Spectroscopic investigation in the mid- and far-infrared regions of phosphorus fertilizers derived from thermochemically treated sewage sludge ash

Inorganic phosphorus and nitrogen-phosphorus-potassium (NPK) fertilizers based on phosphates from thermochemically treated sewage sludge ash were analyzed using mid-infrared (mid-IR) and far-infrared (FIR) spectroscopy. The different compounds present in the fertilizers were qualitatively determined with the help of recorded reference spectra of pure substances. Differentiation between various phosphates and other compounds such as sulfates, nitrates, and oxides was possible using combined interpretation of the mid-IR and FIR spectra. The results are in agreement with previous X-ray diffraction (XRD) measurements of the same samples. The main phosphate phases detected were NH(4)H(2)PO(4), MgHPO(4)·3H(2)O, Mg(3)(PO(4))(2), Ca(5)(PO(4))(5)Cl, CaHPO(4)·2H(2)O, Ca(H(2-)PO(4))(2)·H(2)O, and AlPO(4). Furthermore, K(2)SO(4), NH(4)NO(3), Fe(2)O(3), and SiO(2) were identified in the IR spectra. However, ammonium and sulfate compounds were only identified in the mid-IR region but were not detectable in the FIR region.     

Non-aqueous synthesis of water-dispersible Fe3O4-Ca3(PO4)2 core-shell nanoparticles

The Fe(3)O(4)-Ca(3)(PO(4))(2) core-shell nanoparticles were prepared by one-pot non-aqueous nanoemulsion with the assistance of a biocompatible triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO), integrating the magnetic properties of Fe(3)O(4) and the bioactive functions of Ca(3)(PO(4))(2) into single entities. The Fe(3)O(4) nanoparticles were pre-formed first by thermal reduction of Fe(acac)(3) and then the Ca(3)(PO(4))(2) layer was coated by simultaneous deposition of Ca(2+) and PO(4)(3-). The characterization shows that the combination of the two materials into a core-shell nanostructure retains the magnetic properties and the Ca(3)(PO(4))(2) shell forms an hcp phase (a = 7.490 ?, c = 9.534 ?) on the Fe(3)O(4) surface. The magnetic hysteresis curves of the nanoparticles were further elucidated by the Langevin equation, giving an estimation of the effective magnetic dimension of the nanoparticles and reflecting the enhanced susceptibility response as a result of the surface covering. Fourier transform infrared (FTIR) analysis provides the characteristic vibrations of Ca(3)(PO(4))(2) and the presence of the polymer surfactant on the nanoparticle surface. Moreover, the nanoparticles could be directly transferred to water and the aqueous dispersion-collection process of the nanoparticles was demonstrated for application readiness of such core-shell nanostructures in an aqueous medium. Thus, the construction of Fe(3)O(4) and Ca(3)(PO(4))(2) in the core-shell nanostructure has conspicuously led to enhanced performance and multi-functionalities, offering various possible applications of the nanoparticles.     

Characterization of aqueous lead removal by phosphatic clay: equilibrium and kinetic studies

Immobilization of heavy metals from contaminated environments is an emerging field of interest from both resource conservation and environmental remediation points of view. This study investigated the feasibility of using phosphatic clay, a waste by-product of the phosphate mining industry, as an effective sorbent for Pb from aqueous effluents. The major parameters controlling aqueous Pb removal, viz. initial metal ion concentrations, solution pH, sorbent amounts, ionic strength and presence of both inorganic and organic ligands were evaluated using batch experiments. Results demonstrated that aqueous Pb removal efficiency of phosphatic clay is controlled mainly by dissolution of phosphatic clay associated fluoroapatite [Ca(10)(PO(4))(5)CaCO(3)(F,Cl,OH)(2)], followed by subsequent precipitation of geochemically stable pyromorphite [Pb(10)(PO(4))(6)(F,Cl,OH)(2)], which was confirmed by both X-ray diffraction (XRD) and scanning electron microscopic (SEM) analysis. Lead removal efficiency of phosphatic clay increased with increasing pH, sorbent amount and decreasing ionic strength. It also depends on the nature of complexing ligands. Formation of insoluble calcium oxalate and lead oxalate in the presence of oxalic acid explained high uptake of Pb by phosphatic clay from aqueous solution. However, Pb sorption kinetics onto phosphatic clay were biphasic, with initially fast reactions followed by slow and continuous Pb removal reactions. The slow reactions may include surface sorption, co-precipitation and diffusion. The exceptional capability of phosphatic clay to remove aqueous Pb demonstrated its potential as a cost effective way to remediate Pb-contaminated water, soils and sediments.     

Boron removal and recovery from concentrated wastewater using a microwave hydrothermal method

Boron compounds are widely-used raw materials in industries. However, elevated boron concentrations in aqueous systems may be harmful to human and plants. In this study, calcium hydroxide (Ca(OH)(2)) alone and Ca(OH)(2) with phosphoric acid (H(3)PO(4)) addition (P-addition) were used to remove and recover boron from wastewater using hydrothermal methods. A microwave (MW) hydrothermal method was used and compared with the conventional heating (CH) method in batch experiments. Physicochemical properties of the precipitates obtained from both methods were analysed by XRD, SEM with EDX and BET. For the case of Ca(OH)(2) alone and the MW method, experimental results showed that boron recovery efficiency reached 90% within 10 min, and crystals of Ca(2)B(2)O(5)·H(2)O were found in the precipitates as indicated by the XRD analysis. For the case of P-addition and the MW method, boron recovery efficiency reached 99% within 10 min, and calcium phosphate species (CaHPO(4)·H(2)O, CaHPO(4) and Ca(10)(PO(4))(6)(OH)(2)) were formed. The experimental results of this study indicate that the required reaction time of the MW method was much less than that of the CH method, and the MW method is an effective and efficient method for boron removal and recovery from concentrated wastewater.     

Preparation, characterization and mechanical performance of dense β-TCP ceramics with/without magnesium substitution

Beta-tricalcium phosphate (beta-TCP) powder was prepared by a two-step process: wet precipitation of apatitic tricalcium phosphate [Ca(9)(HPO(4))(PO(4))(5)(OH)] (beta-TCP 'precursor') and calcination of the precursor at 800 degrees C for 3 h to produce beta-TCP. Magnesium-substituted tricalcium phosphate (beta-TCMP) was produced by adding Mg(NO(3))(2) . 6H(2)O into Ca(NO(3))(2) solution as Mg(2+) source before the precipitation step. The transition temperature from beta-TCP to alpha-TCP increases with the increase of Mg(2+) content in beta-TCMP. beta-TCMP with 3 mol.% Mg(2+) has beta-TCP to alpha-TCP transition temperature above 1,300 degrees C. Dense beta-TCMP (3 mol.% Mg(2+)) ceramics ( approximately 99.4% relative density) were produced by pressing the green bodies at 100 MPa and further sintering at 1,250 degrees C for 2 h. The average compressive strength of dense beta-TCP ceramics sintered at 1,100 degrees C is approximately 540 MPa, while that of beta-TCMP (3 mol.% Mg(2+)) ceramics is approximately 430 MPa.     

Phosphate removal using sludge from fuller's earth production

This study assesses the phosphate removal capacity and mechanism of precipitation or adsorption from aqueous solutions in batch experiments by an industrial sludge containing gypsum (CaSO(4).2H(2)O) obtained as a by-product from a fuller's earth process. The potential capacity for phosphate removal was tested using various solution concentrations, pH values, reaction times, and amount of sludge. The maximum phosphate adsorption capacity calculated using the Langmuir equation was 2.0 g kg(-1). The pH for the maximum adsorption by the sludge was neutral to alkaline (pH 7-12). Over 99% of phosphate was removed from a phosphate solution of 30 mg L(-1) using 0.15 g of sludge in a 9-h reaction. Sulfate (SO(4)(2-)) concentration increased with increasing initial phosphate concentration, possibly because of dissolution of gypsum and adsorption of both sulfate and phosphate. At high phosphate concentration (>1000 mg L(-1)), relative constant concentration of Ca(2+) was not consistent with adsorption of the most important phosphate removal mechanism. Results suggest that precipitation of calcium phosphate is principally responsible for phosphate removal under its high concentration. Agglomerated precipitate in the reaction sludge was observed by SEM and identified as brushite (CaHPO(4).2H(2)O) by XRD, FT-IR, and DTA. Based on thermodynamic considerations, it is suggested that the brushite will readily transform to more stable phases, such as hydroxyapatite (Ca(5)(PO(4))(3).OH).     

Electrolytic deposition of amorphous and crystalline zinc–calcium phosphates

Amorphous Zn–Ca phosphates and crystalline Zn3(PO4)2·4H2O conversion layers on cathode substrates were prepared by electrolysis of mixtures of acidic solutions saturated with metal phosphates. The solutions contained tricalcium phosphate (Ca3(PO4)2) and/or zinc phosphate dihydrate (Zn3(PO4)2·2H2O). The depositions was carried out with constant or pulsating cathode current densities in the range 20–70 mA cm-2 at 20–70 °C. The deposition of the uniform crystalline Zn3(PO4)2·4H2O was performed at a pulsating cathode current density of 70 mA cm-2 at 70 °C for periods up to 10 min. Amorphous deposits of Zn–Ca phosphates containing 20 wt% H2O with variable Zn-to-Ca ratios were deposited at a constant cathodic current of 30 mA cm-2 at 20 °C for 3 min. Surface areas of the amorphous deposits were of the order of 28 m2 g-1. X-ray diffraction, differential thermal analysis and thermogravimetry were used to investigate phase formation and transitions at increasing temperatures. The amorphous Zn–Ca phosphate deposit was after calcination at 900 °C transformed to crystalline phosphates containing the -Ca3(PO4)2 or Ca3-xZnx(PO4)2 and -CaZn2(PO4) phases. © 1998 Kluwer Academic Publishers     

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 1. Artificially aged model samples

On several paintings by artists of the end of the 19th century and the beginning of the 20th Century a darkening of the original yellow areas, painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is observed. The most famous of these are the various Sunflowers paintings Vincent van Gogh made during his career. In the first part of this work, we attempt to elucidate the degradation process of chrome yellow by studying artificially aged model samples. In view of the very thin (1-3 μm) alteration layers that are formed, high lateral resolution spectroscopic methods such as microscopic X-ray absorption near edge (μ-XANES), X-ray fluorescence spectrometry (μ-XRF), and electron energy loss spectrometry (EELS) were employed. Some of these use synchrotron radiation (SR). Additionally, microscopic SR X-ray diffraction (SR μ-XRD), μ-Raman, and mid-FTIR spectroscopy were employed to completely characterize the samples. The formation of Cr(III) compounds at the surface of the chrome yellow paint layers is particularly observed in one aged model sample taken from a historic paint tube (ca. 1914). About two-thirds of the chromium that is present at the surface has reduced from the hexavalent to the trivalent state. The EELS and μ-XANES spectra are consistent with the presence of Cr(2)O(3)·2H(2)O (viridian). Moreover, as demonstrated by μ-XANES, the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide], is likely.     

Sorption of aqueous phosphorus onto bituminous and lignitous coal ashes

Aiming at the development of a phosphorus removal technology for waste water, phosphate (PO(4)(3-)) retention behavior of bituminous and lignitous coal ashes was investigated using a batch reactor. Ash samples, including fresh and weathered fly and bottom ashes, were studied for their sorption isotherms and reversibility. Fly ashes had a much higher phosphate retention capacity (4000-30,000mgP/kg) than bottom ashes (15-600mgP/kg). Lignitous coal ashes were more capable of retaining phosphate than bituminous coal ashes. The retention process was largely irreversible, and the irreversibility increased with the increase in the retention capacity. Weathering enlarged the retention capacity of the bituminous bottom ash, but substantially lowered that of the fly ash, likely due to the difference in the weather-induced changes between the fly and bottom ashes. Sorption isotherms of fly ashes were found to be adequately represented by the Langmuir model while those of bottom ashes fitted better to the Freundlich model. Concentrations of Ca(2+) and PO(4)(3-) in the aqueous phase were measured at the end of sorption and desorption experiments, and were compared with solubilities of three calcium phosphate minerals. The aqueous solutions were saturated or super-saturated with respect to tricalcium phosphate (Ca(3)(PO(4))(2)) and hydroxyapatite (Ca(5)(PO(4))(3)OH), and slightly under-saturated with respect to amorphous calcium phosphate. It is concluded that precipitation of calcium phosphate is the predominant mechanism for phosphate retention by coal ash under the conditions studied. There is a strong and positive correlation between alkalinity and phosphate sorption capacity. Consequently, acid neutralization capacity (ANC) can be used as an indicator of phosphate sorption capacity of coal ashes.     

The influence of Sr and H3PO4 concentration on the hydration of SrCaHA bone cement

Sr-contained calcium hydroxyapatite (SrCaHA) cement is a potential biomaterial for in vivo bone repair and surgery fixation due to its excellent biodegradability, bioactivity, biocompatibility, easily shaping and self-hardening. We had ever reported the in vitro physiochemical properties, biocompatibility and in vivo degradability of the SrCaHA cement obtained by mixing a cement powder of Ca(4)(PO(4))(2)O/CaHPO(4)/SrHPO(4) and a cement liquid of diluted H(3)PO(4) aqueous solution. In the present study, we intensively studied the influences of both Sr content and H(3)PO(4) concentration in diluted phosphoric acid aqueous solution on the setting time, hydration heat-liberation behaviours, and real-time microstructure and phase evolutions of the SrCaHA cement. The results show that both PO(4)(3-) and H(+) ions in PA solution attended the hydration reaction as reactants, and thus the increase of the PA concentration not only promoted the dissolution of Ca(4)(PO(4))(2)O but also pushed the hydration progress of SrCaHA bone cement. Sr content exhibits a remarkable retardation role on the apatite transformation of the SrCaHA cement pastes which probably attributed to its higher degree of supersaturation for yielding apatite crystals and lower transformation rate when exposed to the Sr(2+)-containing hydration system. This present results contribute to a better understanding on the hydration mechanism of the new SrCaHA cement and help to the more precisely controlling of its hydration process.     

溶胶凝胶法制备磷酸锆钠陶瓷材料

以Zr(NO3)4.5H2O、NH4H2PO4和NaNO3为原材料,采用溶胶凝胶法合成了磷酸锆钠(NaZr2(PO4)3)陶瓷粉体,采用TG-DTA,XRD和SEM测试方法对粉体性能进行了表征,研究了烧结温度和pH值等反应条件对粉体合成的影响.结果表明,要获纯的磷酸锆钠粉体,合成温度需控制在800～1 000℃之间,其中最合适合成温度为900℃左右.前驱体pH值对合成温度基本没有影响,但会影响产物微观形貌.当合成温度为900℃,pH值为9时可以制备出团聚较少、颗粒均匀、分散性较好且平均粒径为100nm的磷酸锆钠粉体.     

Surface characterization of hydroxyapatite and related calcium phosphates by XPS and TOF-SIMS

The surfaces of six biologically interesting calcium phosphate (CaP) phases (hydroxyapatite, dibasic calcium phosphate dihydrate, dibasic calcium phosphate, monobasic calcium phosphate, beta-tribasic calcium phosphate, octacalcium phosphate) have been examined by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The intensity of an O(1s) shake-up satellite correlates with the phosphate oxygen content. Together with the Ca/P and O/Ca XPS peak ratios, this feature helps provide identification of the CaP phase(s) present in the surface of unknown samples and establish their mole fractions, as proven with a bone sample. Contributions from carbonate impurities can be quantified using its C(1s) peak at 279.9 eV and subtracted from the O(1s) line shape to aid identification. Principal component analysis (PCA) has been applied successfully to analyze TOF-SIMS spectra of these six CaP phases. Multivariate analysis can help differentiate these CaP phases using the first two PCs, which are dominated by the relative intensities of only a few key ions: PO3-, O-, Ca+, CaOH+, PO2-, and OH-.     

