Selenium and arsenic speciation in fly ash from full-scale coal-burning utility plants

X-ray absorption fine structure spectroscopy has been used to determine directly the oxidation states and speciation of selenium and arsenic in 10 fly ash samples collected from full-scale utility plants. Such information is needed to assess the health risk posed by these elements in fly ash and to understand their behavior during combustion and in fly ash disposal options, such as sequestration in tailings ponds. Selenium is found predominantly as Se(IV) in selenite (SeO3(2-)) species, whereas arsenic is found predominantly as As(V) in arsenate (AsO4(3-)) species. Two distinct types of selenite and arsenate spectra were observed depending upon whether the fly ash was derived from eastern U.S. bituminous (Fe-rich) coals or from western subbituminous or lignite (Ca-rich) coals. Similar spectral details were observed for both arsenic and selenium in the two different types of fly ash, suggesting that the postcombustion behavior and capture of both of these elements are likely controlled by the same dominant element or phase in each type of fly ash.     

Formation of dioxins from combustion micropollutants over MSWI fly ash

Formation of polychlorinated dibenzofurans and dibenzo-p-dioxins (PCDD/Fs) from a model mixture of products of incomplete combustion (PICs) representative of municipal solid waste incineration (MSWI) flue gases, over a fixed bed of MSWI fly ash has been investigated. For comparison, a single model compound (chlorobenzene) was also briefly studied. A newly developed lab-scale system enabled the application of (very) low and stable concentrations of organic substances--of 10(-6) M or less-to approach realistic conditions. Samples taken at several time intervals allowed the observation of changes in rates and patterns due to depletion of the carbon in fly ash. The model flue gas continuously produced PCDDs and PCDFs after the de novo reaction had ceased to occur. Dioxin output levels are comparable to those of "old" MSW incinerators. Replacing the PIC trace constituent phenol by its fully 13C-labeled analogue led to, e.g., PCDD with one labeled ring as prominent product, meaning that the formation is about first order in phenol, contrary to earlier assumptions. The meaning of the results for the formation of dioxins in the MSWI boiler is discussed.     

Co-detoxification of transformer oil-contained PCBs and heavy metals in medical waste incinerator fly ash under sub- and supercritical water

The simultaneous detoxification processes of transformer oil-contained PCBs and heavy metals in medical waste incinerator (MWI) fly ash were developed under sub- and supercritical water. The addition of MWI fly ash to transformer oil-contained PCBs was found to increase the destruction efficiency of PCBs, at the same time, it facilitated reducing the leaching concentration of toxic metals from residues (obtained after reaction) for harmless disposal. In this study, we elucidated primarily the catalysis possibility of heavy metals in raw MWI fly ash for PCBs degradation by adopting the sequential extraction procedure. For both MWI fly ashes, more than 90% destruction efficiency of PCBs was achieved at ≥375 °C for 30 min, and trichlorobenzene (TCB) existing in the transformer oil was also completely decomposed. The correlation of catalytic performance to PCBs degradation was discussed based on structural characteristics and dechlorinated products. Likewise, such process rendered residues innocuous through supercritical water treatment for reuse or disposal in landfill.     

Elution of sodium caseinate from agar-based gel matrixes in simulated gastric fluids

Elution of sodium caseinate from agar/psyllium composite gels was investigated in simulated gastric fluids to determine predominant mechanical parameters of gels for the elution kinetics and to predict the kinetics using the parameters. When the concentration of agar was fixed at 0.5% in the composite gels, elastic moduli determined by creep tests decreased with increasing concentration of psyllium, while viscosities increased. Compression load upon syringing through an enteral tube increased with increasing concentration of psyllium, whereas the surface-volume diameter d_3,2 of gel particles after syringing decreased. The elution kinetics of sodium caseinate from cylindrical gels was described using two different diffusion coefficients; D₁ and D₂ (D₁ > D₂) and the diameter of gels. Both diffusion coefficients decreased with increasing concentration of psyllium, resulting in 1.9 × 10⁻⁶ (for D₁) and 6.7 × 10⁻⁸ (for D₂) cm²/min by 1.5% addition, which corresponded to approx. 30% and 45% of the control (i.e., 0% psyllium), respectively. The fraction ratio of sodium caseinate having D₁ was not sensitive to psyllium concentration; approx. 80%–85% in the concentration range tested. D₁ was inversely proportional to viscosities determined by creep tests, particularly one from the Voigt body η₁ in the 4-element mechanical model. When cube gels were divided into smaller ones without changing the total volume, elution rates were inversely proportional to the cube length, where the diffusion coefficients did not change. The elution kinetics of sodium caseinate from the gel matrixes was anticipated using η₁ of gels before syringing and d_3,2 of gel particles after syringing when the usage of gels for percutaneous endoscopic gastrostomy is assumed.     

