Vaporization Mechanisms of Water-Insoluble Cs in Ash During Thermal Treatment with Calcium Chloride Addition.

The vaporization mechanisms of water-insoluble Cs in raw ash and Cs-doped ash during thermal treatment with CaCl2 addition was systematically examined in a lab-scale electrical heating furnace over a temperature range of 500-1500 °C. The results indicate that the water-insoluble Cs in the ash was associated with aluminosilicate as pollucite. Addition of 10% CaCl2 caused the maximum vaporization ratio of Cs in the raw ash to reach approximately 80% at temperatures higher than 1200 °C, whereas approximately 95% of Cs was vaporized at temperatures higher than 1300 °C when 30% CaCl2 was added. The formation of an intermediate compound, CsCaCl3, through the chemical reaction of Cs with CaCl2 was responsible for Cs vaporization by means of the subsequent decomposition of this intermediate upon the increase in temperature. The indirect chlorination of Cs by the gaseous chlorine released from the decomposition of CaCl2 was insignificant. A high CaCl2 content in the resulting annealed products with 30% CaCl2 addition delayed the decomposition of CsCaCl3 and thus lowered the Cs vaporization ratio compared to that with 10% CaCl2 addition at 900-1250 °C. Thermal treatment with CaCl2 addition is a proposed method to remove Cs from Cs-contaminated incineration ash.

Use of synchrotron XANES and Cr-doped coal to further confirm the vaporization of organically bound Cr and the formation of chromium(VI) during coal oxy-fuel combustion.

Through the use of synchrotron XANES and Cr-doped brown coal, extensive efforts have been made to clarify the volatility of organically bound Cr during oxy-fuel combustion and the mode of occurrence and leachability of Cr in resulting fly ashes. As the continuation of our previous study using raw coal, the Cr-doped coal has been tested in this study to improve the signal-to-noise ratio for Cr K-edge XANES spectra, and hence the accuracy for Cr(VI) quantification. As has been confirmed, the abundant CO(2) as a balance gas for oxy-firing has the potential to inhibit the decomposition of organically bound Cr, thereby favoring its retention in solid ash. It also has the potential to promote the oxidation of Cr(III) to Cr(VI) to a minor extent. Increasing the oxygen partial pressure, particularly in the coexistence of HCl in flue gas, favored the oxidation of Cr(III) into gaseous Cr(VI)-bearing species such as CrO(2)Cl(2). Regarding the solid impurities including Na(2)SO(4) and CaO, Na(2)SO(4) has proven to preferentially capture the Cr(III)-bearing species at a low furnace temperature such as 600 °C. Its promoting effect on the oxidation of Cr(III) to Cr(VI), although thermodynamically available at the temperatures examined here, is negligible in a lab-scale drop tube furnace (DTF), where the particle residence time is extremely short. In contrast, CaO has proven facilitating the capture of Cr(VI)-bearing species particularly oxychloride vapors at 1000 °C, forming Ca chromate with the formulas of CaCrO(4) and Ca(3)(CrO(4))(2) via a direction stabilization of Cr(VI) oxychloride vapor by CaO particle or an indirect oxidation of Cr(III) via the initial formation of Ca chromite. The fly ash collected from the combustion of Cr-doped coal alone has a lower water solubility (i.e., 58.7%) for its Cr(VI) species, due to the formation of Ba/Pb chromate and/or the incorporation of Cr(VI) vapor into a slagging phase which is water-insoluble. Adding CaO to coal increased the water-solubility of both Cr(VI) and Cr(III) by forming Ca chromite and chromate, respectively.

Phacoemulsification with vitreous loss using phacoemulsifier and vitrector concurrently: bimanual-bipedal technique.

Vitreous loss is one of the adverse complications that can occur during phacoemulsification. Once vitreous loss is identified, procedural guidelines advise that phacoemulsification be ceased and the probe carefully withdrawn to minimize traction on the vitreous. Bimanual-bipedal technique described in this study holds the phacoemulsification probe in place and inserts the vitrectomy cutter through the pars plana port with the other hand. After removal of vitreous around the phacoemulsification tip, the vitrectomy cutter is switched to a cutting rate of zero. phacoemulsification can then be resumed with the vitrectomy cutter as a retainer of the lens fragments, similar to the hook of bimanual technique. Lens fragments are synergistically retained through aspiration between the vitrectomy cutter and phacoemulsification probe to prevent displacement. The bimanual-bipedal technique may offer a more streamlined and potentially safer approach for phacoemulsification with vitreous loss.

Synchrotron-based XANES speciation of chromium in the oxy-fuel fly ash collected from lab-scale drop-tube furnace.

