Recycled Iron Phosphates: A New Phosphorus Fertilizer for Paddy Rice.

The potential of recycled iron phosphates (FePs), e.g., vivianites (Fe3(PO4)2·8H2O) and Fe(III)-rich phosphorus (P) adsorbent materials, as phosphorus fertilizer is limited by the strong interaction between Fe and P. In this study, the efficiency of FePs as P fertilizer was explored by applying them as granules or powder in flooded strongly P-fixing soils (acid and calcareous), thereby taking advantage of increased P release induced by reductive dissolution of P-bearing Fe(III) minerals. First, no P diffusion from granular FeP fertilizers into flooded soils was detectable by the diffusive gradient in thin films (DGT) technique and microfocused X-ray fluorescence (µ-XRF) analysis of thin soil sections, in contrast to detectable P diffusion away from granules of soluble triple superphosphate (TSP) fertilizer. On the contrary, powdered FePs demonstrated an excellent increase in extractable P (1 mM CaCl2) in a 120-day incubation experiment in flooded soils. Second, a pot experiment was performed with rice (Oryza sativa) grown in flooded acid and calcareous soils. The fertilizer value of FePs was remarkable when dosed as powder, as it was even up to 3-fold higher than TSP in the acid soil and similar to TSP in the calcareous soil. The beneficial effect of FeP over TSP in the acid soil is attributed to the slow release of P from FePs, which allows to partly overcome P fixation. The promising results of FePs as P fertilizer applied as powders in flooded soils debunk the generally accepted idea that FePs are poor sources of P while demonstrating the importance of the timing of FeP fertilizer application.

Enhancing the phosphorus content of layered double hydroxide fertilizers by intercalating polymeric phosphate instead of orthophosphate: A feasibility study.

HYPOTHESIS: Layered double hydroxide (LDH) loaded with orthophosphate (PO4) are suggested as slow-release P fertilizers. However, PO4-LDHs have a low maximal P content, related to high charge HPO42-/PO43- anions occupying the anion exchange capacity (AEC) of LDHs. We postulate that the P content of LDHs can be enhanced by exchanging them with polymeric-P (i.e. trimetaphosphate, P3O9), which has a lower molar charge/P ratio than its monomer. EXPERIMENTS: Adsorption capacities were compared between PO4 and P3O9 for as-synthesized and calcined MgAl LDHs with Mg/Al ratio of 2, 3, or 4; the P-LDHs were characterized (XRD, FTIR). Dialysis and soil incubation experiments were performed with PO4-LDHs, P3O9-LDHs, and corresponding soluble fertilizers to compare their P release and P solubility (CaCl2 extract). FINDINGS: The P adsorption capacities were 1.25-1.60 fold larger for P3O9 compared to PO4, yet the high theoretical P contents with P3O9 were not achieved (incomplete loading, P3O9 depolymerization). P3O9-Mg3Al released polymeric-P whereas P3O9-Mg2Al released depolymerized PO4, and P release from P3O9-LDHs was slower than that of PO4-LDHs. With soil incubation, soluble P from P3O9-LDH was initially lower but later converged to that of PO4-LDH as result of continued hydrolysis, yet did not exceed that of the soluble P3O9 and PO4 fertilizers.

Layered Double Hydroxides as Slow-Release Fertilizer Compounds for the Micronutrient Molybdenum.

Molybdenum (Mo) is an essential plant micronutrient. Despite low plant Mo requirements, deficiencies are not uncommon and soluble Mo fertilizers are often applied. However, soluble Mo may result in poor Mo use efficiency due to strong sorption (acid weathered soils) or leaching (lighter-textured soils). Here, ZnAl layered double hydroxides (LDHs), loaded with molybdate (MoO4), were examined for their potential as slow-release Mo compounds. Chloride-exchanged LDHs with varying Zn/Al ratios (2, 3, and 4) were exchanged with MoO4. Zn2Al LDH indicated MoO4 intercalation, whereas Zn3Al and Zn4Al LDHs bound MoO4 merely on edge sites. Short-term Mo-LDH incubation identified sulfate, carbonate, and phosphate as the most competitive anions for MoO4 exchange. Long-term Mo-LDH incubation in simulated pH-neutral soil solutions demonstrated slow Mo release from Zn2Al LDH (half-life of 35 h), with a total Mo desorption of up to 85%. For Zn3Al and Zn4Al LDHs, Mo desorption was limited to <20%. Finally, several macronutrient fertilizers were tested as possible carriers for Mo-LDH fertilizer compounds.