Relative solubility of cations in Class F fly ash

Coal utilization byproducts (CUB), such as fly ash, contain cations that may be released during exposure to fluids such as acid rain or acid mine drainage. Researchers at the Department of Energy's National Energy Technology Laboratory (DOE/NETL) have conducted a long-term column leaching study of 32 Class F fly ash samples from pulverized coal (PC) combustion, and quantified the release of 19 cations in four leachants with a pH between 1.2 and 12. The relative solubility (M(L/T)) of each cation was defined as the total mass leached (M(L)) relative to the concentration (M(T)) of that element in the fly ash sample. A frequency distribution of relative solubility values was computed with ranges defined as insoluble, slightly soluble, moderately soluble, and very soluble. On the basis of this sample set, Ba, Cd, Fe, Pb, Sb, and Se in PC fly ash are insoluble. The elements Al, Be, Ca, Co, Cr, Cu, K, Mg, Mn, Na, Ni, and Zn are slightly to moderately acid soluble. Only Ca and Na are water soluble; As and Ca are soluble in the basic solution, The results of this study indicate that the extent to which cations in Class F PC fly ash can be leached by naturally occurring fluids is very limited.     

Chloride chemical form in various types of fly ash

Chloride content is a critical problem for the reuse of fly ash as a raw material in cement, and the method used by recyclers to reduce the fly ash chloride content depends on the chemical form of the chlorides. However, limited information is available on the quantitative distribution of chlorides and the identity of some chlorides such as Friedel's salt. We examined chloride forms and percentages using X-ray absorption near edge structure and X-ray diffraction analyses, as well as corresponding washing experiments. Approximately 15% of the chlorine in raw fly ash was estimated to be in the form of NaCI, 10% in KCl, 50% in CaCl2, and the remainder in the form of Friedel's salt. Fly ash collected in a bag filter with the injection of calcium hydroxide for acid gas removal (CaFA) contained 35% chlorine as NaCl, 11% as KCI, 37% as CaCl2, 13% as Friedel's salt, and the remaining 4% as CaClOH. In fly ash collected in a bag filter with the injection of sodium bicarbonate for acid gas removal (NaFA), approximately 79% of chlorine was in NaCl, 12% was in KCl, and 9% was in Friedel's salt.     

Infectivity studies of both ash and air emissions from simulated incineration of scrapie-contaminated tissues

We investigated the effectiveness of 15 min exposures to 600 and 1000 degrees C in continuous flow normal and starved-air incineration-like conditions to inactivate samples of pooled brain macerates from hamsters infected with the 263K strain of hamster-adapted scrapie with an infectivity titer in excess of 10(9) mean lethal doses (LD50) per g. Bioassays of the ash, outflow tubing residues, and vented emissions from heating 1 g of tissue samples yielded a total of two transmissions among 21 inoculated animals from the ash of a single specimen burned in normal air at 600 degrees C. No other ash, residue, or emission from samples heated at either 600 or 1000 degrees C, under either normal or starved-air conditions, transmitted disease. We conclude that at temperatures approaching 1000 degrees C under the air conditions and combustion times used in these experiments, contaminated tissues can be completely inactivated, with no release of infectivity into the environment from emissions. The extent to which this result can be realized in actual incinerators and other combustion devices will depend on equipment design and operating conditions during the heating process.     

粉煤灰制备PASFC及其在处理中段废水中的应用

以粉煤灰为主要原料,通过焙烧、酸浸、碱溶、聚合等步骤制备了一种无机高分子絮凝剂-聚合硅酸铝铁(PSAFC).分别研究了m(NaF):m(粉煤灰)、溶出温度、盐酸浓度及溶出时间对粉煤灰中Al3+、Fe3+溶出率的影响.将制得的PSAFC用于造纸中段废水的处理,并与PAC、PFC的处理效果进行了比较.结果表明:当溶出温度为105℃,盐酸浓度为20%,溶出时间为2h,m(NaF):m(粉煤灰)为0.20:1时,粉煤灰中Al3+的溶出率达39.4%,Fe3+的溶出率达52.1‰PSAFC对造纸中段废水中色度的去除率达95.2%,CODCr去除率达81.3%,其综合效果明显优于PAC和PFC.     