Speciation of chromium (Cr) in the fly ash collected from oxy-firing of Victorian brown coal has been reported for the first time to address the potential formation of toxic Cr(VI) and the variation of the quantities of Cr(III)-bearing species with flue gas composition. Synchrotron-based X-ray absorption near-edge structure (XANES) was employed for Cr speciation. Apart from a pure O(2)/CO(2) mixture (27/73, v/v) versus air, the O(2)/CO(2) mixtures doped with SO(2), HCl, and steam individually or together to simulate real flue gas have also been tested. Under all of the conditions tested here, the fractions of Cr(VI) in the fly ashes are insignificant, constituting no more than 5% of the total Cr. The test of Cr-doped brown coal in pyrolysis further confirmed that the Cr(VI) formation preferentially occurred through a local oxidation of Cr(III) at the oxygen-containing functions sites within coal matrix, rather than through an oxidation by external bulk O(2). This reaction is also highly temperature-dependent and slower than the interaction between Cr(III) and other metals such as iron oxide. Increasing temperature to 1000 °C inhibited the oxidation of Cr(IIII) to Cr(VI). Shifting the combustion gas from air to O(2)/CO(2) exerted little effect on the Cr(VI) formation. Instead, the formation of iron chromite (FeCr(2)O(4)) was facilitated in O(2)/CO(2), probably due to a strong reducing microenvironment formed by the CO(2) gasification reaction within the char matrix. The accumulation of HCl in flue gas favored the vaporization of chromium as gaseous chloride/oxychloride, as expected. The coexistence of SO(2) inhibited this phenomenon by promoting the formation of sulfate. The presence of steam was even beneficial for the inhibition of water-soluble Cr sulfate through stabilizing the majority of Cr into alumino-silicate which is in the slagging phase.

Do FeCl3 and FeCl3/CaO conditioners change pyrolysis and incineration performances, emissions, and elemental fates of textile dyeing sludge?

The pyrolysis and incineration performances of sulfur-rich textile dyeing sludge (TDSS) were determined in response to the additions of FeCl3 or FeCl3 + CaO. The emissions of eight air pollutants from the incineration and pyrolysis were systematically identified. The 3-to-8% FeCl3 additions increased the comprehensive combustibility index by 2.14 and 1.62 times, respectively, as opposed to the 5-to-10% FeCl3 + 8-to-15% CaO additions. The CaO addition inhibited the TDSS incineration, while the FeCl3 addition increased HCl emission. NOx, SO2, and H2S emissions decreased initially and increased between 600 and 950 °C. SO2 and NOx emissions rose with FeCl3 but FeCl3 + CaO. FeCl3 catalyzed NOx, while CaO retained SO2. The main pyrolysis gas/liquid products were alkane, alkenes, nitrile, heterocyclic compounds, benzene, and its derivatives. Benzene and its derivatives accounted for 55.33% of the control group and 42.25-57.23% of the treatment groups. The FeCl3 and FeCl3 + CaO additions did not significantly influence the pyrolysis products. The measured versus thermodynamically simulated SOx and HCl emissions were consistent. Neural network-based simultaneous optimizations of the non-linear dynamics of eight kinds of gases pointed to 50% and 14.4% reductions in the emissions and the pyrolytic temperature, respectively, with the 3% FeCl3, relative to the control.

Use of thermal treatment with CaCl2 and CaO to remove 137Cs in the soil collected from the area near the Fukushima Daiichi Nuclear Power Plant.

A massive amount of soils and inflammable materials of plants etc. contaminated by radiocesium are generated from decontamination work in the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident affected area. In present study, the removal experiments of 137Cs in a soil collected from the FDNPP accident affected area were carried out in a lab-scale electrical heating horizontal furnace through thermal treatment with CaCl2 addition over a temperature of 900 - 1300 °C. The results indicated that the average radioactive concentration of 137Cs in the soil was 52.8 Bq/g. The removal ratio of 137Cs in the soil treated at 1300 °C was 96.3 % when 20 % CaCl2 was added. The addition of CaCl2 and CaO mixture exhibited a synergistic effect on the removal of 137Cs, relative to the addition of CaCl2 alone. Accordingly, the addition of CaCl2 or its mixture with CaO during thermal treatment is suggested to remove 137Cs in the soil collected from the FDNPP accident affected area. Additionally, segregation of the soil sample to fine and coarse fraction and then treated individually are also recommended.

Conduction-band effective mass and bandgap of ZnSnN2 earth-abundant solar absorber.