Granulation and calcination of alum sludge for the development of a phosphorus adsorbent: From lab scale to pilot scale.

Alum sludge, an Al-oxyhydroxide rich waste product from water treatment practices, has the potential to be valorized as a P adsorbent material. However, several challenges currently prevent its application as an adsorbent in industrial setting, i.e. a limited P adsorption capacity due to saturation by organic matter and a fine nature resulting in percolation problems in adsorption bed setups. In this study, granulation and subsequent calcination of alum sludge were proposed to overcome these issues and to improve the P adsorption properties of alum-based adsorbent (ABA) materials. The effect of calcination temperature on the physicochemical properties of granular material was examined using X-ray diffraction, mass-spectroscopy coupled thermogravimetric analysis, Fourier-transform infrared spectrometry and specific surface area analysis, combined with density and crushing strength measurements. The ABA material obtained at 550 °C showed superior P adsorption properties and, therefore, this material was selected for further P adsorption testing and characterization (scanning electron microscopy and sieving). Batch P adsorption tests showed that this material had a maximum P adsorption capacity of 7.27 mg-P g-1. Kinetic adsorption tests determined the effect of the solid-to-liquid ratio and the granule particle size on the P removal. Finally, the performance of the ABA-550 material was tested in a pilot-scale adsorption setup, using a surface water stream (0.47 mg-P L-1) at a flow rate of 200 L h-1. During the test, the P removal efficiency always exceeded 86%, while the material maintained its structural stability. The results of this study illustrate the potential of granulated/calcined ABA materials for P adsorption, paving the way for the industrial application of this novel, sustainable P removal technology.

Carbonation is affecting biodegradability testing of fiber cement composites.

Fiber cement composites (FCCs) containing natural cellulosic fibres are emerging materials in the building industry. At the end of life, FCCs are often disposed of as part of the C&DW in a landfill. The production of landfill gasses in landfills needs to be kept as low as possible. Generally, leaching of total dissolved organic carbon (DOC) is used as a proxy for the biodegradability of a waste material and the subsequent production of landfill gasses, and is, therefore, used to evaluate biodegradability of waste. In this study, FCC samples with varying average diameter and varying age were subjected to both a batch leaching test (determine DOC leaching) and to a standardized biodegradability test. The batch leaching showed that the DOC leaching ranged between 520 and 1300 mg kg-1 for the tested samples, and that leaching of DOC decreases with increasing particle diameter and with increasing effects of ageing. Yet, the biodegradability results indicated that the leaching of DOC from FCCs does not result in the release of landfill gasses. This study hypothises that the DOC that leaches from the FCCs is being degraded to CO2, but that the formed CO2 is immediately captured by the material itself through the process of carbonation. An inpermeable layer is formed around the material that stops further leaching of DOC. The results of this study therefore suggest that leaching of DOC is a poor indicator for the biodegradability of FCCs.

Optimization of phosphate recovery from urine by layered double hydroxides.

Urine contains sufficient phosphorus (P) to consider P recycling form urine as an interesting strategy. In this study, the potential of MgAl or ZnAl layered double hydroxides (LDHs) to be used in such recovery was assessed. LDHs are anion exchangers with a high P selectivity, and P-loaded LDHs have demonstrated fertiliser potential. A critical factor for efficient P recycling with LDH is the stability of these materials, which can be compromised by urinary citrate, complexing aluminium (Al3+) and by the low pH of fresh urine dissolving the alkaline LDHs. Different phase pure ZnAl and MgAl LDHs were synthesised by coprecipitation in scenarios of varying synthesis pH and Mg/Al or Zn/Al ratios. The obtained materials were incubated in P solutions at different pH, with or without citrate in full factorial combinations, and in fresh and stored human urine. The P sorption capacities increased for LDHs synthesised at lower pH, at increasing Al content and for sorption solutions with lower pH. These trends are explained by an increased anion exchange capacity (AEC) and by P speciation (charge) in the LDHs, an interpretation supported by XRD measurements. The P capacity reached 61mg P/g LDH, which equals 85% of the theoretical LDH exchange capacity. Only 1g LDH is required to remove 90% of P from 1L urine and evidence is found that sorption, not struvite precipitation, is the P removal mechanism involved. The ZnAl LDHs were equally effective in P uptake compared to the MgAl LDHs, but the ZnAl materials showed more irreversible P sorption in contrast with the high desorption yields (53mg P/g) of the MgAl LDHs. Therefore, the large potential of MgAl LDHs for P recovery from urine is supported by this study.

