses serious environmental risks. In this work, detailed experimental research was carried out to investigate the potential reuse of PG after calcination modification as a novel building material for cast-in-place concrete products. The calcination modification mechanism was studied, and the environmental risk assessment of modified PG was presented. The results showed that the calcination modification includes crystal phase transformation, removal of impurities, and modifying the pH value. The calcination was carried out at 280 °C for 5 h, where the resulting product was a pH value of 7.1, and the soluble fluorine and phosphorus removal rates reached up to 69.2% and 71.2%, respectively. These removal rates met the requirements of the China national standard Phosphogypsum (GB/T 23456-2018). To ensure the environmental safety, ecological risk assessment methods for determining the leaching toxicity of the modified PG were employed. The toxicity of Ba and P elements in the modified PG products was assessed, as well as the leaching toxicity concentrations of all particular heavy metals, which were found well below the limits set by the national standards. All the results presented strongly suggest that the 280 °C modified PG presented here has excellent application potential as a raw component in building materials.

Flotation purification of waste high-silica phosphogypsum.

High-silica phosphogypsum (PG) is a kind of industrial by-product with great utilization potential. However, it is difficult to reuse PG directly due to the related gangue minerals (e.g., SiO2), and thus efficient purification is required to allow its further applications. Herein, a typical high-silica phosphogypsum waste was purified by a new "reverse-direct flotation" method. The organic matters and fine slimes were removed by reverse flotation, and then, the silica impurity was removed by direct flotation. Via the closed-circuit flotation process, the whiteness of the PG concentrate is improved from 33.23 to 63.42, and the purity of gypsum in the PG concentrate increases from 83.90% to 96.70%, with a gypsum recovery of 85%. Additionally, the content of SiO2 is significantly reduced from 11.11% to 0.07%. In-depth investigations suggest that the difference in the floatability of gypsum and quartz is prominently intensified by flotation reagents at pH = 2-2.5, and thus leads to good desilication performance. Further characteristics of the PG concentrate prove that impurities have been well removed, and the PG concentrate meets the requirement of related standards for gypsum building materials. The flotation method reported here paves the way for the purification of high-silica phosphogypsum, which can be extended to the purification and value-added reutilization of other industrial solid wastes.

Potential uses of phosphogypsum: A review.

Phosphogypsum (PG) is a by-product of the phosphate fertilizer industry that is produced during the phosphoric acid production process. Annual global PG production ranges between 100 to 300 Mt, with only 15% of that utilized while the rest is usually placed on large dumps with potential serious human and environmental impacts. The aim of this study is to give an overview and to evaluate the existing and potential uses of PG that extend from soil stabilization to cement and chemical industry and for agricultural to geotechnical, human impacts, and environmental applications. More specifically, PG can be used as a substitute in the cement industry, in building materials and in road construction, as a fertilizer for soil improvement, as a raw material for the production of some chemicals, and as a backfilling material for the rehabilitation of abandoned mines and quarries, while the recovery of gypsum and the extraction of rare earth elements signifies the potential importance of PG to cyclic economy. The paper offers an extensive overview of existing and potential uses of PG, discusses their adequacy, and reveals that PG can be widely used under certain conditions, rather than disposed as waste in stockpiles.

Utilization path of bulk industrial solid waste: A review on the multi-directional resource utilization path of phosphogypsum.

Phosphogypsum is one of the hottest issues in the field of environmental solid waste treatment, with complex and changeable composition. Meanwhile, phosphogypsum contains a large number of impurities, thus leading to the low resource utilization rate, and it can only be stockpiled in large quantities. Phosphogypsum occupies a lot of land and poses a serious pollution threat to the ecological environment. This paper mainly summarizes the existing pretreatment and resource utilization technology of phosphogypsum. The pretreatment mainly includes dry method and wet method. The resource utilization technology mainly includes building materials, chemical raw materials, agriculture, environmental functional materials, filling materials, carbon sequestration and rare and precious extraction. Although there are many aspects of resource utilization of phosphogypsum, the existing technology is far from being able to consume a large amount of accumulated and generated phosphogypsum. Through the analysis, the comparison and mechanism analysis of the existing multifaceted and multi-level resource treatment technologies of phosphogypsum, the four promising resource utilization directions of phosphogypsum are put forward, mainly including prefabricated building materials, eco-friendly materials and soil materials, and new green functional materials and chemical fillers. Moreover, this paper summarizes the research basis of multi field and all-round treatment and disposal of phosphogypsum, which reduces repeated researches and development, as well as the treatment cost of phosphogypsum. This paper could provide a feasible research direction for the resource treatment technology of phosphogypsum in the future, so as to improve the consumption of phosphogypsum and reduce environmental risks.

