TY - JOUR A1 - Karafiludis, Stephanos A1 - de Oliveira Guilherme Buzanich, Ana A1 - Kochovski, Z. A1 - Feldmann, Ines A1 - Emmerling, Franziska A1 - Stawski, Tomasz T1 - Ni- and Co-Struvites: Revealing Crystallization Mechanisms and Crystal Engineering toward Applicational Use of Transition Metal Phosphates JF - Crystal Growth & Design N2 - Industrial and agricultural waste streams (waste water, sludges, tailings, etc.) which contain high concentrations of NH4+, PO43–, and transition metals are environmentally harmful and toxic pollutants. At the same time, phosphorous and transition metals constitute highly valuable resources. Typically, separate pathways have been considered to extract hazardous transition metals or phosphate independently from each other. Investigations on the simultaneous removal of multiple components have been carried out only to a limited extent. Here, we report the synthesis routes for Ni- and Co-struvites (NH4MPO4·6H2O, M = Ni2+ and Co2+), which allow for P, ammonia, and metal co-precipitation. By evaluating different reaction parameters, the phase and stability of transition metal struvites as well as their crystal morphologies and sizes could be optimized. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P) ratios, whereas Co-struvite only forms at low M/P ratios. Detailed investigations of the precipitation process using ex situ and in situ techniques provided insights into the crystallization mechanisms/crystal engineering of these materials. M-struvites crystallize via intermediate colloidal amorphous nanophases, which subsequently aggregate and condense to final crystals after extended reaction times. However, the exact reaction kinetics of the formation of a final crystalline product varies significantly depending on the involved metal cation in the precipitation process: several seconds (Mg) to minutes (Ni) to hours (Co). The achieved level of control over the morphology and size makes precipitation of transition metal struvites a promising method for direct metal recovery and binding them in the form of valuable phosphate raw materials. Under this paradigm, the crystals can be potentially up-cycled as precursor powders for electrochemical or (electro)catalytic applications, which require transition metal phosphates. KW - Crystallization KW - Struvite KW - Nickel KW - Cobalt KW - Phosphorous recovery KW - Up-cycling KW - Aqueous synthesis PY - 2022 DO - https://doi.org/10.1021/acs.cgd.2c00284 VL - 22 IS - 7 SP - 4305 EP - 4315 PB - ACS Publications CY - Washington D.C. AN - OPUS4-55286 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raniro, H.R. A1 - Teles, A.P. A1 - Pavinato, P.S. A1 - Adam, Christian T1 - Phosphorus solubility and dynamics in a tropical soil under sources derived from wastewater and sewage sludge JF - Journal of Environmental Management N2 - Conventional phosphate fertilizers are usually highly water-soluble and rapidly solubilize when moistened by the soil solution. However, if this solubilization is not in alignment with plants demand, P can react with the soil colloidal phase, becoming less available over time. This is more pronounced in acidic, oxidic tropical soils, with high P adsorption capacity, reducing the efficiency of P fertilization. Furthermore, these fertilizers are derived from phosphate rock, a non-renewable resource, generating an environmental impact. To assess these concerns, waste-recycled P sources (struvite, hazenite and AshDec®) were studied for their potential of reducing P Fixation by the soil and improving the agronomic efficiency of the P fertilization. In our work, we compared the solubilization dynamics of struvite, hazenite, AshDec® to triple superphosphate (TSP) in a sandy clay loam Ferralsol, as well as their effect on solution pH and on soil P pools (labile, moderately-labile and non-labile) via an incubation experiment. Leaching columns containing 50 g of soil with surface application of 100 mg per column (mg col􀀀 1) of P from each selected fertilizer and one control (nil-P) were evaluated for 60 days. Daily leachate samples from the column were analyzed for P content and pH. Soil was stratified in the end and submitted to P fractionation. All results were analyzed considering p < 0.05. Our findings showed that TSP and struvite promoted an acid P release reaction (reaching pHs of 4.3 and 5.5 respectively), while AshDec® and hazenite reaction was alkaline (reaching pHs of 8.4 and 8.5 respectively). Furthermore, TSP promoted the highest P release among all sources in 60 days (52.8 mg col􀀀 1) and showed rapid release dynamic in the beginning, while struvite and hazenite showed late release dynamics and lower total leached P (29.7 and 15.5 mg col􀀀 1 P respectively). In contrast, no P-release was detected in the leachate of the AshDec® over the whole trial period. Struvite promoted the highest soil labile P concentration (7938 mg kg􀀀 1), followed by hazenite (5877 mg kg􀀀 1) and AshDec® (4468 mg kg􀀀 1), all higher than TSP (3821 mg kg􀀀 1), while AshDec® showed high moderately-labile P (9214 mg kg􀀀 1), reaffirming its delayed release potential. KW - Phosphate dynamics KW - Struvite KW - Wastewater KW - Sewage sludge ash KW - CaNaPO4 KW - P speciation PY - 2022 DO - https://doi.org/10.1016/j.jenvman.2021.113984 VL - 302 IS - Part A SP - 113984 PB - Elsevier Ltd. AN - OPUS4-53600 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raniro, H.R. A1 - Soares, T.de M. A1 - Adam, Christian A1 - Pavinato, P.S. T1 - Waste-derived fertilizers can increase phosphorus uptake by sugarcane and availability in a tropical soil JF - J. Plant Nutr. Soil. Sci. N2 - The use of highly water-soluble phosphorus (P) fertilizers can lead to P fixation in the soil, reducing fertilization efficiency. Waste-derived, low water-solubility sources can potentially increase sugarcane’s P uptake compared to triple superphosphate by reducing adsorption to the soil. Aims:We aimed to test struvite, hazenite, and AshDec® for their agronomic potential as recycled fertilizers for sugarcane production in a typical tropical soil.We hypothesize that these sources can reduce P fixation in the soil, increasing its availability and sugarcane’s absorption. Methods: In a greenhouse pot experiment, two consecutive sugarcane cycles, 90 days each, were conducted in a Ferralsol. The recovered sources struvite, hazenite, AshDec®, and the conventional triple superphosphate were mixed in the soil in three P doses (30, 60, and 90 mg kg–1), aside a control (nil-P). At both harvests, sugarcane number of sprouts, plant height, stem diameter, dry mass yield, shoot phosphorus, and soil P fractionation were investigated. Results: At 90 days, struvite and hazenite performed better for dry mass yield (70.7 and 68.3 g pot–1, respectively) than AshDec® and triple superphosphate (59.8 and 57.4 g pot–1, respectively) and for shoot P, with 98.1, 91.6, 75.6, and 66.3 mg pot–1, respectively. At 180 days, struvite outperformed all treatments for dry mass yield (95.3 g pot–1) and AshDec® (75.5 mg pot–1) for shoot P. Struvite was 38% and hazenite 21% more efficient than triple superphosphate in P uptake, while AshDec® was 6% less efficient. Soil had higher labile P under struvite, hazenite, and AshDec® than triple superphosphate by the end of the first cycle, while only the later increased nonlabile P by the end of the experiment (180 days). Conclusions:Waste-derived P sources were more efficient in supplying P for sugarcane and delivering labile P in 180 days than triple superphosphate. KW - AshDec KW - Hazenite KW - P-efficiency KW - Recycled sources KW - Struvite PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-544216 DO - https://doi.org/10.1002/jpln.202100410 SN - 1436-8730 SP - 1 EP - 12 PB - Wiley-VCH GmbH AN - OPUS4-54421 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -