Formation and transformation of manganese(III) intermediates in the photochemical generation of manganese(IV) oxide minerals.

As important natural oxidants and adsorbents, manganese (Mn) oxide minerals affect the speciation, bioavailability and fate of pollutants and nutrient elements. It was found that birnessite-type Mn(IV) oxide minerals can be formed in the presence of NO3- and solar irradiation. However, the photochemical formation and transformation processes from Mn2+ to Mn(IV) oxide minerals remain unclear. In this work, the Mn(IV) oxide minerals were confirmed to be photochemically formed mainly due to the disproportionation of Mn(III) intermediates generated from the oxidation of Mn2+ in the presence of NO3- under UV light irradiation. The oxidation rate of Mn2+ to Mn(IV) oxide minerals decreased with increasing initial Mn2+ concentration due to the lower disproportionation rate. The increase in NO3- concentration, pH and temperature promoted Mn2+ photochemical oxidation. The photochemical formation rate of Mn(IV) oxide minerals increased with increasing ligand concentrations at low ligand concentrations. Ligands affected the formation of Mn(IV) oxide minerals by promoting the formation and reducing the reactivity of Mn(III) intermediates. Overall, this work reveals the important role of Mn(III) intermediates in the formation of natural Mn oxide minerals.

Unravelling the Origin of the Yellow-Orange Luminescence in Natural and Synthetic Scapolites.

After decades of speculation without material proof, the yellow-orange luminescence of scapolite is definitely assigned to (S2)- activators trapped in [Na4] square cages. Synthetic sulfur-doped scapolites confirm the implication of sulfur species in luminescence. Formally, the emission and excitation spectra of various polysulfide species were calculated. The excellent match between theory and experiments for (S2)- dimers provides definitive proof that it is the cause of the yellow-orange luminescence in scapolite.

Insights on photochemical activities of organic components and minerals in dissolved state biochar in the degradation of atorvastatin in aqueous solution.

This study systematically investigated the photocatalytic activity of dissolved state biochar (DSB) with different pyrolysis temperature to the degradation of atorvastatin (ATV), a medicine widely used to combat hyperlipidemia. It was found that the photocatalytic efficiency of DSB increased with the decrease of pyrolysis temperature, that is, DSB300 (DSB with 300 °C of pyrolysis temperature) had the greatest photocatalytic activity in same condition, which was attributed to the dual role of DSB300 as heterogeneous photocatalyst and photosensitizer. The mineral components were responsible for the heterogeneous photocatalytic activity of DSB300. Organic carbon components could synergistically enhance the heterogeneous photocatalytic activity by enhancement of electron-hole separation, and contribute to the formation of singlet oxygen (1O2) and triplet-excited state (3DSB*) as well. The identification of intermediate products and X-ray photoelectron spectroscopy (XPS) analysis of irradiated DSB300/ATV revealed that cross-coupling reaction between ATV and DSB existed in the photodegradation process of ATV. The detailed photodegradation pathways of ATV were proposed, which was triggered by oxygen insertion of pyrrole ring and hydroxyl addition. Meanwhile, the modification of DSB300 under irradiation was evidently attenuated with ATV as shown by multiple characterizations, which helped to keep the stability of DSB300 in photochemical reaction process.

In Situ Geochronology on Mars and the Development of Future Instrumentation.

We review the in situ geochronology experiments conducted by the Mars Science Laboratory mission's Curiosity rover to understand when the Gale Crater rocks formed, underwent alteration, and became exposed to cosmogenic radiation. These experiments determined that the detrital minerals in the sedimentary rocks of Gale are ∼4 Ga, consistent with their origin in the basalts surrounding the crater. The sedimentary rocks underwent fluid-moderated alteration 2 Gyr later, which may mark the closure of aqueous activity at Gale Crater. Over the past several million years, wind-driven processes have dominated, denuding the surfaces by scarp retreat. The Curiosity measurements validate radiometric dating techniques on Mars and guide the way for future instrumentation to make more precise measurements that will further our understanding of the geological and astrobiological history of the planet.

Emergency EPR and OSL dosimetry with table vitamins and minerals.