Pseudo III-V nitride ZnSnN2 is an earth-abundant semiconductor with a high optical absorption coefficient in the solar spectrum. Its bandgap can be tuned by controlling the cation sublattice disorder. Thus, it is a potential candidate for photovoltaic absorber materials. However, its important basic properties such as the intrinsic bandgap and effective mass have not yet been quantitatively determined. This paper presents a detailed optical absorption analysis of disordered ZnSnN2 degenerately doped with oxygen (ZnSnN2-x O x ) in the ultraviolet to infrared region to determine the conduction-band effective mass (m c*) and intrinsic bandgap (E g). ZnSnN2-x O x epilayers are n-type degenerate semiconductors, which exhibit clear free-electron absorption in the infrared region. By analysing the free-electron absorption using the Drude model, m c* was determined to be (0.37 ± 0.05)m 0 (m 0 denotes the free electron mass). The fundamental absorption edge in the visible to ultraviolet region shows a blue shift with increasing electron density. The analysis of the blue shift in the framework of the Burstein-Moss effect gives the E g value of 0.94 ± 0.02 eV. We believe that the findings of this study will provide important information to establish this material as a photovoltaic absorber.

Toric intraocular lenses in eyes with with-the-rule, against-the-rule, and oblique astigmatism: One-year results.

PURPOSE: To assess 1-year clinical results of toric intraocular lenses (IOLs) in eyes having with-the-rule (WTR), against-the-rule (ATR), or oblique corneal astigmatism. SETTING: Four ophthalmic surgical sites, Japan. DESIGN: Prospective case series. METHODS: One of 3 toric IOLs or 1 nontoric IOL was implanted in eyes having phacoemulsification and IOL implantation. RESULTS: The study comprised 218 eyes (155 patients). Based on the suggestion of an online toric calculator with anterior corneal curvature data, 63 eyes received the SN6AT3 IOL with a cylinder power of 1.50 diopters [D] at IOL plane (1.50 D cylinder IOL) 55 eyes the SN6AT4 IOL with a cylinder power of 2.25 D at IOL plane (2.25 D cylinder IOL), and 58 eyes the SN6AT5 IOL with a cylinder power of 3.00 D at IOL plane (3.00 D cylinder IOL) (all Acrysof IQ toric), and 42 eyes received the SN60WF IOL (nontoric IOL). One hundred ninety-four eyes (89.0%) completed 1-year of follow-up. The centroid error in predicted residual astigmatism calculated using vector analysis was close to the origin in eyes with WTR astigmatism (0.17 diopter [D] @ 174.9 ± 0.54 D), while those with ATR and oblique astigmatism were significantly shifted toward the ATR direction (P < .001). The distance from the origin was significantly smaller in the WTR group than in ATR and oblique groups (P < .05). The centroid errors were shifted toward ATR in all toric IOL groups (P < .001); however, the distance from the origin was not different between groups (P = .52). Postoperatively, the mean absolute misalignment of the IOLs was 5.92 degrees ± 5.59 (SD) at 1 day and 6.24 ± 5.87 degrees at 1 year. The results of other clinical parameters were excellent, with no significant differences between astigmatism categories or IOL models. CONCLUSION: Based on anterior corneal curvature alone, toric IOLs undercorrected ATR and oblique astigmatism; however, 1-year clinical results of toric IOLs were highly stable and satisfactory. FINANCIAL DISCLOSURE: None of the authors has a financial or proprietary interest in any material or method mentioned.

Retinal pigment epithelium wound healing in human Bruch's membrane explants.

PURPOSE: To compare retinal pigment epithelium (RPE) resurfacing on the RPE basement membrane and inner collagenous layer (ICL) in human submacular Bruch's membrane explants. METHODS: Debridements were created in RPE-choroid-sclera explants (mean donor age 71.91 +/- 7.76 years) to create defects exposing the RPE basement membrane (RPEbm(+) defects), the ICL immediately below the RPE basement membrane (superficial ICL, [SICL]) or deeper layers of the ICL (DICL). Eleven pairs of eyes--four pairs with one eye having an RPEbm(+) defect and the fellow eye having an SICL defect and seven pairs with corresponding RPEbm(+) and DICL defects--were observed for 10 days by visualizing RPE ingrowth with 4',6'-diamino-2-phenylindole (DAPI) filters. At day 10, specimens were processed for scanning electron microscopy. RESULTS: Resurfacing of localized RPE defects occurred to some degree in all 11 pairs of eyes. No significant difference in the percentage of resurfacing of RPEbm(+) defects (67.35% +/- 18.82%) and SICL defects (64.26% +/- 16.07%) was observed although healing of the SICL showed more variability in the morphology of RPE cells migrating into the defect. Significant differences in healing were observed between pairs with RPEbm(+) defects versus DICL defects (84.07% +/- 15.35% and 54.00% +/- 14.54% resurfacing, respectively). RPE ingrowth into DICL defects exhibited the greatest morphologic variability. CONCLUSIONS: RPE basement membrane supports RPE resurfacing of localized RPE defects. The deeper portion of the ICL of aged submacular human Bruch's membrane does not support RPE resurfacing to the same extent as does the RPE basement membrane. The poor RPE resurfacing observed in DICL defects mimics the histopathological findings in patients with age-related macular degeneration after excision of choroidal new vessels.

