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This research presented six natural clay minerals (NCM) evaluated for the effectiveness of NH4+ adsorption from aqueous solution. For the first time, the NH4+ adsorption capacities of kaolinite, halloysite, montmorillonite, vermiculite, palygorskite, and sepiolite were examined and compared in the same study. All the NCM were fully characterized by XRD, SEM/EDS, XRF,FTIR, CEC, zeta potential and nitrogen adsorption-desorption isotherms to better understand the adsorption mechanism-property relationship. Adsorption kinetics showed that the adsorption behavior followed the pseudo-second-order kinetic model. The adsorption isotherms fitted by the Langmuir model illustrated that among all the NCM studied, vermiculite (50.06 mg/g) and montmorillonite (40.84 mg/g) showed the highest ammonium adsorption capacities. Our results revealed that the cation exchange is the main mechanism for the NH4+ adsorption. Additionally, negatively charged surface, water absorption process and surface morphology of NCM might also contribute to the high adsorption capacity for the NH4+. The maximum adsorption capacities for all NCM were rapidly obtained within 30 min with a dosage of 0.3 g/25 mL at pH of 7. The results illustrated that the NCM have significant potential as economic, safe and effective adsorbent materials for the NH4+ adsorption from the aqueous solution.

This work aims to prepare and characterize novel organo-montmorillonites (OMts) using a nonionic surfactant - octylphenol polyoxyethylene ether (OP-10), and apply the materials for the removal of cationic organic dyes. The nonionic surfactant OP-10 can be successfully intercalated into the interlayer of montmorillonite and the obtained OMts still keep cation exchange capacity. The structural configuration of surfactant molecules between clay mineral layers varies from the surfactant loadings. Moreover, OMts with higher surfactant loadings have higher organic carbon content but lower specific surface area. The prepared OMts showed enhanced adsorption capacities towards cationic organic dye methylene blue (MB), and the adsorption amount increases with an increase of surfactant loading. The high adsorption capacity can be attributed to the fact that the novel OMts still keep cationic exchange capacity and OP-10 has plentiful polyoxyethylene ether chains in its molecule structure, which can capture MB molecules through hydrogen bonding. A probable mechanism for the removal of MB was proposed to be a synergistic effect of ion exchange, partition adsorption, hydrogen bonding and electrostatic interactions. Kinetic and isotherm data could be fitted with pseudo-second order model and Langmuir isotherm. The adsorption thermodynamics study has proved the spontaneous and endothermic nature of the adsorption process. The nonionic surfactant modified OMts could be promising candidate adsorbents for the removal of cationic organic dyes.

A novel and efficient photocatalyst was synthesized by surface hybridizing Zn/Ti-LDH (LDH) with C60 molecules. The structural characteristics of the resulting products (C60/LDH) were studied using a variety of characterization methods, and the photocatalytic activities of C60/LDH were tested using Orange II (OII) as a model contaminant under simulated solar irradiation. The FT-IR spectra showed that the characteristic mode of C60 at 1182 cm-1 split into two peaks at approximately 1240 and 1156 cm-1; in addition, the Raman spectra showed the band at 1422 cm-1 for C60 was upshifted to 1431 cm-1 with the increased doping amount of C60. In addition, the XPS spectra revealed that the peaks of O1s, Zn 2p, and Ti 2p were downshifted slightly. These results demonstrated that chemical interaction existed between C60 and LDH on C60/LDH. The UV-vis diffuse reflectance spectra confirmed that the absorbance of C60/LDH in visible-light region enhanced markedly, as compared with that of pristine LDH. The photoluminescence (PL) spectroscopic measurement revealed that the C60/LDH composites exhibited much weaker PL intensity than that of LDH sample, and the transient photocurrent (I-V) analysis showed that C60/LDH had higher photocurrent density than pristine LDH. The results of PL spectra and I-V analysis suggested that C60 molecule could effectively transfer the photoelectrons from the conduction band of LDH, leading to a lower recombination rate of the photo-induced electrons and holes. The photocatalytic experiments showed that C60/LDH had much higher photocatalytic activity in the decolorization of OII than that of pristine LDH, and 2%C60/LDH composite exhibited the highest photocatalytic activity. Furthermore, the stability test indicated that the decolorization efficiency of OII by 2%C60/LDH was still quite efficient after being used for 5 cycles.

Fe–montmorillonite (Fe–Mt) was prepared and tested for its potential application in the simultaneous removal of hexavalent chromium (Cr(VI)) and rhodamine B (RhB) from aqueous solution. The adsorption kinetics and capacities of Fe–Mt toward Cr(VI) and RhB were determined in relation to the initial contaminant concentration, pH of the solution and concentration of coexist contaminant. The adsorption kinetics of Cr(VI) or/and RhB in both single and simultaneous systems were investigated, which showed that an equilibrium time of a few hours was needed for the adsorption of Cr(VI) and RhB on Fe–Mt. The pseudo-second order model offers a better fit than pseudo-first order model for the Cr(VI) and RhB adsorption. Compared with the single adsorption systems, adsorption rates and quantities of Cr(VI) and RhB adsorbed on Fe–Mt were slightly enhanced in the simultaneous adsorption system. The most effective pH range for the removal of Cr(VI) and RhB was found to be 3.0–4.0. Cr(VI) adsorption isotherms were best represented by the two-site Langmuir model while RhB isotherms followed the Freundlich model. For both contaminants, the adsorption of one contaminant increases with increase in the initial concentration of the other one. Therefore, Fe–Mt could simultaneously remove Cr(VI) and RhB from water. The properties of Fe–Mt were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and thermogravimetric analysis (TG). The findings of this study provide novel information for the development of clay-based adsorbents toward dyes and heavy metals.

Uniform iron pyrite mesocrystals were synthesized in a polyol solution. The growth processes of the iron pyrite mesocrystals include classical nucleation and growth, aggregative growth through oriented attachment, and Ostwald ripening. The growth mechanism may improve the controllable synthesis of iron pyrite crystals in terms of size, shape, properties, and potential applications such as electrocatalysis and photoelectrocatalysis.