Hydrothermal synthesis and electrochemical properties of Li₃V₂(PO₄)₃/C-based composites for lithium-ion batteries

To improve performance at higher rates, we developed a hydrothermal method to prepare carbon-coated monoclinic lithium vanadium phosphate (Li(3)V(2)(PO(4))(3)) powder to be used as a cathode material for Li-ion batteries. The structural, morphological and electrochemical properties were characterized by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and galvanostatic charge-discharge cycling. A superior cycle and rate behavior are demonstrated for Li(3)V(1.85)Sc(0.15)(PO(4))(3)/C and Li(2.96)Ca(0.02)V(2)(PO(4))(3)/C electrodes at charge-discharge current rates above 5C.     

The transformation of single-crystal calcium phosphate ribbon-like fibres to hydroxyapatite spheres assembled from nanorods

Two precursors of ribbon-like anhydrous dicalcium phosphate (DCPA) and calcium phosphate fibres were successfully synthesized at 85?°C through a simple and mild pathway from Ca(NO(3))(2)·4H(2)O and (NH(4))(2)HPO(4) upon the hydrolysis of urea. Different molar concentrations of urea resulted in different precursors, including precursor I (DCPA phase) and precursor II (calcium phosphate with DCPA, octacalcium phosphate (OCP) and hydroxyapatite (HAp) phase). By immersing the two precursors in ammonium hydroxide solution (pH = 12), the transformation from precursors to hydroxyapatite could be achieved. X-ray diffraction (XRD) results combined with transmission electron microscopy (TEM) indicated that DCPA fibres (precursor I) were transformed to HAp nanorods in transformation I. In transformation II, dandelion-like spheres assembled by HAp nanorods were obtained from calcium phosphate (precursor II). The mechanisms of transformations I and II are also proposed and discussed based on the XRD and TEM results.     

In Vivo Characteristics of Premixed Calcium Phosphate Cements When Implanted in Subcutaneous Tissues and Periodontal Bone Defects

Previous studies showed that water-free, premixed calcium phosphate cements (Pre-CPCs) exhibited longer hardening times and lower strengths than conventional CPCs, but were stable in the package. The materials hardened only after being delivered to a wet environment and formed hydroxyapatite as the only product. Pre-CPCs also demonstrated good washout resistance and excellent biocompatibility when implanted in subcutaneous tissues in rats. The present study evaluated characteristics of Pre-CPCs when implanted in subcutaneous tissues (Study I) and used for repairing surgically created two-wall periodontal defects (Study II). Pre-CPC pastes were prepared by combining CPC powders that consisted of CPC-1: Ca(4)(PO(4))(2)O and CaHPO(4), CPC-2: α-Ca(3)(PO(4))(2) and CaCO(3) or CPC-3: DCPA and Ca(OH)(2) with a glycerol at powder-to-liquid mass ratios of 3.5, 2.5, and 2.5, respectively. In each cement mixture, the Ca to P molar ratio was 1.67. The glycerol contained Na(2)HPO(4) (30 mass %) and hydroxypropyl methylcellulose (0.55 %) to accelerate cement hardening and improve washout resistance, respectively. In Study I, the test materials were implanted subcutaneously in rats. Four weeks after the operation, the animals were sacrificed and histopathological observations were performed. The results showed that all of the implanted materials exhibited very slight or negligible inflammatory reactions in tissues contacted with the implants. In Study II, the mandibular premolar teeth of mature beagle dogs were extracted. One month later, two-wall periodontal bone defects were surgically created adjacent to the teeth of the mandibular bone. The defects were filled with the Pre-CPC pastes and the flaps replaced in the preoperative position. The dogs were sacrificed at 1, 3 and 6 months after surgery and sections of filled defects resected. Results showed that one month after surgery, the implanted Pre-CPC-1 paste was partially replaced by bone and was converted to bone at 6 months. The pockets filled with Pre-CPC-2 were completely covered by newly formed bone in 1 month. The Pre-CPC-2 was partially replaced by trabecular bone in 1 month and was completely replaced by bone in 6 months. Examination of 1 month and 3 month samples indicated that Pre-CPC-2 resorbed and was replaced by bone more rapidly than Pre-CPC 1. Both Pre-CPC pastes were highly osteoconductive. When implanted in periodontal defects, Pre-CPC-2 was replaced by bone more rapidly than Pre-CPC-1.     