Several table vitamins, minerals and L-lysine amino acid have been preliminarily tested as potential emergency dosemeters using electron paramagnetic resonance (EPR) and optically stimulated luminescence (OSL) techniques. Radiation-induced EPR signals were detected in samples of vitamin B2 and L-lysine while samples of multivitamins of different brands as well as mineral Mg demonstrated prominent OSL signals after exposure to ionizing radiation doses. Basic dosimetric properties of the radiation-sensitive substances were studied, namely dose response, fading of the EPR or OSL signals and values of minimum measurable doses (MMDs). For EPR-sensitive samples, the EPR signal is converted into units of dose using a linear dose response and correcting for fading using the measured fading dependence. For OSL-sensitive materials, a multi-aliquot, enhanced-temperature protocol was developed to avoid the problem of sample sensitization and to minimize the influence of signal fading. The sample dose in this case is also evaluated using the dose response and fading curves. MMDs of the EPR-sensitive samples were below 2 Gy while those of the OSL-sensitive materials were below 500 mGy as long as the samples are analyzed within 1 week after exposure.

Mineralization of hetero bi-functional reactive dye in aqueous solution by Fenton and photo-Fenton reactions.

This study focused on the advanced oxidation of the hetero bi-functional reactive dye Sumifix Supra Yellow 3RF (CI Reactive Yellow 145) using dark Fenton and photo-Fenton conditions in a lab-scale experiment. A 2(3) factorial design was used to evaluate the effects of the three key factors: temperature, Fe(II) and H2O2 concentrations, for a dye concentration of 250 mg L(-1) with chemical oxygen demand (COD) of 172 mg L(-1) O2 at pH=3. The response function was the COD reduction. This methodology lets us find the effects and interactions of the studied variables and their roles in the efficiency of the treatment process. In the optimization, the correlation coefficients for the model (R2) were 0.948 and 0.965 for Fenton and photo-Fenton treatments, respectively. Under optimized reaction conditions: pH=3, temperature=298 K, [H2O2]=11.765 mM and [Fe(II)]=1.075 mM; 60 min of treatment resulted in a 79% and 92.2% decrease in COD, for the dye taken as the model organic compound, after Fenton and photo-Fenton treatments, respectively.

Dissolution and reconstitution of casein micelle containing dairy powders by high shear using ultrasonic and physical methods.

The effect of shear on the solubilization of a range of dairy powders was investigated. The rate of solubilization of low solubility milk protein concentrate and micellar casein powders was examined during ultrasonication, high pressure homogenization and high-shear rotor-stator mixing and compared to low-shear overhead stirring. The high shear techniques were able to greatly accelerate the solubilization of these powders by physically breaking apart the powder agglomerates and accelerating the release of individual casein micelles into solution. This was achieved without affecting the structure of the solubilized proteins. The effect of high shear on the re-establishment of the mineral balance between the casein micelles and the serum was examined by monitoring the pH of the reconstituted skim milk powder after prior exposure to ultrasonication. Only minor differences in the re-equilibration of the pH were observed after sonication for up to 3 min, suggesting that the localized high shear forces exerted by sonication did not significantly affect the mass transfer of minerals from within the casein micelles.

Light-activated bleaching: effects on surface mineral change on enamel.

AIM: This study evaluated the in vitro effect of 35% hydrogen peroxide (HP) on surface enamel change when activated with different light curing units (LCUs). MATERIALS AND METHODS: Enamel blocks (4 × 4 × 2 mm) were obtained from bovine incisors. The initial microhardness of the enamel was determined for each specimen. After this enamel blocks were randomly divided into four groups (n = 10) and treated as follows: Control, no bleaching procedure performed; HP - LCU, application of 35% HP gel without light activation; HP + QTH, application of 35% HP gel and light activation with a Quartz Tungsten-Halogen (QTH); and HP + Light Emitting Diode, application of 35% HP gel and light-activation with a LED. New microhardness measurements were obtained, immediately, 7 and 14 days after treatment. The percentage of surface mineral change was calculated according to the baseline and post-treatment microhardness values. Additionally, six samples from each group were randomly selected and prepared for scanning electron microscopy (SEM) characterization. The data were analyzed using an analysis of variance (ANOVA) to detect differences between the three time periods, and an ANOVA and Tukey's test with a confidence level of 95%. RESULTS: There was no significant difference between the initial hardness values and hardness values after treatment in any of the groups or time periods (p > 0.05). No major surface alterations were detected with SEM when comparing control groups to those undergoing bleaching treatments. CONCLUSION: The use of 35% HP in combination to QTH or LED light curing units LCU does not have detrimental effect on the enamel surface topography or in the mineral content, when compared with unbleached enamel or enamel submitted to 35% HP treatment alone.