The mineral lamprophyllite is fundamentally a silicate based upon tetrahedral siloxane units with extensive substitution in the formula. Lamprophyllite is a complex group of sorosilicates with general chemical formula given as A2B4C2Si2O7(X)4, where the site A can be occupied by strontium, barium, sodium, and potassium; the B site is occupied by sodium, titanium, iron, manganese, magnesium, and calcium. The site C is mainly occupied by titanium or ferric iron and X includes the anions fluoride, hydroxyl, and oxide. Chemical composition shows a homogeneous phase, composed of Si, Na, Ti, and Fe. This complexity of formula is reflected in the complexity of both the Raman and infrared spectra. The Raman spectrum is characterized by intense bands at 918 and 940 cm−1. Other intense Raman bands are found at 576, 671, and 707 cm−1. These bands are assigned to the stretching and bending modes of the tetrahedral siloxane units.

We have studied the mineral kornerupine, a borosilicate mineral, by using a combination of scanning electron microscopy with energy-dispersive analysis and Raman and infrared spectroscopy. Qualitative chemical analysis of kornerupine shows a magnesium–aluminum silicate. Strong Raman bands at 925, 995, and 1051 cm−1 with bands of lesser intensity at 1035 and 1084 cm−1 are assigned to the silicon–oxygen stretching vibrations of the siloxane units. Raman bands at 923 and 947 cm−1 are attributed to the symmetrical stretching vibrations of trigonal boron. Infrared spectra show greater complexity and the infrared bands are more difficult to assign. Two intense Raman bands at 3547 and 3612 cm−1 are assigned to the stretching vibrations of hydroxyl units. The infrared bands are observed at 3544 and 3610 cm−1. Water is also identified in the spectra of kornerupine.

The molecular structure of the copper-lead silicate mineral luddenite has been analysed using vibrational spectroscopy. The mineral is only one of many silicate minerals containing copper. The intense Raman band at 978 cm(-1) is assigned to the ν1 (A1g) symmetric stretching vibration of Si5O14 units. Raman bands at 1122, 1148 and 1160 cm(-1) are attributed to the ν3 SiO4 antisymmetric stretching vibrations. The bands in the 678-799 cm(-1) are assigned to OSiO bending modes of the (SiO3)n chains. Raman bands at 3317 and 3329 cm(-1) are attributed to water stretching bands. Bands at 3595 and 3629 cm(-1) are associated with the stretching vibrations of hydroxyl units suggesting that hydroxyl units exist in the structure of luddenite.

Priceite is a calcium borate mineral and occurs as white crystals in the monoclinic pyramidal crystal system. We have used a combination of Raman spectroscopy with complimentary infrared spectroscopy and scanning electron microscopy with Energy-dispersive X-ray Spectroscopy (EDS) to study the mineral priceite. Chemical analysis shows a pure phase consisting of B and Ca only. Raman bands at 956, 974, 991, and 1019 cm−1 are assigned to the BO stretching vibration of the B10O19 units. Raman bands at 1071, 1100, 1127, 1169, and 1211 cm−1 are attributed to the BOH in-plane bending modes. The intense infrared band at 805 cm−1 is assigned to the trigonal borate stretching modes. The Raman band at 674 cm−1 together with bands at 689, 697, 736, and 602 cm−1 are assigned to the trigonal and tetrahedral borate bending modes. Raman spectroscopy in the hydroxyl stretching region shows a series of bands with intense Raman band at 3555 cm−1 with a distinct shoulder at 3568 cm−1. Other bands in this spectral reg...

Raman spectra of two well-defined ferrimolybdite samples, Fe2(3+)(Mo6+O4)3·7-8H2O, from the Krupka deposit (northern Bohemia, Czech Republic) and Hůrky near Rakovník occurrence (central Bohemia, Czech Republic) were studied and tentatively interpreted. Observed bands were assigned to the stretching and bending vibrations of molybdate anions, Fe-O units and water molecules. Number of Raman and infrared bands assigned to (MoO4)(2-) units and water molecules proved that symmetrically (structurally) nonequivalent (MoO4)(2-) and H2O are present in the crystal structure of ferrimolybdite. Approximate O-H⋯O hydrogen bond lengths (2.80-2.73 Å) were inferred from the published infrared spectra.

The mineral beraunite from Boca Rica pegmatite in Minas Gerais with theoretical formula Fe(2+)Fe5(3+)(PO4)4(OH)5⋅4H2O has been studied using a combination of electron microscopy with EDX and vibrational spectroscopic techniques. Raman spectroscopy identifies an intense band at 990 cm(-1) and 1011 cm(-1). These bands are attributed to the PO4(3)(-) ν1 symmetric stretching mode. The ν3 antisymmetric stretching modes are observed by a large number of Raman bands. The Raman bands at 1034, 1051, 1058, 1069 and 1084 together with the Raman bands at 1098, 1116, 1133, 1155 and 1174 cm(-1) are assigned to the ν3 antisymmetric stretching vibrations of PO4(3-) and the HOPO3(2-) units. The observation of these multiple Raman bands in the symmetric and antisymmetric stretching region gives credence to the concept that both phosphate and hydrogen phosphate units exist in the structure of beraunite. The series of Raman bands at 567, 582, 601, 644, 661, 673, and 687 cm(-1) are assigned to the PO4(3-) ν2 bending modes. The series of Raman bands at 437, 468, 478, 491, 503 cm(-1) are attributed to the PO4(3-) and HOPO3(2-) ν4 bending modes. No Raman bands of beraunite which could be attributed to the hydroxyl stretching unit were observed. Infrared bands at 3511 and 3359 cm(-1) are ascribed to the OH stretching vibration of the OH units. Very broad bands at 3022 and 3299 cm(-1) are attributed to the OH stretching vibrations of water. Vibrational spectroscopy offers insights into the molecular structure of the phosphate mineral beraunite.

Raman spectroscopy complimented with infrared spectroscopy has been used to study the molecular structure of the mineral of plumbophyllite. The Raman spectrum is dominated by a very intense sharp peak at 1027 cm(-1), assigned to the SiO stretching vibrations of (SiO3)n units. A very intense Raman band at 643 cm(-1) is assigned to the bending mode of (SiO3)n units. Raman bands observed at 3215, 3443, 3470, 3494 and 3567 cm(-1) are assigned to water stretching vibrations. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate surfaces. Because of the close similarity in the structure of plumbophyllite and apophyllite, a comparison of the spectra with that of apophyllites is made. By using vibrational spectroscopy an assessment of the molecular structure of plumbophyllite has been made.