Synthesis of a novel layered double hydroxides [MgAl(4)(OH)(12)](Cl)(2)·2.4H(2)O and its anion-exchange properties

A novel layered double hydroxide of Mg and Al with composition [Mg(0.96)Al(4.00)(OH)(12)]Cl(1.86)(CO(3))(0.03)·2.4H(2)O, designated as MgAl(4)-Cl, was synthesized by mixing crystalline gibbsite (γ-Al(OH)(3)) and solid MgCl(2)·6H(2)O with subsequent hydrothermal treatment at 160 °C for 72h. The MgAl(4)-Cl exhibited a crystalline material of a layered structure, as evidenced from X-ray diffraction. Anion uptake experiments with the MgAl(4)-Cl showed that Cl(-) in the interlayer space can be exchanged with anions such as Br(-), H(2)PO(4)(-), CO(3)(2-) or dodecyl sulfate (DS(-)) from aqueous solutions with preservation of the layered structure. Uptake of NO(3)(-), BrO(3)(-) or SO(4)(2-) on the MgAl(4)-Cl showed different behavior; these anions can be exchanged within 1h maintaining the layered structure, but a release of Mg(2+) cations from the sample was observed with increased reaction time, resulting in collapse of the layered structure and formation of the gibbsite phase, as determined from chemical analyses and X-ray diffraction.     

An investigation of the chemical synthesis and high-temperature sintering behaviour of calcium hydroxyapatite (HA) and tricalcium phosphate (TCP) bioceramics

The experimental conditions for the synthesis of sub-micrometre,spherical particles of calcium hydroxyapatite[Ca10(PO4)6(OH)2] (HA) andtricalcium phosphate [Ca3(PO4)2] (TCP) areinvestigated through chemical coprecipitation from the aqueous solutions ofcalcium nitrate and di-ammonium hydrogen phosphate salts. The precipitationprocess employed was also found to be suitable for the production ofsub-micrometre HA/TCP composite powders in situ. The synthesized pureHA and TCP powders were found to be stable even at 1300°C in air forprolonged heating times. Bioceramic sample characterization was achieved bypowder X-ray diffraction (XRD), scanning electron microscopy (SEM), energydispersive X-ray spectroscopy (EDX), and density and surface area measurements.Crystallographic analyses of HA powders were performed by the Rietveld method onthe powder XRD data.     

Raman and infrared spectroscopic investigations on aqueous alkali metal phosphate solutions and density functional theory calculations of phosphate-water clusters

Phosphate (PO(4)(3-)) solutions in water and heavy water have been studied by Raman and infrared spectroscopy over a broad concentration range (0.0091-5.280 mol/L) including a hydrate melt at 23 degrees C. In the low wavenumber range, spectra in R-format have been constructed and the R normalization procedure has been briefly discussed. The vibrational modes of the tetrahedral PO(4)(3-)(aq) (T(d) symmetry) have been assigned and compared to the calculated values derived from the density functional theory (DFT) method for the unhydrated PO(4)(3-)(T(d)) and phosphate-water clusters: PO(4)(3-).H(2)O (C(2v)), PO(4)(3-).2H(2)O (D(2d)), PO(4)(3-).4H(2)O (D(2d)), PO(4)(3-).6H(2)O (T(d)), and PO(4)(3-).12H(2)O (T), a cluster with a complete first hydration sphere of water molecules. A cluster with a second hydration sphere of 12 water molecules and 6 in the first sphere, PO(4)(3-).18H(2)O (T), has also been calculated. Agreement between measured and calculated vibrational modes is best in the case of the PO(4)(3-).12H(2)O cluster and the PO(4)(3-).18H(2)O cluster but far less so in the case of the unhydrated PO(4)(3-) or phosphate-water cluster with a lower number of water molecules than 12. The asymmetric, broad band shape of v(1)(a(1)) PO(4)(3-) in aqueous solutions has been measured as a function of concentration and the asymmetric and broad band shape was explained. However, the same mode in heavy water has only half the full width at half-height compared to the mode in normal water. The PO(4)(3-) is strongly hydrated in aqueous solutions. This has been verified by Raman spectroscopy comparing v(2)(H(2)O), the deformation mode of water, and the stretching modes, the v(1)OH and v(3)OH of water, in K(3)PO(4) solutions as a function of concentration and comparison with the same modes in pure water. A mode at approximately 240 cm(-1) (isotropic R spectrum) has been detected and assigned to the restricted translational mode of the strong hydrogen bonds formed between phosphate and water, P-O...HOH. In very concentrated K(3)PO(4) solutions (C(0) > or = 3.70 mol/L) and in the hydrate melt, formation of contact ion pairs (CIPs) could be detected. The phosphate in the CIPs shows a symmetry lowering of the T(d) symmetry to C(3v). In the less concentrated solutions, PO(4)(3-)(aq) solvent separated ion pairs and doubly solvent separated ion pairs exist, while in very dilute solutions fully hydrated ions are present (C(0) < or = 0.005 mol/L). Quantitative Raman measurements have been carried out to follow the hydrolysis of PO(4)(3-)(aq) over a very broad concentration range. From the hydrolysis data, the pK(3) value for H(3)PO(4) has been determined to be 12.45 at 23 degrees C.     