Identifying alternative antibiotics that elute from calcium sulfate beads for treatment of orthopedic infections.

There has been increasing interest in the use of a synthetic absorbable calcium sulfate (CaSO4 ) for local antibiotic delivery in orthopaedic infections. The purpose of this study was to quantify elution kinetics of six antibiotics (amikacin, meropenem, fosfomycin, minocycline, cefazolin, and dalbavancin) from a clinically relevant CaSO4 bead model and compare elution and antimicrobial activity to the current clinical gold standards: vancomycin and tobramycin. Antibiotic-loaded synthetic CaSO4 beads were immersed in phosphate buffered saline and incubated at 37°C. Eluent was harvested at eight time points over 28 days. Antibiotic concentrations were measured by high performance liquid chromatography to quantify elution rates. CaSO4 beads demonstrated burst release kinetics. Dalbavancin, cefazolin, and minocycline all demonstrated similar elution profiles to vancomycin. Amikacin and meropenem demonstrated favorable elution profiles and durations of above-minimum inhibitory concentration when compared to tobramycin. Clinical Significance: This study provides important novel data regarding the utility of amikacin, meropenem and dalbavancin as alternative choices to place in CaSO4 carriers when treating orthopaedic infections.

Effects of increasing concentrations of unamended and gypsum modified bauxite residues on soil microbial community functions and structure - A mesocosm study.

Bauxite residues (BR), commonly named red muds, are the saline-sodic waste produced during the extraction of alumina from bauxite. In this study, four kinds of BR were mixed at increasing concentrations with two soils in a mesososm experiment. Unamended BR from Provence (PRO) and Guinea (GUI) bauxite were selected, and Modified Bauxite Residues from PRO and GUI (MBR-PRO and MBR-GUI) were obtained by gypsum application and repeated leaching, in order to reduce their pH, electrical conductivity (EC) and exchangeable sodium percentage (ESP). Several indicators of microbial community functions and structure (growth of culturable bacteria; enzymatic activities; C-sourced substrates degradation (Biolog®); bacteria and fungi PCR-RFLP fingerprints) were measured after 35 days of incubation. Results showed that PRO residue had stronger negative effects than GUI on all the tested indicators. Residues modified by gypsum addition (MBR-PRO, MBR-GUI) were equally or sometimes less harmful compared to unamended residues. Microbial activities (bacterial growth and enzyme activities) were more inhibited than the diversity of microbial functions (Biolog®), and the structure of bacterial and fungal communities was not affected by increasing concentrations of bauxite residues. EC and ESP were the main factors explaining the inhibition of microbial activities, although the origin of bauxite residue is of great importance too.

Nanominerals assemblages and hazardous elements assessment in phosphogypsum from an abandoned phosphate fertilizer industry.

The present work investigates hazardous elements and nanomineralogical assemblages of phosphogypsum waste from an abandoned phosphate fertilizer industry located in Santa Catarina state (Brazil). Correlations between the chemical composition, nanominerals, and ultrafine particles are discussed. Multifaceted physical-geochemical study provided a careful understanding of the nanomineralogical assemblage of the phosphogypsum waste. The electron beam investigation revealed the presence of many hazardous elements in the ultrafine particles. Cr, Pb, Mn, Se, Sr, and Zr, among others, were found in individual ultrafine particles and nanominerals in all studied samples. Besides that, rare earth elements were found in different concentration ranges, being Ce, La, and Nd, the rare earth elements, found in the higher concentrations, above 900 mg kg-1. The data supplied by this article are important to characterize the phosphogypsum waste, assessing the potential hazard to the environment and human health, and also, provides information to enable the designing of alternatives to manage this waste.