We have studied the hydrated hydroxyl silicate mineral inesite of formula Ca2(Mn,Fe)7Si10O28(OH)⋅5H2O using a combination of scanning electron microscopy with EDX and Raman and infrared spectroscopy. SEM analysis shows the mineral to be a pure monomineral with no impurities. Semiquantitative analysis shows a homogeneous phase, composed by Ca, Mn(2+), Si and P, with minor amounts of Mg and Fe. Raman spectrum shows well resolved component bands at 997, 1031, 1051, and 1067 cm(-1) attributed to a range of SiO symmetric stretching vibrations of [Si10O28] units. Infrared bands found at 896, 928, 959 and 985 cm(-1) are attributed to the OSiO antisymmetric stretching vibrations. An intense broad band at 653 cm(-1) with shoulder bands at 608, 631 and 684 cm(-1) are associated with the bending modes of the OSiO units of the 6- and 8-membered rings of the [Si10O28] units. The sharp band at 3642 cm(-1) with shoulder bands at 3612 and 3662 cm(-1) are assigned to the OH stretching vibrations of the hydroxyl units. The broad Raman band at 3420 cm(-1) with shoulder bands at 3362 and 3496 cm(-1) are assigned to the water stretching vibrations. The application of vibrational spectroscopy has enabled an assessment of the molecular structure of inesite to be undertaken.

Phosphohedyphane Ca2Pb3(PO4)3Cl is rare Ca and Pb phosphate mineral that belongs to the apatite supergroup. We have analysed phosphohedyphane using SEM with EDX, and Raman and infrared spectroscopy. The chemical analysis shows the presence of Pb, Ca, P and Cl and the chemical formula is expressed as Ca2Pb3(PO4)3Cl. The very sharp Raman band at 975 cm−1 is assigned to the PO 4 3 - ν1 symmetric stretching mode. Raman bands noted at 1073, 1188 and 1226 cm−1 are to the attributed to the PO 4 3 - ν3 antisymmetric stretching modes. The two Raman bands at 835 and 812 cm−1 assigned to the AsO 4 3 - ν1 symmetric stretching vibration and AsO 4 3 - ν3 antisymmetric stretching modes prove the substitution of As for P in the structure of phosphohedyphane. A series of bands at 557, 577 and 595 cm−1 are attributed to the ν4 out of plane bending modes of the PO4 units. The multiplicity of bands in the ν2, ν3 and ν4 spectral regions provides evidence for the loss of symmetry of the phosphate anion in the phosphohedyphane structure. Observed bands were assigned to the stretching and bending vibrations of phosphate tetrahedra. Some Raman bands attributable to OH stretching bands were observed, indicating the presence of water and/or OH units in the structure.

Vibrational spectroscopy has been used to study the rare earth mineral churchite of formula (REE)(PO4)⋅2H2O. The mineral contains a range of rare earth metals including yttrium depending on the locality. The Raman spectra of churchite-(REE) are characterized by an intense sharp band at 984 cm−1 assigned to the ν1 ( PO 4 3 - ) symmetric stretching mode. A lower intensity band observed at around 1067 cm−1 is attributed to the ν3 ( PO 4 3 - ) antisymmetric stretching mode. The ( PO 4 3 - ) bending modes are observed at 497 cm−1 (ν2) and 565 cm−1(ν4). Raman bands at 649 and 681 cm−1 are assigned to water librational modes. Vibrational spectroscopy enables aspects of the structure of churchite to be ascertained.

The mineral glauberite is one of many minerals formed in evaporite deposits. The mineral glauberite has been studied using a combination of scanning electron microscopy with energy dispersive X-ray analysis and infrared and Raman spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by sulfur, calcium, and sodium. Glauberite is characterized by a very intense Raman band at 1002 cm−1 with Raman bands observed at 1107, 1141, 1156, and 1169 cm−1 attributed to the sulfate ν3 antisymmetric stretching vibration. Raman bands at 619, 636, 645, and 651 cm−1 are assigned to the ν4 sulfate bending modes. Raman bands at 454, 472, and 486 cm−1 are ascribed to the ν2 sulfate bending modes. The observation of multiple bands is attributed to the loss of symmetry of the sulfate anion. Raman spectroscopy is superior to infrared spectroscopy for the determination of glauberite.

Raman and infrared spectra of two well-defined fluellite samples, Al2(PO4)F2(OH)·7H2O, from the Krásno near Horní Slavkov (Czech Republic) and Kapunda, South Australia (Australia) were studied and tentatively interpreted. Observed bands were assigned to the stretching and bending vibrations of phosphate tetrahedra, aluminum oxide/hydroxide/fluoride octahedra, water molecules and hydroxyl ions. Approximate O-H⋅⋅⋅O hydrogen bond lengths were inferred from the Raman and infrared spectra.

There are a large number of boron-containing minerals, of which vonsenite is one. Some discussion about the molecular structure of vonsenite exists in the literature. Whether water is involved in the structure is ill-determined. The molecular structure of vonsenite has been assessed by the combination of Raman and infrared spectroscopy. The Raman spectrum is characterized by two intense broad bands at 997 and 1059 cm−1 assigned to the BO stretching vibrational mode. A series of Raman bands in the 1200–1500 cm−1 spectral range are attributed to BO antisymmetric stretching modes and in-plane bending modes. The infrared spectrum shows complexity in this spectral range. No Raman spectrum of water in the OH stretching region could be obtained. The infrared spectrum shows a series of overlapping bands with bands identified at 3037, 3245, 3443, 3556, and 3614 cm−1. It is important to understand the structure of vonsenite in order to form nanomaterials based on its structure. Vibrational spectroscopy ena...

Burkeite formation is important in saline evaporites and in pipe scales. Burkeite is an anhydrous sulphate-carbonate with an apparent variable anion ratio. Such a formula with two oxyanions lends itself to vibrational spectroscopy. Two symmetric sulphate stretching modes are observed, indicating at least at the molecular level the nonequivalence of the sulphate ions in the burkeite structure. The strong Raman band at 1065 cm−1 is assigned to the carbonate symmetric stretching vibration. The series of Raman bands at 622, 635, 645, and 704 cm−1 are assigned to the ν4 sulphate bending modes. The observation of multiple bands supports the concept of a reduction in symmetry of the sulphate anion from T d to C 3v or even C 2v.