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.     

De novo synthesis of polychlorinated dibenzo-p-dioxins and dibenzofurans on fly ash from a sintering process

Fly ash, collected in the electrostatic precipitator of a sinter plant in Belgium, has been examined and characterized in terms of its behavior with respect to thermal polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzofurans (PCDF) formation. Thermal experiments of the fly ash were conducted in a flow of air. The temperature was varied from 250 to 450 degrees C, and the reaction time varied from 30 min to 6 h. For comparison, the oxidative degradation of carbon in the fly ash was studied by differential scanning calorimetry (DSC) in the temperature range from 50 to 500 degrees C. Besides the known maximum of formation of PCDD/Fs around 325 degrees C generally found on experiments with incinerator fly ash, a second maximum of formation around 400 degrees C is observed on the sinter fly ash used in this study. DSC measurements on the fly ash show that the oxidative degradation of carbon appears at these two different temperatures confirming that the de novo synthesis on this kind of fly ash take place at two different optimum temperatures. About the reaction time, already after 30 min, an important quantity of PCDD/Fs is formed; the fast increase in PCDD/Fs amount is followed by a slower formation rate between 2 and 4 h. At longer reaction time, the formation slows down, and decomposition reactions become important. Analysis of homologue distribution indicates that the profile of PCDD/Fs is independent of the reaction time but that an increase of the temperature leads to a rise of lower chlorinated species. In all experiments, PCDF are formed preferentially (total PCDF/PCDD ratios larger than 5). The PCDF/PCDD ratio is clearly independent of the reaction time. Concerning the temperature, the apparently better stability of PCDF at high temperature (PCDF/PCDD ratio higher at high temperature) results in the fact of different PCDF/PCDD ratios for the different family and modifications of homologue distribution with the temperature. The isomer distribution shows little reaction time or temperature dependency, which is an argument in favor of a thermodynamic control of the isomer distribution during de novo formation of PCDD/Fs. Differences within the isomer distribution patterns of PCDD/Fs obtained from the laboratory de novo synthesis experiments and the original fly ash, reflecting the formation under the industrial process, suggest a different mechanism of formation in the sinter plant for the PCDD and PCDF. The de novo synthesis is sufficient to explain the PCDF formation in the real process, but synthesis from precursors must play a role for the PCDD formation.     

Integrity and cell-monolayer permeability of chitosan nanoparticles in simulated gastrointestinal fluids

The objective of this study was to assess the integrity and intestinal permeability of chitosan nanoparticles (CNPs) in simulated gastrointestinal fluids (SGIF). The cell-associated and transported chitosan was quantified and visualized after incubation of the CNPs with Caco-2 cell monolayer with/without SGIF treatment. In order to establish the role of proteins in the SGIF, CNPs were incubated with 4 proteins having different isoelectric points (pI). CNPs incubated with the fluids did not attach to the cell monolayer in contrast to the intact CNPs. Negatively-charged protein formed the complex with CNPs leading to particle size increase, but protected CNPs from disintegration. In contrary, positively-charged protein interacted with cross-linker causing disintegration of CNPs. CNPs incubated with the fluids did not attach to the cell monolayer in contrast to the intact CNPs. The results suggested that the surface charges of CNPs and proteins play a critical role in structural changes of CNPs in biological environment.     

Distribution of mono to octa-chlorinated PCDD/Fs in fly ash from a municipal solid-waste incinerator

We have estimated the concentration and distribution of the mono to octa-chlorinated congeners of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in fly ashes at various sampling points in a large-scale municipal solid waste incinerator at Ume?, Sweden, as they cooled from 700 to 170 degrees C. Differences between the ashes were observed, the PCDD homologue profile was found to vary with temperature. The total amount of PCDD and PCDF increased as the temperature decreased in the postcombustion zone. The increase was due to both adsorption to the fly ash and formation of PCDD and PCDF. Mono-to trichlorinated PCDD predominated at high temperatures, whereas hepta- and octachlorinated PCDD predominated at temperatures below 400 degrees C. PCDF predominated over PCDD in the whole temperature range. However,the changes in homologue profile for PCDFwere minor. The isomer distribution within the homologue groups was not changed asthetemperature decreased in the postcombustion zone.     

