Mineralogical-geochemical study of the anionic competition effect on the octacalcium phosphate reaction into fluorapatite.

The unstable compound octacalcium phosphate (OCP) is one of the crystalline precursors of the apatite mineral series composed by hydroxyapatite, fluorapatite and chlorapatite. The feature of OCP to react into apatite, depending on the media conditions, has been mainly exploited for biomedical applications as bone and tooth substitute material. Recently, some important applications of OCP have been documented: e.g. as electrode material for supercapacitors and as fluoride remover reagent for environmental purposes. With the aim of deepening the property of OCP to be the crystalline precursor of apatite and assessing if and how the anionic competition can influence the formation of the different apatite end-members, the OCP → apatite reaction has been here investigated placing 0.223 mmol of OCP in 50 mL aqueous solution with 0.368 mmol of dissolved fluoride, chloride, hydroxyl and carbonate anions (fluoride alone, fluoride with each of the other anions, and all the anions together) at room temperature. The post-experiment analyses of solid and liquid phases, conducted by using XRD, ESEM and ICP-OES, show that fluoride is always the main anion removed from solution during the OCP transformation reaction. The precise mineralogical characterization of solid phases formed, performed using the Rietveld algorithm, shows that fluorapatite is always the main resulting apatitic phase, followed by hydroxyapatite. Taking into account the different application fields of OCP, these results could be significant in better defining the OCP → apatite reaction in aqueous solutions where different competing anions are involved.

A two-step pH control method to remove divalent metals from near-neutral mining and metallurgical waste drainages by inducing the formation of layered double hydroxide.

A neutral M2+-rich and M3+-poor (M = metal) metallurgical waste drainage was used to test a metal removal method based on the precipitation of layered double hydroxide (LDH). The LDH precipitation was induced by adding a salt of Al3+ (trivalent metal missing in the drainage) and maintaining or restoring the pH to a circum-neutral value. The precipitates were characterized by chemical analysis, XRD, ESEM, HRTEM and XAS. The main parameter controlling the removal of metals and the type of precipitate appeared to be the pH. As a function of pH variation during the experiments, analyses of precipitates and solutions showed either the formation of poor crystalline LDH combined with very high removal of Zn, Ni and Pb (92-100%), more variable removal of Mn (46-98%) and less Cd (33-40%), or the formation of more crystalline LDH combined with lower removal of Zn (62%), Mn (43%), Ni (88%), Pb (64%) and especially Cd (1%). The different metal removal efficiency in the two cases is only indirectly due to the different LDH crystallinity, and it is clearly affected by the following factors: 1) the two pH steps of the method; 2) the direction of pH variation within each step. In particular, the highest removal of metals is obtained when the first pH step goes towards acidic conditions, as a consequence of Al salt addition, and precipitation of a quasi-amorphous hydrated hydroxysulfate of Al (probably a precursor of felsÓ§bányaite Al4(SO4)(OH)10 · 4H2O) occurs. This first acidic pH step removes little or no metals (just 0-3%) but it is essential so that the second pH step towards slightly alkaline conditions, as a consequence of NaOH addition, can be highly efficient in removing divalent metals as the quasi-amorphous hydrated hydroxysulfate of Al gradually turns into an LDH incorporating Zn, Mg and other metals. On the contrary, when both pH steps remain in the neutral-alkaline range, only LDH precipitation occurs and a lower metal removal is observed. These results encourage further investigations on the removal of metals by inducing LDH precipitation as a simple and effective method for the treatment of circum-neutral polluted drainages.

Application of Octacalcium Phosphate with an Innovative Household-scale Defluoridator Prototype and Behavioral Determinants of its Adoption in Rural Communities of the East African Rift Valley.

Natural fluoride contamination of drinking water is a serious issue that affects several countries of the world. Its negative health impact is well documented in the East African Rift Valley, where water consumption with fluoride ( F - ) concentration greater than 1.5 mg/L can cause fluorosis to people. Within the framework of the European Union (EU) Horizon 2020 FLOWERED project, we first designed an effective defluoridation device based on innovative application of octacalcium phosphate (OCP) and then explored its acceptance within rural communities. The prototype (FLOWERED Defluoridator Device [FDD]) essentially is composed of a 20-L tank and a recirculating pump that guarantees the interaction between water and OCP. The device is powered by a car battery for a fixed pumping working time using a fixed amount of OCP for every defluoridation cycle. The results of tests performed in the rural areas of Tanzania show that a standardized use of the prototype can lower the dissolved F - from an initial concentration of 21 mg/L to below the World Health Organization (WHO) drinkable limit of 1.5 mg/L in 2 h without secondary negative effects on water quality. The approximate cost of this device is around US$220, whereas that of OCP is about $0.03/L of treated water. As with any device, acceptance requires a behavioral change on behalf of rural communities that needed to be investigated. To this end, we piloted a survey to explore how psychological and socioeconomic factors influence the consumption of fluoride-free water. Results show that the adoption of FDD and OCP is more appealing to members of the rural communities who are willing to pay more and have a high consumption of water. Moreover, we suggest that given the low level of knowledge about fluorosis diseases, the government should introduce educational programs to make rural communities aware of the negative health consequences. Integr Environ Assess Manag 2020;16:856-870. © 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Defluoridation of water through the transformation of octacalcium phosphate into fluorapatite.