The mineral barahonaite is in all probability a member of the smolianinovite group. The mineral is an arsenate mineral formed as a secondary mineral in the oxidized zone of sulphide deposits. We have studied the barahonaite mineral using a combination of Raman and infrared spectroscopy. The mineral is characterized by a series of Raman bands at 863 cm−1 with low wavenumber shoulders at 802 and 828 cm−1. These bands are assigned to the arsenate and hydrogen arsenate stretching vibrations. The infrared spectrum shows a broad spectral profile. Two Raman bands at 506 and 529 cm−1 are assigned to the triply degenerate arsenate bending vibration (F 2, ν4), and the Raman bands at 325, 360, and 399 cm−1 are attributed to the arsenate ν2 bending vibration. Raman and infrared bands in the 2500–3800 cm−1 spectral range are assigned to water and hydroxyl stretching vibrations. The application of Raman spectroscopy to study the structure of barahonaite is better than infrared spectroscopy, probably because of...

Vibrational spectroscopy enables subtle details of the molecular structure of whiteite to be determined. Single crystals of a pure phase from a Brazilian pegmatite were used. The infrared and Raman spectroscopy were applied to compare the molecular structure of whiteite with that of other phosphate minerals. The Raman spectrum of whiteite shows an intense band at 972 cm(-1) assigned to the ν1PO4(3-) symmetric stretching vibrations. The low intensity Raman bands at 1076 and 1173 cm(-1) are assigned to the ν3PO4(3-) antisymmetric stretching modes. The Raman bands at 1266, 1334 and 1368 cm(-1) are assigned to AlOH deformation modes. The infrared band at 967 cm(-1) is ascribed to the PO4(3-)ν1 symmetric stretching vibrational mode. The infrared bands at 1024, 1072, 1089 and 1126 cm(-1) are attributed to the PO4(3-)ν3 antisymmetric stretching vibrations. Raman bands at 553, 571 and 586 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4(3-) unit. Raman bands at 432, 457, 479 and 500 cm(-1) are attributed to the ν2 PO4 and H2PO4 bending modes. In the 2600 to 3800 cm(-1) spectral range, Raman bands for whiteite are found 3426, 3496 and 3552 cm(-1) are assigned to AlOH stretching vibrations. Broad infrared bands are also found at 3186 cm(-1). Raman bands at 2939 and 3220 cm(-1) are assigned to water stretching vibrations. Raman spectroscopy complimented with infrared spectroscopy has enabled aspects of the structure of whiteite to be ascertained and compared with that of other phosphate minerals.

Gilalite is a copper silicate mineral with a general formula of Cu5Si6O17 · 7H2O. The mineral is often found in association with another copper silicate mineral, apachite, Cu9Si10O29 · 11H2O. Raman and infrared spectroscopy have been used to characterize the molecular structure of gilalite. The structure of the mineral shows disorder, which is reflected in the difficulty of obtaining quality Raman spectra. Raman spectroscopy clearly shows the absence of OH units in the gilalite structure. Intense Raman bands are observed at 1066, 1083, and 1160 cm−1. The Raman band at 853 cm−1 is assigned to the –SiO3 symmetrical stretching vibration and the low-intensity Raman bands at 914, 953, and 964 cm−1 may be ascribed to the antisymmetric SiO stretching vibrations. An intense Raman band at 673 cm−1 with a shoulder at 663 cm−1 is assigned to the ν4 Si-O-Si bending modes. Raman spectroscopy complemented with infrared spectroscopy enabled a better understanding of the molecular structure of gilalite.

Maxwellite NaFe(3+)(AsO4)F is an arsenate mineral containing fluoride and forms a continuous series with tilasite CaMg(AsO4)F. Both maxwellite and tilasite form a continuous series with durangite NaAl(3+)(AsO4)F. We have used the combination of scanning electron microscopy with EDS and vibrational spectroscopy to chemically analyse the mineral maxwellite and make an assessment of the molecular structure. Chemical analysis shows that maxwellite is composed of Fe, Na and Ca with minor amounts of Mn and Al. Raman bands for tilasite at 851 and 831cm(-1) are assigned to the Raman active ν1 symmetric stretching vibration (A1) and the Raman active triply degenerate ν3 antisymmetric stretching vibration (F2). The Raman band of maxwellite at 871cm(-1) is assigned to the ν1 symmetric stretching vibration and the Raman band at 812cm(-1) is assigned to the ν3 antisymmetric stretching vibration. The intense Raman band of tilasite at 467cm(-1) is assigned to the Raman active triply degenerate ν4 bending vibration (F2). Raman band at 331cm(-1) for tilasite is assigned to the Raman active doubly degenerate ν2 symmetric bending vibration (E). Both Raman and infrared spectroscopy do not identify any bands in the hydroxyl stretching region as is expected.

Gaudefroyite Ca 4 Mn 3 - x 3 + ( BO 3 ) 3 ( CO 3 ) ( O,OH ) 3 is an unusual mineral containing both borate and carbonate groups and is found in the oxidation zones of manganese minerals, and it is black in color. Vibrational spectroscopy has been used to explore the molecular structure of gaudefroyite. Gaudefroyite crystals are short dipyramidal or prismatic with prominent pyramidal terminations, to 5 cm. Two very sharp Raman bands at 927 and 1076 cm−1 are assigned to trigonal borate and carbonate respectively. Broad Raman bands at 1194, 1219 and 1281 cm−1 are attributed to BOH in-plane bending modes. Raman bands at 649 and 670 cm−1 are assigned to the bending modes of trigonal and tetrahedral boron. Infrared spectroscopy supports these band assignments. Raman bands in the OH stretching region are of a low intensity. The combination of Raman and infrared spectroscopy enables the assessment of the molecular structure of gaudefroyite to be made.

Tunellite is a strontium borate mineral with formula: SrB6O9(OH)2·3(H2O) and occurs as colorless crystals in the monoclinic pyramidal crystal system. An intense Raman band at 994 cm−1 was assigned to the BO stretching vibration of the B2O3 units. Raman bands at 1043, 1063, 1082 and 1113 cm−1 are attributed to the in-plane bending vibrations of trigonal boron. Sharp Raman bands observed at 464, 480, 523, 568 and 639 cm−1 are simply defined as trigonal and tetrahedral borate bending modes. The Raman spectrum clearly shows intense Raman bands at 3567 and 3614 cm−1, attributed to OH units. The molecular structure of a natural tunellite has been assessed by using vibrational spectroscopy.