Elucidating the mechanism of Cr(VI) formation upon the interaction with metal oxides during coal oxy-fuel combustion.

The thermodynamics underpinning the interaction of Cr-bearing species with basic metal oxides, i.e. K2O, Fe2O3, MgO and CaO, during the air and oxy-fuel combustion of coal have been examined. The synchrotron-based X-ray adsorption near-edge spectroscopy (XANES) was used for Cr speciation. For the oxides tested, Cr(VI) formation is dominated by the reduction potential of the metals. The oxides of Ca(2+) with high reduction potential favored the oxidation of Cr(III), same for K(+). The other two basic metals, Fe2O3 and MgO with lower reduction potentials reacted with Cr(III) to form the corresponding chromites at the temperatures above 600°C. Coal combustion experiments in drop-tube furnace have confirmed the rapid capture of Cr vapors, either trivalent or hexavalent, by CaO into solid ash. The existence of HCl in flue gas favored the vaporization of Cr as CrO2Cl2, which was in turn captured by CaO into chromate. Both Fe2O3 and MgO exhibited less capability on scavenging the Cr(VI) vapor. Particularly, MgO alone exhibited a low capability for capturing the vaporized Cr(III) vapors. However, its co-existence with CaO in the furnace inhibited the Cr(VI) formation. This is beneficial for minimizing the toxicity of Cr in the coal combustion-derived fly ash.

Characteristics of slag, fly ash and deposited particles during melting of dewatered sewage sludge in a pilot plant.

This study examines slag, fly ash, and deposited particles during melting of dewatered sewage sludge in a pilot plant. In addition, the chemical composition of particles in flue gas was simulated using a thermodynamics program, namely FACTSage 5.2. The results showed that the main components of slag were Al, Fe, Ca, P and Si; the minor components were Na, K, Mg, Cu, and Zn. The main chemical compound of slag was Ca4(Mg,Fe)5(PO4)6. For fly ash particles, heavy metals with the highest concentrations were in the order of Zn and As, Pb, Cu, and Cd, respectively. For non-heavy metals, Al, Fe and P were also found in significant amounts. The majority of deposited particles were composed of elements of Zn, P, S, Na, Fe, Al, Si, and Ca and such chemical compounds as Zn3(PO4)2, AlPO4, FePO4 and Fe(OH)3 while the minority consisted of elements of As, Cu, and Pb. Moreover, the compositions of deposited particles in each chamber differed due to different flue gas temperatures inside. In the secondary chamber at 760 degrees C, the amounts of Fe and Al were higher than Zn, whereas, in the other chambers (600-400 degrees C), the amount of Zn was higher. In other words, at the lower temperature the deposition of Zn was higher than the deposition of Fe and Al. In the water cooling section, volatile elements (i.e. Zn, As, Cu, Pb) were found in the highest concentrations due to a big difference in temperature between the wall surface and flue gas. From the simulation results, most of the elements in the gas phase were found to be chloride compounds, whereas those in the solid phase were in the form of oxide, sulfate, and phosphate compounds.

Ultrastructural analysis of hydraulic and abrasive retinal pigment epithelial cell debridements.

Differential changes in Bruch's membrane, choriocapillaris, retinal pigment epithelium, retina, and tapetum after hydraulic or abrasive debridement of the retinal pigment epithelium in the cat area centralis were documented by fluorescein angiography, histology, and transmission electron microscopy at 1-hour, 1-day, 3-day, 1-week, or 4-week time points. Abrasive debridement is associated with abnormal fluorescein angiography and incomplete ingrowth of retinal pigment epithelial cells. Transmission electron microscopy shows that abrasive debridement inflicts more long-lasting ultrastructural damage to Bruch's membrane, the choriocapillaris, tapetum, and retina than does hydraulic debridement. Because the retinal pigment epithelium can resurface abrasively debrided Bruch's membrane that is disorganized, split, reduplicated, or missing, we cannot correlate the ultrastructural appearance of Bruch's membrane with the likelihood of complete resurfacing of the debrided area. Primary choriocapillary or retinal damage in abrasive debridements may contribute to the poor outcome. Regions of retinal degeneration with no underlying retinal pigment epithelial cell monolayer were significantly larger in abrasive debridements at the 4-week than at the 1-week time point. Reduced resurfacing at the later time point suggests that not all cells resurfacing abrasively debrided areas survived over the longer term. This finding may mean that retinal pigment epithelial cells are not able to resurface completely and permanently areas showing geographic atrophy of the choriocapillaris.