Potential mechanism for the laser-fluoride effect on enamel demineralization.

Laser-induced prevention of dental caries has been studied extensively. However, the cariostatic mechanisms of a combined fluoride-laser treatment are not well-understood. Using micro- computed tomography (micro-CT), we quantified the effect of fluoride and/or Er:YAG laser treatment on enamel demineralization. The mean mineral loss (%/V) for each group was 4,870 ± 1,434 (fluoride followed by laser treatment), 6,341 ± 2,204 (laser treatment), 7,669 ± 2,255 (fluoride treatment), and 10,779 ± 2,936 (control). The preventive effect of the laser (p < 0.001) and fluoride (p = 0.010) treatment was statistically significant. Characterized by micro-x-ray diffraction (XRD) analysis, the significant contraction in the a-axis after both laser and combined laser/fluoride treatment was revealed (both p < 0.05). In conclusion, subablative low-energy Er:YAG laser irradiation following fluoride treatment may instantaneously transform enamel hydroxyapatite into fluoridated hydroxyapatite to reduce enamel solubility as a preventive treatment for enamel demineralization.

Photooxidation of chloride by oxide minerals: implications for perchlorate on Mars.

We show that highly oxidizing valence band holes, produced by ultraviolet (UV) illumination of naturally occurring semiconducting minerals, are capable of oxidizing chloride ion to perchlorate in aqueous solutions at higher rates than other known natural perchlorate production processes. Our results support an alternative to atmospheric reactions leading to the formation of high concentrations of perchlorate on Mars.

Performance quantification of applicators for microwave treatment of crushed mineral ore.

Exposure of crushed mineral ores to microwaves at high power density (-10(9) to 10(11) W/ m3(abs)) and for short exposure times (< 0.1 s) induces grain boundary fracture around the grains of the value minerals at economically viable energy inputs (-1 kWh/t). In subsequent processing steps, liberation of the value minerals is enhanced, improving the efficiency of the process. In this paper the performance of transverse E-field applicators for the continuous treatment of 30 t/h of crushed ore was quantified using damage maps. These provide the amount of microwave-induced grain boundary damage and the fraction of the load treated as a function of input power and throughput. The damage maps are created by combining the outputs from thermal stress simulations (for the determination of thermal damage) with those from electromagnetic simulations (for the determination of the 3d dissipation of power in the load). The results are to be used to select the optimal applicator structure and operating parameters (bed height and speed) for a given ore. Results from two applicator configurations for a coarser and finer-grained galena-calcite ore are used to exemplify the results. It is shown high the texture of the ore significantly reduces performance in terms of achievable throughput and required energy input. It is also shown that sub-optimal electromagnetic design also results in reduced throughput and increased energy requirement.

Ultrasonic degradation, mineralization and detoxification of diclofenac in water: optimization of operating parameters.

The 20 kHz ultrasound-induced degradation of non-steroidal, anti-inflammatory drug diclofenac (DCF) was investigated. Several operating conditions, such as power density (25-100 W/L), substrate concentration (2.5-80 mg/L), initial solution pH (3.5-11), liquid bulk temperature and the type of sparging gas (air, oxygen, argon), were tested concerning their effect on DCF degradation (as assessed measuring absorbance at 276 nm) and hydroxyl radicals generation (as assessed measuring H(2)O(2) concentration). Sample mineralization (in terms of TOC and COD removal), aerobic biodegradability (as assessed by the BOD(5)/COD ratio) and ecotoxicity to Daphnia magna and Artemia salina were followed too. DCF conversion is enhanced at increased applied power densities and liquid bulk temperatures, acidic conditions and in the presence of dissolved air or oxygen. The reaction rate increases with increasing DCF concentration in the range 2.5-5mg/L but it remains constant in the range 40-80 mg/L, indicating different kinetic regimes (i.e. first and zero order, respectively). H(2)O(2) production rates in pure water are higher than those in DCF solutions, implying that decomposition basically proceeds through hydroxyl radical reactions. Mineralization is a slow process as reaction by-products are more stable than DCF to total oxidation; nonetheless, they are also more readily biodegradable. Toxicity to D. magna increases during the early stages of the reaction and then decreases progressively upon degradation of reaction by-products; nevertheless, complete toxicity elimination cannot be achieved at the conditions in question. Neither the original nor the treated DCF samples are toxic to A. salina.