Natural single-crystal specimens of althausite from Brazil, with general formula Mg2(PO4)(OH,F,O) were investigated by Raman and infrared spectroscopy. The mineral occurs as a secondary product in granitic pegmatites. The Raman spectrum of althausite is characterized by bands at 1020, 1033 and 1044 cm(-1), assigned to ν1 symmetric stretching modes of the HOPO3(3-) and PO4(3-) units. Raman bands at around 1067, 1083 and 1138 cm(-1) are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 575, 589 and 606 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. Raman bands at 439, 461, 475 and 503 cm(-1) are attributed to the ν2 PO4 and H2PO4 bending modes. Strong Raman bands observed at 312, 346 cm(-1) with shoulder bands at 361, 381 and 398 cm(-1) are assigned to MgO stretching vibrations. No bands which are attributable to water were found. Vibrational spectroscopy enables aspects of the molecular structure of althausite to be assessed.

We have studied the mineral väyrynenite from the Viitaniemi pegmatite, located in the Eräjärvi area, Finland using a combination of electron microscopy electron microprobe and vibrational spectroscopic techniques. Chemical analysis shows the formula of the mineral to be (Mn0.88, Fe0.08, Mg0.01)Σ0.97Be1.02(PO4)1.00(OH)1.02. Vibrational spectroscopy enables an assessment of the molecular structure of väyrynenite to be assessed. An intense Raman band at 1004 cm-1 is to the PO4 3- ν1 symmetric stretching mode. The observation of multiple bands in the phosphate stretching region, offers support for the concept of different phosphate units in the väyrynenite structure. Infrared spectroscopy confirms this multiplicity of vibrational bands. Multiple bands are observed in the phosphate bending region.

Natural single-crystal specimens of the herderite-hydroxylherderite series from Brazil, with general formula CaBePO4(F,OH), were investigated by electron microprobe, Raman, infrared and near-infrared spectroscopies. The minerals occur as secondary products in granitic pegmatites. Herderite and hydroxylherderite minerals show extensive solid solution formation. The Raman spectra of hydroxylherderite are characterized by bands at around 985 and 998 cm(-1), assigned to ν1 symmetric stretching mode of the HOPO3(3-) and PO4(3-) units. Raman bands at around 1085, 1128 and 1138 cm(-1) are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 563, 568, 577, 598, 616 and 633 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. The OH Raman stretching vibrations of hydroxylherderite were observed ranging from 3626 cm(-1) to 3609 cm(-1). The infrared stretching vibrations of hydroxylherderites were observed between 3606 cm(-1) and 3599 cm(-1). By using a Libowitzky type function, hydrogen bond distances based upon the OH stretching bands were calculated. Characteristic NIR bands at around 6961 and 7054 cm(-1) were assigned to the first overtone of the fundamental, whilst NIR bands at 10,194 and 10,329 cm(-1) are assigned to the second overtone of the fundamental OH stretching vibration. Insight into the structure of the herderite-hydroxylherderite series is assessed by vibrational spectroscopy.

We have used a combination of scanning electron microscopy with EDX and vibrational spectroscopy to study the mineral ardennite-(As). The mineral ardennite-(As) of accepted formula Mn 4 2 + (Al,Mg)6(Si3O10)(SiO4)2(AsO4,VO4)(OH)6 is a silicate mineral which may contain arsenate and/or vanadates anions. Because of the oxyanions present, the mineral lends itself to analysis by Raman and infrared spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by Si, Mn, Al and As. Ca and V were also observed in partial substitution for Mn and As. Raman bands at 1197, 1225, 1287 and 1394 cm−1 are assigned to SiO stretching vibrations. The strong Raman bands at 779 and 877 cm−1 are assigned to the AsO 4 3 - antisymmetric and symmetric stretching vibrations. The Raman band at 352 cm−1 is assigned to the ν2 symmetric bending vibration. The series of Raman bands between 414 and 471 cm−1are assigned to the ν4 out of plane bending modes of the AsO 4 3 - units. Intense Raman bands observed at 301 and 314 cm−1 are attributed to the MnO stretching and bending vibrations. Raman bands at 3041, 3149, 3211 and 3298 cm−1 are attributed to the stretching vibrations of OH units. There is vibrational spectroscopic evidence for the presence of water adsorbed on the ardennite-(As) surfaces.

The mineral series triplite-zwieselite with theoretical formula (Mn2+)2(PO4)(F)-(Fe2+)2(PO4)(F) from the El Criolo granitic pegmatite, located in the Eastern Pampean Ranges of Cordoba Province, was studied using electron microprobe, thermogravimetry, and Raman and infrared spectroscopy. The analysis of the mineral provided a formula of (Fe1.00, Mn0.85, Ca0.08, Mg0.06)∑2.00(PO4)1.00(F0.80, OH0.20)∑1.00. An intense Raman band at 981 cm−1 with a shoulder at 977 cm−1 is assigned to the ν1 symmetric stretching mode. The observation of two bands for the phosphate symmetric stretching mode offers support for the concept that the phosphate units in the structure of triplite-zwieselite are not equivalent. Low-intensity Raman bands at 1012, 1036, 1071, 1087, and 1127 cm−1 are assigned to the ν3 antisymmetric stretching modes. A set of Raman bands at 572, 604, 639, and 684 cm−1 are attributed to the ν4 out-of-plane bending modes. A single intense Raman band is found at 3508 cm−1 and is assigned to the stretching vibration of hydroxyl units. Infrared bands are observed at 3018, 3125, and 3358 cm−1 and are attributed to water stretching vibrations. Supplemental materials are available for this article. Go to the publisher's online edition of Spectroscopy Letters to view the supplemental file.

We have studied the mineral goyazite using Raman and infrared spectroscopy. Goyazite is a member of the crandallite subgroup of the alunite supergroup. The crystal structure is of the alunite-type and consists of sheets of corner-sharing AlO6 octahedra parallel to (0001). The octahedrally coordinated Sr(2+) cations occupy cavities between pairs of octahedral sheets and are surrounded by six oxygen atoms from the Al(3+)O6 octahedra. The very intense sharp band at 983 cm(-1) is assigned to the ν1PO4(3-) symmetric stretching mode. The observation of a single band supports the concept that all the phosphate units are equivalent in the structure of goyazite. Raman bands observed at 1029 cm(-1) and 1037 cm(-1) are assigned to the ν3PO4(3-) antisymmetric stretching vibrations. Two Raman bands at 895 and 927 cm(-1) are attributed to the stretching vibrations of H2PO4; thus indicating some hydrogen phosphate units in the structure of goyazite. Raman bands at 556, 581, 596 and 612 cm(-1) are assigned to the ν4PO4(3-) bending modes, suggesting a reduction of symmetry of phosphate units. Two sharp Raman bands at 3609 and 3631 cm(-1) are attributed to OH stretching vibrations from the goyazite hydroxyl units. Broad Raman bands at 2924, 3043, 3210, 3429 and 3511 cm(-1) are assigned to water stretching vibrations. This research shows that from a vibrational spectroscopic point of view, the formula SrAl3(H PO4,PO4)2(OH)6 · H2O is a better formulation for the mineral goyazite. Vibrational spectroscopy enables subtle details of the molecular structure of goyazite to be determined.