Coal fly ash as a source of iron in atmospheric dust

Anthropogenic coal fly ash (FA) aerosol may represent a significant source of bioavailable iron in the open ocean. Few measurements have been made that compare the solubility of atmospheric iron from anthropogenic aerosols and other sources. We report here an investigation of iron dissolution for three FA samples in acidic aqueous solutions and compare the solubilities with that of Arizona test dust (AZTD), a reference material for mineral dust. The effects of pH, simulated cloud processing, and solar radiation on iron solubility have been explored. Similar to previously reported results on mineral dust, iron in aluminosilicate phases provides the predominant component of dissolved iron. Iron solubility of FA is substantially higher than of the crystalline minerals comprising AZTD. Simulated atmospheric processing elevates iron solubility due to significant changes in the morphology of aluminosilicate glass, a dominant material in FA particles. Iron is continuously released into the aqueous solution as FA particles break up into smaller fragments. These results suggest that the assessment of dissolved atmospheric iron deposition fluxes and their effect on the biogeochemistry at the ocean surface should be constrained by the source, environmental pH, iron speciation, and solar radiation.     

粉煤灰在印染废水处理中的应用

介绍了粉煤灰在印染、染料废水处理方面的研究现状及应用情况,分析讨论了粉煤灰处理废水的机理,指出了应用中存在的问题并对今后的研究方向进行了展望。     

絮凝沉降／粉煤灰吸附法处理印染废水

聚合氯化铝(PAC)是一种低廉的絮凝剂,对胶体或以悬浮状态存在于废水中的染料具有良好的脱色效果.粉煤灰是火力发电厂排放的固体废弃物,具有较小的颗粒、较多的微孔及较大的比表面积,对水中杂质有较好的吸附性能.研究了聚合氯化铝絮凝沉降和粉煤灰吸附对100 mL印染废水(COD 708 mg/L,色度120倍)处理的最佳工艺条件.结果表明:在碱性条件下,聚合氯化铝(质量浓度为20 g/L)用量为2.0 mL、pH值为8.0、搅拌时间为14 min时.COD值去除率为42.23%,色度去除率为82.5%.用聚合氯化铝处理后的废水,再用粉煤灰吸附时,粉煤灰用量为5 g、pH值为7.5、搅拌时间为20 min,COD去除率为73.51%,色度去除率为89.17%.     

Utilization of zeolites synthesized from coal fly ash for the purification of acid mine waters

Two pilot plant products containing 65 and 45% NaP1 zeolite were obtained from two Spanish coal fly ashes (Narcea and Teruel Power Station, respectively). The zeolitic product obtained showed a cation exchange capacity (CEC) of 2.7 and 2.0 mequiv/g, respectively. Decontamination tests of three acid mine waters from southwestern Spain were carried out using the zeolite derived from fly ash and commercial synthetic zeolite. The results demonstrate that the zeolitic material could be employed for heavy metal uptake in the water purification process. Doses of 5-30 g of zeolite/L have been applied according on the zeolite species and the heavy metal levels. Moreover, the application of zeolites increases the pH. This causes metal-bearing solid phases to precipitate and enhances the efficiency of the decontamination process.     

Adsorption and desorption of phenanthrene on carbon nanotubes in simulated gastrointestinal fluids

Adsorption of phenanthrene on carbon nanotubes (CNTs) and bioaccessibility of adsorbed phenanthrene were studied in simulated gastrointestinal fluids. Adsorption of phenanthrene on CNTs was suppressed in pepsin (800 mg/L) solution (gastric) and bile salt (500 and 5000 mg/L) fluids (intestinal). In addition to competitive sorption, pepsin and high-concentration bile salt (5000 mg/L, above critical micelle concentration) solubilized phenanthrene (3 and 30 times of the water solubility, respectively), thus substantially reduced phenanthrene adsorption on CNTs. Pepsin and bile salts also increased the rapidly desorbing phenanthrene fraction from CNTs. The rapidly desorbing phase lasted less than 1 h for all CNTs. Further, 43-69% of phenanthrene was released from CNTs after desorption in the simulated gastric and intestinal fluid at low bile salt concentration while 53-86% was released in the gastric and intestinal fluid at high bile salt concentration. These findings suggest that the release of residual hydrophobic organic compounds from CNTs could be enhanced by biomolecules such as pepsin and bile salts in the digestive tract, thus increasing the bioaccessibility of adsorbed phenanthrene and possibly the overall toxicity of phenanthrene associated CNTs.