Progress towards a polymineral single-aliquot OSL dating procedure.

Published single-aliquot regenerative-dose (SAR) procedures for quartz use a 'cutheat' different from the pre-heat. In contrast, previous work has shown that the SAR procedure can be used to correct for sensitivity changes exhibited by feldspars if the cutheat is equal to the pre-heat. In this paper, a procedure that corrects for sensitivity changes in both quartz and feldspar is tested. The results indicate that for sedimentary quartz the cutheat can be equal to the pre-heat. Thus, it may be possible to develop one procedure to measure equivalent doses in a polymineral sample. We also tested several different optical stimulation methods. Using the infrared (IR)-stimulated signal from a post-IR blue-stimulated optically stimulated luminescence sequence extends the potential age range when using feldpathic materials. In addition, since the post-IR blue-stimulated signal from feldspar is much smaller than the blue-stimulated signal from quartz, the possibility exists of extracting a 'quartz signal' from a mixed mineral sample.

ESR dosimetric properties of some biomineral materials.

Dosimetric properties of g-irradiated modern coral and bioactive glass (Bio-G) samples analyzed with electron spin resonance (ESR) have been separately reported (Hassan et al., 2004; Sharaf and Hassan, 2004) and compared with alanine. These are combined here to allow a three-way comparison between these materials.

Peripheral thermal and mechanical damage to dentin with microsecond and sub-microsecond 9.6 microm, 2.79 microm, and 0.355 microm laser pulses.

BACKGROUND AND OBJECTIVES: It is desirable to minimize peripheral thermal damage during laser irradiation, since thermal damage to collagen and mineral compromises the bond strength to restorative materials in dentin and inhibits healing and osteointegration in bone. There were two primary objectives of this study. The first objective was to measure the degree of thermal damage peripheral to incisions in dentin produced with lasers resonant to the specific absorption bands of water, collagen, and hydroxyapatite with varying pulse duration using polarized-light microscopy (PLM). The second objective was to use synchrotron radiation infrared spectromicroscopy (SR-FTIR) to identify the specific chemical nature of the optical changes observed under PLM in the respective zones of thermal damage peripheral to the laser incisions. STUDY DESIGN/MATERIALS AND METHODS: Precise incisions were produced in 3 x 3 mm2 blocks of human dentin using CO2 (9.6 microm), Er:YSGG (2.79 microm), and Nd:YAG (355 nm) lasers with and without a computer controlled water-spray. Optical coherence tomography (OCT) was used to obtain optical cross-sections of each incision to determine the rate of ablation. The peripheral thermal damage zone around each incision was analyzed using PLM and SR-FTIR. RESULTS: Thermally induced chemical changes to both mineral and the collagen matrix were observed with SR-FTIR with a 10 microm spatial resolution and those changes were correlated with optical changes observed with PLM. Minimal (<10 microm) thermal damage was observed for pulse durations less than the thermal relaxation time (Tr) of the deposited laser energy, with and without applied water at 9.6 microm and with only applied water at 2.79 microm. For pulse durations greater than Tr, greater peripheral thermal damage was observed for both IR laser wavelengths with and without the water-spray. There was minimal thermal damage for 355 nm laser pulses less than Tr with and without applied water; however, extensive mechanical damage (cracks) was observed. CONCLUSIONS: High resolution SR-FTIR is well suited for characterization of the chemical changes that occur due to thermal damage peripheral to laser incisions in proteinaceous hard tissues. Sub-microsecond pulsed IR lasers resonant with water and mineral absorption bands ablate dentin efficiently with minimal thermal damage. Similar laser parameters are expected to apply to the ablation of alveolar bone.

Effects of heating on the emanation rates of radon-222 from a suite of natural minerals.