Microwave Radiation as a Pre-Treatment for Standard and Innovative Fragmentation Techniques in Concrete Recycling.

Recent advances in concrete recycling technology focus on novel fragmentation techniques to obtain aggregate fractions with low cement matrix content. This study assesses the aggregate liberation effectiveness of four different treatment processes including standard and innovative concrete fragmentation techniques. Lab-made concrete samples were subjected to either standard mechanical crushing technique (SMT) or electrodynamic fragmentation (EDF). For both fragmentation processes, the influence of a microwave weakening pre-treatment technique (MWT) was investigated. A detailed analysis of the particle size distribution was carried out on samples after fragmentation. The >5.6 mm fraction was more deeply characterized for aggregate selective liberation (manual classification to separate liberated aggregates) and for cement matrix content (thermogravimetric measurements). Results highlight that EDF treatment is more effective than SMT treatment to selectively liberate aggregates and to decrease the cement matrix content of the >5.6 mm fraction. EDF fully liberates up to 37 wt.% of the >5.6 mm natural aggregates, while SMT only liberates 14⁻16 wt.%. MWT pre-treatment positively affects aggregate liberation and cement matrix removal only if used in combination with SMT; no significant effect in combination with EDF was recorded. These results of this study can provide insights to successfully implement innovative technology in concrete recycling plants.

Solid-state speciation of interlayer anions in layered double hydroxides.

Layered double hydroxides (LDH) have been proposed for phosphate (PO4) recovery and recycling from waste streams due to their high anion exchange capacity, good stability and high affinity towards PO4. The high affinity towards PO4 strongly relates to the electrostatic interaction with PO4, and thus the charge of PO4. However, the anion speciation of intercalated PO4, i.e. either H2PO4-, HPO42- or PO43- is often overlooked. This study was set up to measure solid phase PO4 speciation through ion exchange stoichiometry, X-ray diffraction (XRD), attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) and modelling. Six phase pure Mg/Al LDH materials were synthesized using co-precipitation of metal nitrate (NO3-) solutions with varying M2+/M3+ ratio at pH 12 and pH 10. The LDHs synthetized at pH 12 contained larger equivalent fractions of intercalated OH-, smaller fractions of NO3- and smaller interlayer distance than those prepared at pH 10, likely because of the higher OH- concentration in the more alkaline synthesis solutions. Two high charge LDHs prepared at pH 12 or 10 were selected, exchanged with PO4 (0-20 mM initial PO4, 24 h) at one starting pH (7.20); desorption was subsequently performed with carbonate (3 mM, initial pH 8.4) during 480 h. The resulting solution concentrations of NO3, PO4 and CO3 and the pH allowed the identification of the anion exchange stoichiometry. The LDH synthesized at pH 12, which had a large fraction of exchangeable OH-, adsorbed PO4 as HPO42-/PO43-, in exchange for both NO3- and OH- anions. The material synthesized at pH 10 containing a lower fraction of exchangeable OH-, therefore, adsorbed mainly HPO42- in exchange for NO3- anions. The carbonate exchange was consistent with adsorption of divalent CO32-. The pH dependent speciation modelling showed that the exchanged PO4 ions have higher charge compared to those in the contacting solution. This study suggests that the highest P content of LDH is obtained in high charge materials holding divalent PO4 anions, i.e. materials synthesized at lower pH and/or exchanged in solutions with low alkalinity.

Limited Dissolved Phosphorus Runoff Losses from Layered Double Hydroxide and Struvite Fertilizers in a Rainfall Simulation Study.