The mineral natrodufrenite a secondary pegmatite phosphate mineral from Minas Gerais, Brazil, has been studied by a combination of scanning electron microscopy and vibrational spectroscopic techniques. Electron probe analysis shows the formula of the studied mineral as (Na 0.88 Ca 0.12 ) ∑1.00 ( Fe 0.72 2 + Mn 0.11 Mg 0.08 Ca 0.04 Zr 0.01 Cu 0.01 ) ∑0.97 ( Fe 4.89 3 + Al 0.02 ) ∑4.91 (PO 4 ) 3.96 (OH 6.15 F 0.07 ) 6.22 ⋅2.05(H 2 O). Raman spectroscopy identifies an intense peak at 1003 cm −1 assigned to the PO 4 3 - ν 1 symmetric stretching mode. Raman bands are observed at 1059 and 1118 cm −1 and are attributed to the PO 4 3 - ν 3 antisymmetric stretching vibrations. A comparison is made with the spectral data of other hydrate hydroxy phosphate minerals including cyrilovite and wardite. Raman bands at 560, 582, 619 and 668 cm −1 are assigned to the ν 4 PO 4 3 - bending modes and Raman bands at 425, 444, 477 and 507 cm −1 are due to the ν 2 PO 4 3 - bending modes. Raman bands in the 2600–3800 cm −1 spectral range are attributed to water and OH stretching vibrations. Vibrational spectroscopy enables aspects of the molecular structure of natrodufrenite to be assessed.

Natural single-crystal specimens of barbosalite from Brazil, with general formula Fe2+Fe3+ 2 (PO4)2(OH)2 were investigated by Raman and infrared spectroscopy. The mineral occurs as secondary products in granitic pegmatites. The Raman spectrum of barbosalite is characterized by bands at 1020, 1033 and 1044 cm−1 cm−1, assigned to ν1 symmetric stretching mode of the HOPO3- 3 and PO3- 4 units. Raman bands at around 1067, 1083 and 1138 cm−1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 575, 589 and 606 cm−1 are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. Raman bands at 439, 461, 475 and 503 cm−1 are attributed to the ν2 PO4 and H2PO4 bending modes. Strong Raman bands observed at 312, 346 cm−1 with shoulder bands at 361, 381 and 398 cm−1 are assigned to FeO stretching vibrations. No bands which are attributable to water vibrations were found. Vibrational spectroscopy enables aspects of the molecular structure of barbosalite to be assessed.

The mineral kulanite BaFe2Al2(PO4)3(OH)3, a barium iron aluminum phosphate, has been studied by using a combination of electron microscopy and vibrational spectroscopy. Scanning electron microscopy with EDX shows the mineral is homogenous with no other phases present. The Raman spectrum is dominated by an intense band at 1022cm(-1) assigned to the PO4(3-)ν1 symmetric stretching mode. Low intensity Raman bands at 1076, 1110, 1146, 1182cm(-1) are attributed to the PO4(3-)ν3 antisymmetric stretching vibrations. The infrared spectrum shows a complex spectral profile with overlapping bands. Multiple phosphate bending vibrations supports the concept of a reduction in symmetry of the phosphate anion. Raman spectrum at 3211, 3513 and 3533cm(-1) are assigned to the stretching vibrations of the OH units. Vibrational spectroscopy enables aspects on the molecular structure of kulanite to be assessed.

Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral huanghoite with possible formula given as BaCe(CO3)2F and compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of huanghoite displays three bands are at 1072, 1084 and 1091 cm^-1 attributed to the (CO3)^2- symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of (CO3)^2- symmetric stretching vibration varies with mineral composition. Infrared spectroscopy of huanghoite show bands at 1319, 1382, 1422 and 1470 1091 cm^-1. No Raman bands of huanghoite were observed in these positions. Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 1091 cm^-1 assigned to the m3 (CO3)^2- antisymmetric stretching mode. The observation of additional Raman bands for the m3 modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands for huanghoite are observed at 687, 704, 718 and 730 1091 cm^-1 and assigned to the (CO3)^2- m2 bending modes. Raman bands are observed for huanghoite at around 627 1091 cm^-1 and are assigned to the (CO3)^2- m4 bending modes. Raman bands are observed for the carbonate m4 in phase bending modes at 722 1091 cm^-1 for bastnasite, 736 and 684 1091 cm^-1 for parisite, 714 1091 cm^-1 for northupite. Raman bands for huanghoite observed at 3259, 3484 and 3589 1091 cm^-1 are attributed to water stretching bands. Multiple bands are observed in the OH stretching region for bastnasite and parisite indicating the presence of water and OH units in their mineral structure. Vibrational spectroscopy enables new information on the structure of huanghoite to be assessed.

The pegmatite mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3 has been studied by a combination of SEM and EMP, Raman and infrared spectroscopy. The studied sample was collected from the Santa Ana pegmatite, Argentina. The mineral occurs as a primary mineral in lithium bearing pegmatite, in association with beausite and lithiophilite. The Raman spectrum is characterized by a very sharp intense Raman band at 980 cm−1 assigned to the PO 4 3 - symmetric stretching mode. Multiple Raman bands are observed in the PO 4 3 - antisymmetric stretching region, providing evidence for the existence of more than one phosphate unit in the structure of qingheiite and evidence for the reduction in symmetry of the phosphate units. This concept is affirmed by the number of bands in the ν4 and ν2 bending regions. No intensity was observed in the OH stretching region in the Raman spectrum but significant intensity is found in the infrared spectrum. Infrared bands are observed at 2917, 3195, 3414 and 3498 cm−1 are assigned to water stretching vibrations. It is suggested that some water is coordinating the metal cations in the structure of qingheiite.