The consumption of water with fluoride concentration higher than 1.5 mg/L (WHO recommended limit) is recognized to cause serious diseases, and fluoride removal from natural contaminated waters is a health priority for more than 260 million people worldwide. The octacalcium phosphate (OCP), a mineralogical precursor of bio-apatite, is here tested as a fluoride remover. A new two-step method for the synthesis of OCP is proposed: 1) synthesis of brushite from calcium carbonate and phosphoric acid; 2) subsequent hydrolysis of brushite. Fluoride removal experiments are performed in batch-mode using different initial concentrations of fluoride (from 40 to 140 mg/L) and reaction times. Most of fluoride is removed within the first 2 h of all experiments, and the drinkable limit of 1.5 mg/L is reached within a minimum of 3 h for an initial fluoride concentration of 40 mg/L. The experimental fluoride removal capacity of OCP is 25.7 mg/g, and 4 g of OCP can effectively treat 1 L of water with fluoride concentration up to 50 times higher than the drinking limit of 1.5 mg/L. XRD and chemical characterization of the solid phases, before and after the removal experiments, indicate that OCP transforms into fluorapatite (FAP) uptaking fluoride from solution.

Antimonate uptake by calcined and uncalcined layered double hydroxides: effect of cationic composition and M2+/M3+ molar ratio.

This study gives a contribution to assess the efficacy of some LDHs (layered double hydroxides) in Sb(V) uptake and understand the mechanisms involved in the removal process. Uncalcined nitrate Mg/Al LDHs and the mixed Mg-Al oxides derived from calcined carbonate Mg/Al LDHs mainly remove Sb(OH)6- from aqueous solution through the formation of a brandholzite-like phase (a non-LDH compound with general formula Mg[Sb(OH)6]2·6H2O), although with a different efficiency (< 50 and 90-100% of Sb(V) removed, respectively). The formation of a brandholzite-like compound highlights the fundamental role of Mg in the removal process. The Sb(OH)6- removal capacity of uncalcined nitrate Mg/Al LDHs increases from 22 to 46% as the Mg/Al molar ratio decreases from 4 to 2 thanks to the increasing excess of positive charge of brucite-like sheets and the expanding interlayer thickness due to the different spatial orientations of nitrate groups (flat for Mg/Al = 4, perpendicular for Mg/Al = 2). The presence of Fe3+ in the trivalent cationic site of carbonate LDHs (Mg/(Al + Fe) = 3/(0.5 + 0.5)) improves the Sb(OH)6- removal capacity of their calcined products. When Mg is replaced by Zn in the divalent cationic site of carbonate LDHs and the sorption experiments are performed using the mixed Zn-Al oxides derived from calcination, Sb(OH)6- is mainly removed from the solution through the reconstruction of an antimonate LDH structure (i.e., a zincalstibite-like compound with general formula Zn2Al(OH)6[Sb(OH)6]). The removal efficiency of calcined carbonate Zn/Al LDHs is high and comparable to that of calcined carbonate Mg/Al LDHs; however, the mechanisms involved in the removal process are substantially different: entrance of Sb(OH)6- in the interlayer in the first case, adsorption of Sb(OH)6- onto the surface and formation of a new phase (a brandholzite-like compound) in the second case. In both cases, the removal processes are described with the pseudo-second-order kinetic model; the theoretical maximum adsorption capacity determined with the Langmuir isotherm results to be 4.54 and 4.37 mmol g-1 for calcined carbonate Mg/AlFe and Zn/Al LDHs, respectively.

Stream water chemistry in the arsenic-contaminated Baccu Locci mine watershed (Sardinia, Italy) after remediation.

The abandoned Pb-As Baccu Locci mine represents the first and only case of mine site remediation in Sardinia, Italy. Arsenic is the most relevant environmental concern in the Baccu Locci stream watershed, with concentrations in surface waters up to and sometimes over 1 mg/L. The main remediation action consisted in creation of a "storage site", for the collection of contaminated materials from different waste-rock dumps and most of tailings piles occurring along the Baccu Locci stream. This paper reports preliminary results on the level of contamination in the Baccu Locci stream after the completion of remediation measures. Post-remediation stream water chemistry has not substantially changed compared to the pre-remediation situation. In particular, dissolved As maintains an increasing trend along the Baccu Locci stream, with a concentration of about 400 µg/L measured at a distance of 7 km from the storage site. Future monitoring will provide fundamental information on the effectiveness of remediation actions conducted and their applicability to other mine sites in Sardinia. At the stage of mine site characterisation of future remediation plans, it is recommended to pay more attention to the understanding of mineralogical and geochemical processes responsible for pollution. Moreover, mixing of materials with different composition and reactivity in a storage site should require careful consideration and long-term leaching tests.

The chemical state of arsenic in minerals of environmental interest--an XPS and an XAES study.

A systematic analytical study using X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) has been carried out to characterize the chemical state of arsenic in complex environmental samples. The conventional approach, which relies on the chemical shift of the core levels As3d, provides ambiguous results in determining the chemical environment of arsenic. A more accurate approach, based on the Auger parameter and on the Wagner (Chemical State) plot, which combines AsLMM kinetic energy and As3d binding energy, was adopted. This novel method for determining the chemical state of arsenic was employed to completely characterize arsenic in complex environmental samples.