The enrichment of P in surface waters has been linked to P runoff from agricultural fields amended with fertilizers. Novel slow-release mineral fertilizers, such as struvite and P-exchanged layered double hydroxides (LDHs), have received increasing attention for P recycling from waste streams, and these fertilizers may potentially reduce the risk of runoff losses. Here, a rainfall simulation experiment was performed to evaluate P runoff associated with the application of recycled slow-release fertilizers relative to that of a soluble fertilizer. Monoammonium phosphate (MAP), struvite, and LDH granular fertilizers were broadcasted at equal total P doses on soil packed in trays (5% slope) and covered with perennial ryegrass ( L.). Four rainfall simulation events of 30 min were performed at 1, 5, 15, and 30 d after the fertilizer application. Runoff water from the trays was collected, filtered, and analyzed for dissolved P. For the MAP treatment, P runoff losses were high in the first two rain events and leveled off in later rain events. In total, 42% of the applied P in the MAP treatment was lost due to runoff. In the slow-release fertilizer treatments, P runoff losses were limited to 1.9 (struvite) and 2.4% (LDH) of the applied doses and were more similar over the different rain events. The use of these novel P fertilizer forms could be beneficial in areas with a high risk of surface water eutrophication and a history of intensive fertilization.

The isotopic exchangeability of phosphate in Mg-Al layered double hydroxides.

Layered double hydroxides (LDH) of Mg/Al are anion exchangers that are candidate materials for phosphate (PO4) recovery and recycling from waste streams. However, PO4 recycling in agriculture might be limited by incomplete desorption of PO4 from the minerals. This study was set up to identify the factors explaining irreversible PO4 sorption ("fixation") on LDHs by comparing the isotopic exchangeability (33PO4) with the PO4 desorption from LDH materials and from boehmite as a P fixing reference mineral. Six different Mg-Al LDH materials were synthesized, by varying the synthesis pH and exposing obtained materials to hydrothermal (HT) treatment. Phase pure LDH materials were obtained from syntheses at pH 10 and 12, while at pH 8 Al-rich phase impurities such as a boehmite or gibbsite were formed. Crystallite size increased significantly during HT treatment. The LDHs were first loaded with PO4 prior to 33PO4 isotopic exchange (0-20 days, 1 mM NaHCO3) or PO4 desorption (0-20 days, NaHCO3 concentrations increasing from 0 to 20 mM). The isotopic PO4 exchangeability was 85-95% of total PO4 after 72 h in the phase pure LDHs with intercalated PO4 whereas this value was 40-54% in the presence of Al-rich phase impurities in non-HT treated materials and in boehmite. In contrast, the maximally desorbed PO4 fractions were only 55-63% for the phase pure LDHs, indicating that not all of the isotopically exchangeable PO4 can be desorbed. Samples at different stages of desorption (different initial NaHCO3 concentrations) were subjected to isotopic exchange after desorption. In the LDHs with PO4 intercalation, PO4 was increasingly less isotopically exchangeable as the initial NaHCO3 concentrations increased, while this trend was not observed for samples without intercalated PO4. This suggests that PO4 becomes increasingly less accessible for isotopic exchange as the fraction binding sites occupied with HCO3- increases. The interlayer outward diffusion of PO4 might be increasingly rate limited upon H2PO4-/HCO3- exchange, which explains the PO4 fixation in LDHs.

Agronomic Effectiveness of Granulated and Powdered P-Exchanged Mg-Al LDH Relative to Struvite and MAP.

Layered double hydroxides (LDHs) used to recover P from wastewater have recently been proposed as new slow-release fertilizers. Here, the use of P-exchanged Mg-Al LDHs as powdered or granulated fertilizer is explored and compared with monoammonium phosphate (MAP), a fully water-soluble fertilizer, and with struvite, a recycled phosphate fertilizer with lower solubility. First, these three fertilizers were compared in a 100-day incubation experiment using P diffusion visualization and chemical analysis to assess P release from either granules or powdered fertilizer in three different soils. By the end of the incubation, 74-90% of P remained within the LDH granule, confirming a slow release. Second, a pot experiment was performed with wheat (Triticum aestivum) in an acid and a calcareous soil. The granular treatment resulted in a considerably higher P uptake for MAP compared to LDH and struvite. For the powder treatments, the P uptake was less than for granular MAP and was largely unaffected by the chemical form. The LDHs and struvite showed a lower agronomic effectiveness than granular MAP, but the benefits of their use in P recycling, potential residual value, and environmental benefits may render these slow-release fertilizers attractive.