The mineral kovdorskite Mg2PO4(OH)·3H2O was studied by electron microscopy, thermal analysis and vibrational spectroscopy. A comparison of the vibrational spectroscopy of kovdorskite is made with other magnesium bearing phosphate minerals and compounds. Electron probe analysis proves the mineral is very pure. The Raman spectrum is characterized by a band at 965 cm(-1) attributed to the PO4(3-) ν1 symmetric stretching mode. Raman bands at 1057 and 1089 cm(-1) are attributed to the PO4(3-) ν3 antisymmetric stretching modes. Raman bands at 412, 454 and 485 cm(-1) are assigned to the PO4(3-) ν2 bending modes. Raman bands at 536, 546 and 574 cm(-1) are assigned to the PO4(3-) ν4 bending modes. The Raman spectrum in the OH stretching region is dominated by a very sharp intense band at 3681 cm(-1) assigned to the stretching vibration of OH units. Infrared bands observed at 2762, 2977, 3204, 3275 and 3394 cm(-1) are attributed to water stretching bands. Vibrational spectroscopy shows that no carbonate bands are observed in the spectra; thus confirming the formula of the mineral as Mg2PO4(OH)·3H2O.

The metal lithium is very important in industry, including lithium batteries. An important source of lithium besides continental brines is granitic pegmatites as in Australia. Lithiophilite is a lithium and manganese phosphate with chemical formula LiMnPO4 and forms a solid solution with triphylite, its Fe analog, and belongs to the triphylite group that includes karenwebberite, natrophilite, and sicklerite. The mineral lithiophilite was characterized by chemical analysis and spectroscopic techniques. The chemical is: Li1.01(Mn0.60, Fe0.41, Mg0.01, Ca0.01)(PO4)0.99 and corresponds to an intermediate member of the triphylite-lithiophilite series, with predominance of the lithiophilite member. The mineral lithiophilite is readily characterized by Raman and infrared spectroscopy.

The mineral ettringite has been studied using a number of techniques, including XRD, SEM with EDX, thermogravimetry and vibrational spectroscopy. The mineral proved to be composed of 53% of ettringite and 47% of thaumasite in a solid solution. Thermogravimetry shows a mass loss of 46.2% up to 1000 ◦C. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1072 cm−1 attributed to a carbonate symmetric stretching mode, confirming the presence of thaumasite. The observation of multiple bands in the _4 spectral region between 700 and 550 cm−1 offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3629 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3487 cm−1 to water stretching bands. Vibrational spectroscopy enables an assessment of the molecular structure of natural ettringite to be made.

A natural single-crystal specimen of the krohnkite from Chuquicamata, Chile, with the general formula Na2Cu(SO4)2 · 2H2O, was investigated by Raman and infrared spectroscopy. The mineral krohnkite is found in many parts of the world's arid areas. Krohnkite crystallizes in the monoclinic crystal system with point group 2/m and space group P21/c. It is an uncommon secondary mineral formed in the oxidized zone of copper deposits, typically in very arid climates. The Raman spectrum of krohnkite dominated by a very sharp intense band at 992 cm−1 is assigned to the ν1 symmetric stretching mode and Raman bands at 1046, 1049, 1138, 1164, and 1177 cm−1 are assigned to the ν3 antisymmetric stretching vibrations. The infrared spectrum shows an intense band at 992 cm−1. The Raman bands at 569, 582, 612, 634, 642, 655, and 660 cm−1 are assigned to the ν4 bending modes. Three Raman bands observed at 429, 445, and 463 cm−1 are attributed to the ν2 bending modes. The observation that three or four bands are seen...

The mineral olshanskyite is one of many calcium borate minerals which has never been studied using vibrational spectroscopy. The mineral is unstable and decomposes upon exposure to an electron beam. This makes the elemental analysis using EDX techniques difficult. Both the Raman and infrared spectra show complexity due to the complexity of the structure. Intense Raman bands are found at 989, 1,003, 1,025 and 1,069 cm−1 with a shoulder at 961 cm−1 and are assigned to trigonal borate units. The Raman bands at 1,141, 1,206 and 1,365 cm−1 are assigned to OH in-plane bending of BOH units. A series of Raman bands are observed in the 2,900–3,621 cm−1 spectral range and are assigned to the stretching vibrations of OH and water. This complexity is also reflected in the infrared spectra. Vibrational spectroscopy enables aspects of the structure of olshanskyite to be elucidated.

The mineral leightonite, a rare sulphate mineral of formula K 2 Ca 2 Cu(SO 4 ) 4 ⋅2H 2 O, has been studied using a combination of electron probe and vibrational spectroscopy. The mineral is characterized by an intense Raman band at 991 cm −1 attributed to the SO 4 2 - ν 1 symmetric stretching mode. A series of Raman bands at 1047, 1120, 1137, 1163 and 1177 cm −1 assigned to the SO 4 2 - ν 3 antisymmetric stretching modes. The observation of multiple bands shows that the symmetry of the sulphate anion is reduced. Multiple Raman and infrared bands in the OH stretching region shows that water in the structure of leightonite is in a range of molecular environments.

An assessment of the molecular structure of carletonite a rare phyllosilicate mineral with general chemical formula given as KNa4Ca4Si8O18(CO3)4(OH,F).H2O has been undertaken using vibrational spectroscopy. Carletonite has a complex layered structure. Within one period of c, it contains a silicate layer of composition NaKSi8O18 H2O, a carbonate layer of composition NaCO3 0.5H2O and two carbonate layers of composition NaCa2CO3(F,OH)0.5. Raman bands are observed at 1066, 1075 and 1086 cm 1. Whether these bands are due to the CO2 3 m1 symmetric stretching mode or to an SiO stretching vibration is open to question. Multiple bands are observed in the 300–800 cm 1 spectral region, making the attribution of these bands difficult. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate and carbonate surfaces.

We have analyzed a frondelite mineral sample from the Cigana mine, located in the municipality of Conselheiro Pena, a well-known pegmatite in Brazil. In the Cigana pegmatite, secondary phosphates, namely eosphorite, fairfieldite, fluorapatite, frondelite, gormanite, hureaulite, lithiophilite, reddingite and vivianite are common minerals in miarolitic cavities and in massive blocks after triphylite. The chemical formula was determined as (Mn0.68, Fe0.32)(Fe(3+))3,72(PO4)3.17(OH)4.99. The structure of the mineral was assessed using vibrational spectroscopy. Bands attributed to the stretching and bending modes of PO4(3-) and HOPO3(3-) units were identified. The observation of multiple bands supports the concept of symmetry reduction of the phosphate anion in the frondelite structure. Sharp Raman and infrared bands at 3581 cm(-1) is assigned to the OH stretching vibration. Broad Raman bands at 3063, 3529 and 3365 cm(-1) are attributed to water stretching vibrational modes.