A novel method for the stabilization of soluble contaminants in electrolytic manganese residue: Using low-cost phosphogypsum leachate and magnesia/calcium oxide.

Electrolytic manganese residue (EMR) contains a large amount of NH4+-N and Mn2+ and can negatively impact the environment. A stabilization treatment of soluble contaminants in the EMR is necessary for its reuse and safe stacking. This study presents experimental results for the stabilization of NH4+-N and Mn2+ in the EMR using phosphogypsum leachate as a low-cost phosphate source and MgO/CaO (PLMC) process. The results demonstrated that the stabilization efficiency of NH4+-N and Mn2+ was 93.65% and 99.99%, respectively, under the following conditions: a phosphogypsum leachate dose of 1.5 mL g-1, an added MgO dose of 0.036 g g-1, an added CaO dose of 0.1 g g-1 and a reaction time of 2 h. The stabilization effect of the PLMC process was higher and more cost effective than that of using Na3PO4·12H2O and MgO/CaO. The concentration of NH4+-N and Mn2+ in the leaching liquor decreased to 80 mg L-1 and 0.5 mg L-1, respectively, after the stabilization under the optimum conditions. The stabilization characteristics indicated that NH4+-N was stabilized to form NH4MgPO4·6H2O (struvite) and that Mn2+ was stabilized to form Mn5(PO4)2(OH)4, Mn3(PO4)2·3H2O and Mn(OH)2. PO43--P, F-, and heavy metal ions of the phosphogypsum leachate were removed from the leaching liquor and stabilized in the treated EMR.

Chemical behavior of fluorine and phosphorus in chemical looping gasification using phosphogypsum as an oxygen carrier.

In China, the amount of phosphogypsum (PG) has exceeded 250 million tons with more than 55 million tons of growth rates each year. As the micro constituent, fluorine and phosphorus restrict the resourceful disposal of PG. This paper focused on chemical looping gasification (CLG) which used PG as an oxygen carrier, systematically investigated the gasification performance and chemical behavior of fluorine and phosphorus contained in PG during CLG process. Main conclusions are as follows. The main pollutant of chemical looping gasification process was HF, which was transformed from NaF. Phosphorus transformed from water-soluble phosphorus (Ca(H2PO4)2, Ca(HPO4)) into insoluble Ca3(PO4)2.20 reducing-oxidizing cycles were investigated, and a less and less fluorine content in oxygen carrier was found because its phase transformation from solid NaF to gaseous HF, and the phosphorus content in oxygen carrier changed slightly under the current conditions. The Ca3(PO4)2 particle layers existed in both the middle of the reduced solid particles and the middle of the cycled oxygen carrier particles, confirmed to actually act as a glue between the particles. Furthermore, transformation routes of fluorine and phosphorus during the CLG process were discussed and the generation of syngas in CLG process needed to be purified.

Effects of redox oscillations on the phosphogypsum waste in an estuarine salt-marsh system.

Salt marshes are natural deposits of heavy metals in estuarine systems, where sulphide precipitation associated with redox changes often results in a natural attenuation of contamination. In the present study, we focus on the effects of variable redox conditions imposed to a highly-polluted phosphogypsum stack that is directly piled over the salt marsh soil in the Tinto River estuary (Huelva, Spain). The behaviour of contaminants is evaluated in the phosphogypsum waste and in the marsh basement, separately, in controlled, experimentally-induced oscillating redox conditions. The results revealed that Fe, and to a lesser extent S, control most precipitation/dissolution processes. Ferric iron precipitates in the form of phosphates and oxyhydroxides, while metal sulphide precipitation is insignificant and appears to be prevented by the abundant formation of Fe phosphates. An antagonistic evolution with changing redox conditions was observed for the remaining contaminants such as Zn, As, Cd and U, which remained mobile in solution during most of experimental run. Therefore, these findings revealed that high concentrations of phosphates inhibit the typical processes of immobilisation of pollutants in salt-marshes which highlights the elevated contaminant potential of phosphogypsum wastes on coastal environments.