The emanating power of radon provides information on the internal structure of a mineral and the radiation damage caused by the decay of 238U, 235U and 232Th (and their daughters) that are present in the mineral. The concentration of 222Rn in groundwater is primarily controlled by the concentration of U and Th in the underlying rocks, as well as the emanation coefficient for that particular rock. The variations in the emanation coefficient for 222Rn caused when subsurface rocks are subjected to tectonic forces results in changes in 222Rn in groundwater. Increased emanation rates of radon from a mineral grain can potentially alter the 238U-206Pb, 235U-207Pb and 232Th-208Pb chronological clocks. We have measured radon emanation coefficients on a suite of minerals comprised of one oxide (uraninite), three silicates (thorite, zircon, and cerite) and one phosphate (monazite) at room temperature and after heating at 200 degrees C and 600 degrees C. Annealing of some of the nuclear tracks within a mineral significantly reduces the emanation rates of radon in these minerals, suggesting that the tracks created by decay events serve as conduit pathways for the release of 222Rn. Higher emanation rates of 222Rn from mineral grains that are surrounded by liquid as compared to air indicate that a major portion of the escaping 222Rn in air gets embedded into adjacent mineral grains and/or opposite walls of a pore.

Cooperative radiative and nonradiative effects in K2NaScF6 codoped with V3+ and Er3+.

K2NaScF6 crystals codoped with V3+ and Er3+ exhibit some novel cooperative near-IR to visible upconversion processes at cryogenic temperatures. V3+ mainly acts as a broadband sensitizer. The V3+ 3T1g --> 3T2g excitation between 13,500 and 15,500 cm(-1), after fast relaxation to V3+ 1T2g, can be transferred to Er3+ 4I(11/2), and then upconversion takes place. Four upconversion mechanisms are identified and characterized. For narrow-band laser excitation the overall efficiency of the upconversion processes is low. However, at 12 K for broadband excitation, such as in a lamp, between 12,000 and 14,500 cm(-1) the number of emitted visible photons is roughly doubled by codoping V3+ in addition to Er3+.

Dosimetric characterisation of Brazilian natural stones using the thermally stimulated exoelectron emission technique.

A thermally stimulated exoelectron emission (TSEE) measuring system developed and constructed at IPEN was used to verify the feasibility of the use of Brazilian natural semi-precious stones, such as jasper. amethyst, agate (blue and rose) and quartz (rose and white) for gamma and X radiation detection. Its counting system consists of a 2pi windowless gas-flow proportional counter, and the heating system is formed by a temperature programmer that provides linear heating of the samples. The samples were tested in gamma and in X radiation beams and evaluated in relation to their main dosimetric characteristics, as TSEE glow curves, calibration curves and energy dependence. The TSEE results are compared with those of thermoluminescence. The results obtained show the usefulness of Brazilian natural stones as dosimetric materials, using the thermoluminescence and thermally stimulated exoelectron emission techniques.

Combining photolysis and bioprocesses for mineralization of high molecular weight polyacrylamides.

The influence of ultraviolet photolysis as a pretreatment to the aerobic and anaerobic biological mineralization of a 14C-polyacrylamide was assessed using a series of radiorespirometry bioassays. The polyacrylamide studied was non-ionic with molecular weights ranging between 100,000 and 1 million. Aerobic and anaerobic biomineralization of the unphotolysed (raw) polyacrylamide was found to be only 0.60% and 0.70%, respectively, after 6 weeks of incubation, and hence indicative of the natural recalcitrance of polyacrylamide to microbial degradation. The effectiveness of UV irradiation in the physical breakdown of the polyacrylamide chain into oligomers was demonstrated by the shift in the molecular weight distribution and the positive correlation between the time of irradiation and the degree of its biological mineralization. The molecular weight fraction below 3 kD, which represents only 2% of the raw polyacrylamide, was increased to 41, 60 and 80% after 12, 24 and 48 hours of photolysis, respectively. This in turn, yielded, after 6 weeks of incubation, an aerobic mineralization of 5, 17 and 29% of 150 mg/L polyacrylamide, respectively, and an anaerobic mineralization of 3, 5 and 17%, respectively. Biomass acclimation substantially improved the specific initial rate of biomineralization of the photolysed polyacrylamides, but not the overall percentage of polyacrylamides mineralized.