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Effects of pH and Ca/P molar ratio on the quantity and crystalline structure of calcium phosphates obtained from aqueous solutions

pH Ca/P

Effets du pH et du ratio molaire Ca/P sur la quantité et la structure cristalline des phosphates de calcium obtenus à partir de solutions aqueuses

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Dairy Science & Technology

Abstract

Milk and dairy products contain large amounts of calcium phosphate salts that can precipitate. The chemical composition and the crystalline structure of the calcium phosphate precipitates that are formed in dairy industry depend on the physico-chemical conditions, particularly, pH and mineral composition. The objective of this study was to determine, using mineral solutions, the effects of pH and of the concentrations of calcium and phosphate on the quantity and crystalline structure of calcium phosphate precipitates. Experiments were carried out at 20 °C with 20.00 mmol·L−1 phosphate and three Ca/P molar ratios (1.00, 1.50 and 2.00). The initial pH (5.50, 6.70, 7.50, 8.50 and 9.50) were drifting or kept constant during a reaction time of 3 h. After filtration of the suspensions, the mineral compositions of filtrates were quantified. The lyophilized precipitates were characterized using X-ray diffraction, infrared spectroscopy and scanning electron microscopy techniques. At drifting pH (final pH values were between 4.6 and 6.0), the mineral analyses showed that the Ca/P ratio did not influence the amounts of precipitated calcium and phosphate. The analyses of precipitates revealed the formation of brushite as the main crystalline phase. At constant pH, the mineral analyses showed that the Ca/P ratio strongly influenced the precipitation efficiency of calcium phosphate. The analyses of precipitates revealed the formation of poorly crystallized calcium-deficient apatites. A decrease of crystallinity with an increase in initial pH was observed. In conclusion, pH can be a key factor to control the quantity and crystalline structure of calcium phosphates obtained by precipitation. This factor should be considered for the recovery of calcium phosphates from dairy co-products. pH is also important in the fouling phenomena of membranes and heat exchangers caused by calcium phosphate precipitation.

Abstract

pH pH 20 °C 20.00 mmol·L−1 3 Ca/P (1.00 1.50 2.00) pH (5.50 6.70 7.50 8.50 9.50) 3 X- pH pH 4.6 6.0) Ca/P (CaHPO4·2H2O2) pH Ca/P pH pH pH

Résumé

Le lait et les produits laitiers sont riches en sels de phosphate de calcium qui peuvent précipiter. La composition chimique et la structure cristalline de ces précipités formés en industrie laitière dépendent des conditions physicochimiques de formation, notamment le pH et la composition minérale. L’objectif de ce travail était de déterminer, en utilisant des solutions minérales, les rôles du pH et des concentrations du calcium et du phosphate sur la nature et la quantité des précipités de phosphate de calcium. Les expériences ont été réalisées à 20 °C, avec une concentration en phosphate de 20.00 mmol·L−1 et trois rapports molaires Ca/P (1,00, 1,50 et 2,00). Les pH initiaux (5,50, 6,70, 7,50, 8,50 et 9,50) étaient dérivants ou maintenus constants pendant un temps de réaction de 3 heures. Après filtration des suspensions, les compositions minérales des filtrats ont été analysées. Les précipités lyophilisés ont été caractérisés par diffraction des rayons X, spectroscopie infrarouge et microscopie électronique à balayage. À pH dérivant (pH final des suspensions compris entre 4,6 et 6,0), l’analyse minérale a montré que le rapport Ca/P n’influençait pas les quantités de phosphate et de calcium précipitées. Les analyses des précipités ont montré la formation de brushite comme principale phase cristalline. À pH constant, l’analyse minérale a montré que le rapport Ca/P avait une forte influence sur le taux de précipitation du phosphate de calcium. Les analyses des précipités ont mis en évidence la formation d’apatites déficientes en calcium mal cristallisées. Une diminution de la cristallinité avec l’augmentation du pH initial a été observée. En conclusion, le pH peut être considéré comme un facteur essentiel pour contrôler la quantité et la structure cristalline des phosphates de calcium obtenus par précipitation. Ce facteur est à considérer dans la récupération des phosphates de calcium des co-produits laitiers. Le pH est également important dans les phénomènes d’encrassement des membranes et des échangeurs thermiques suite à la précipitation du phosphate de calcium.

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Authors and Affiliations

  1. UMR1253 Science et Technologie du Lait et de l’Œuf, INRA, 65 rue de Saint Brieuc, 35042, Rennes Cedex, France

    Omar Mekmene, Michel Piot & Frédéric Gaucheron

  2. INSERM, U791 Laboratoire d’Ingénierie Ostéo-Articulaire et Dentaire, Faculté de chirurgie dentaire, Université de Nantes, 1 place Alexis Ricordeau, 44042, Nantes, France

    Omar Mekmene, Sophie Quillard, Thierry Rouillon & Jean-Michel Bouler

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  1. Omar Mekmene
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  2. Sophie Quillard
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  5. Michel Piot
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  6. Frédéric Gaucheron
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Correspondence to Frédéric Gaucheron.

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Mekmene, O., Quillard, S., Rouillon, T. et al. Effects of pH and Ca/P molar ratio on the quantity and crystalline structure of calcium phosphates obtained from aqueous solutions. Dairy Sci. Technol. 89, 301–316 (2009). https://doi.org/10.1051/dst/2009019

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  • DOI: https://doi.org/10.1051/dst/2009019

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