Tributyl phosphate as a sensitivity-enhancing solvent for organotin in carbon furnace atomic absorption spectrometry

Tributyl phosphate (TBP) has been found to be a sensitivity-enhancing solvent for organotin compounds in graphite furnace atomic absorption spectrometry; (C(4)H(9))(2)Sn(O(2)CCH(3))(2), (C(4)H(9))(2)Sn(O(2)CC(11)H(23))(2), (C(4)H(9))(3)SnCl, and (C(4)H(9))(4)Sn all give 1 order of magnitude higher sensitivities in TBP than in toluene or ethyl acetate. The sensitivities are enhanced further 1-2 orders of magnitude in TBP, when PdCl(2)(CH(3)CN)(2) is added as a matrix modifier in the organic solvent. Among the four organotin compounds, (C(4)H(9))(2)Sn(O(2)CCH(3))(2) and (C(4)H(9))(2)Sn(O(2)CC(11)H(23))(2) give better sensitivities than (C(4)H(9))(3)SnCl and (C(4)H(9))(4)Sn in the absence of palladium in any organic solvent, which suggests that the oxygen atom in the tin compound might form tin oxides that are resistant to volatilization loss during ashing. Scanning electron microscopic, electrothermal vaporization ICPMS, and powder X-ray diffraction studies show that the final products before atomization include phosphorus-containing compounds Sn(2)P(2)O(7), SnP(2)O(7), and Pd(9)P(2), besides tin-palladium alloys, PdSn, Pd(3)Sn, Pd(2)Sn, Pd(3)Sn(2), and PdSn(3). These phosphorus-containing compounds would more efficiently stabilize tin and suppress tin vaporization loss during ashing, to give higher sensitivity.     

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 2. Original paint layer samples

The darkening of the original yellow areas painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is a phenomenon widely observed on several paintings by Vincent van Gogh, such as the famous different versions of Sunflowers. During our previous investigations on artificially aged model samples of lead chromate, we established for the first time that darkening of chrome yellow is caused by reduction of PbCrO(4) to Cr(2)O(3)·2H(2)O (viridian green), likely accompanied by the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide]. In the second part of this work, in order to demonstrate that this reduction phenomenon effectively takes place in real paintings, we study original paint samples from two paintings of V. van Gogh. As with the model samples, in view of the thin superficial alteration layers that are present, high lateral resolution spectroscopic methods that make use of synchrotron radiation (SR), such as microscopic X-ray absorption near edge (μ-XANES) and X-ray fluorescence spectrometry (μ-XRF) were employed. Additionally, μ-Raman and mid-FTIR analyses were carried out to completely characterize the samples. On both paint microsamples, the local presence of reduced Cr was demonstrated by means of μ-XANES point measurements. The presence of Cr(III) was revealed in specific areas, in some cases correlated to the presence of Ba(sulfate) and/or to that of aluminum silicate compounds.