Vibrational spectroscopy enables subtle details of the molecular structure of cyrilovite to be determined. Single crystals of a pure phase from a Brazilian pegmatite were used. Cyrilovite is the Fe3+ member of the wardite group. The infrared and Raman spectroscopy were applied to compare the structure of cyrilovite with that of wardite. The Raman spectrum of cyrilovite in the 800–1400 cm−1 spectral range shows two intense bands at 992 and 1055 cm−1 assigned to the ν1 PO 4 3 - symmetric stretching vibrations. A series of low intensity bands at 1105, 1136, 1177 and 1184 cm−1 are assigned to the ν3 PO 4 3 - antisymmetric stretching modes. The infrared spectrum of cyrilovite in the 500–1300 cm−1 shows much greater complexity than the Raman spectrum. Strong infrared bands are found at 970 and 1007 cm−1 and are attributed to the ν1 PO 4 3 - symmetric stretching mode. Raman bands are observed at 612 and 631 cm−1 and are assigned to the ν4 out of plane bending modes of the PO 4 3 - unit. In the 2600–3800 cm−1 spectral range, intense Raman bands for cyrilovite are found at 3328 and 3452 cm−1 with a broad shoulder at 3194 cm−1 and are assigned to OH stretching vibrations. Sharp infrared bands are observed at 3485 and 3538 cm−1. Raman spectroscopy complimented with infrared spectroscopy has enabled the structure of cyrilovite to be ascertained and compared with that of wardite.

Raman spectrum of callaghanite, Cu2Mg2(CO3)(OH)6·2H2O, was studied and compared with published Raman spectra of azurite, malachite and hydromagnesite. Stretching and bending vibrations of carbonate and hydroxyl units and water molecules were tentatively assigned. Approximate O-H…O hydrogen bond lengths were inferred from the spectra. Because of the high content of hydroxyl ions in the crystal structure in comparison with low content of carbonate units, callaghanite should be better classified as a carbonatohydroxide than a hydroxycarbonate.

Colemanite CaB 3 O 4 (OH) 3 ·H 2 O is a secondary borate mineral formed from borax and ulexite in evaporate deposits of alkaline lacustrine sediments. The basic structure of colemanite contains endless chains of interlocking BO 2 (OH) triangles and BO 3 (OH) tetrahedrons with the calcium, water and extra hydroxide units interspersed between these chains. The Raman spectra of colemanite is characterized by an intense band at 3605 cm −1 assigned to the stretching vibration of OH units and a series of bands at 3182, 3300, 3389 and 3534 cm −1 assigned to water stretching vibrations. Infrared bands are observed in similar positions. The BO stretching vibrations of the trigonal and tetrahedral boron are characterized by Raman bands at 876, 1065 and 1084 cm −1 . The OBO bending mode is defined by the Raman band at 611 cm −1 . It is important to characterize the very wide range of borate minerals including colemanite because of the very wide range of applications of boron containing minerals.

We have studied bluish green crystals of the mineral florencite-(La) from Serra dos Carajas, Para, Brazil. Qualitative chemical analysis shows a La and Al phosphate with traces of Ce, Nd and Pr in substitution for La. Two sharp Raman bands at 987 and 1021 cm−1 assigned to the PO 4 3 - and HPO 4 2 - symmetric stretching modes. Raman bands at 1064, 1112 and 1221 cm−1 are attributed to the PO 4 3 - and HPO 4 2 - antisymmetric stretching modes. Raman bands at 404, 464, 524 and 526 cm−1 are assigned to the PO 4 3 - ν4 bending modes; An intense Raman band at 614 cm−1 with shoulder bands at 680 and 647 cm−1 are assigned to the PO 4 3 - ν2 bending modes. A sharp Raman band observed at 3649 cm−1 is assigned to the stretching vibration of the OH units. Raman bands at 2906, 2988, 3158 and 3440 cm−1 and infrared bands at 2808, 2956, 3117 and 3416 cm−1 are attributed to water stretching vibrations. The spectra in the OH stretching region support the concept of both hydroxyl and water units in the structure of florencite-La, thus confirming the formula as LaAl3(PO4)2(OH, H2O)6.

Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the phosphate mineral fairfieldite. The Raman phosphate (PO4)(3-) stretching region shows strong differences between the fairfieldite phosphate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists with multiple (PO4)2- antisymmetric stretching vibrations observed, indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 600 cm(-1) are assigned to ν4 phosphate bending modes. Multiple bands in the 400-450 cm(-1) region assigned to ν2 phosphate bending modes provide further evidence of symmetry reduction of the phosphate anion. Three broadbands for fairfieldite are found at 3040, 3139 and 3271 cm(-1) and are assigned to OH stretching bands. By using a Libowitzky empirical equation hydrogen bond distances of 2.658 and 2.730Å are estimated. Vibrational spectroscopy enables aspects of the molecular structure of the fairfieldite to be ascertained.

Zanazziite is the magnesium member of a complex beryllium calcium phosphate mineral group named roscherite. The studied samples were collected from the Ponte do Piaui mine, located in Itinga, Minas Gerais. The mineral was studied by electron microprobe, Raman and infrared spectroscopy. The chemical formula can be expressed as Ca 2.00 (Mg 3.15 ,Fe 0.78 ,Mn 0.16 ,Zn 0.01 ,Al 0.26 ,Ca 0.14 )Be 4.00 (PO 4 ) 6.09 (OH) 4.00 ⋅5.69(H 2 O) and shows an intermediate member of the zanazziite–greinfeinstenite series, with predominance of zanazziite member. The molecular structure of the mineral zanazziite has been determined using a combination of Raman and infrared spectroscopy. A very intense Raman band at 970 cm −1 is assigned to the phosphate symmetric stretching mode whilst the Raman bands at 1007, 1047, 1064 and 1096 cm −1 are attributed to the phosphate antisymmetric stretching mode. The infrared spectrum is broad and the antisymmetric stretching bands are prominent. Raman bands at 559, 568, 589 cm −1 are assigned to the ν 4 out of plane bending modes of the PO 4 and HPO 4 units. The observation of multiple bands supports the concept that the symmetry of the phosphate unit in the zanazziite structure is reduced in symmetry. Raman bands at 3437 and 3447 cm −1 are attributed to the OH stretching vibrations; Raman bands at 3098 and 3256 are attributed to water stretching vibrations. The width and complexity of the infrared spectral profile in contrast to the well resolved Raman spectra, proves that the pegmatitic phosphates are better studied with Raman spectroscopy.