Effects of sintering atmosphere on cement clinkers produced from chromium-bearing sludge.

The purpose of this study was to investigate the effects of sintering atmosphere (oxidizing and reducing) on the polymorphs of dicalcium silicates (Ca2SiO4, C2S) and on the chromium leaching of the belite-rich clinkers made from a chromium-bearing sludge. This sludge was generated in an electroplating factory, and in addition to chromium, it contained nickel, copper and zinc. In the clinker production, air was used as the oxidizing atmosphere, and carbon monoxide, which was produced by burning graphite with an insufficient amount of oxygen, was employed as the reducing atmosphere. Dicalcium silicates were substantially formed under both kinds of sintering atmosphere, but there was some nonhydraulic gamma-C2S in the clinkers produced under the oxidizing atmosphere. In addition, the amount of gamma-C2S decreased with the chromium-bearing sludge addition, whereas that of beta-C2S increased. The clinkers produced under the reducing atmosphere had less residual chromium, a finding that shows that more chromium was evaporated. However, the reducing atmosphere can decrease the proportion of hexavalent chromium (Cr(VI)) in the resulting clinkers. For other heavy metals, the residual amounts of nickel and copper generally increased with the sludge addition, but zinc was absent in most of the clinkers produced under the reducing atmosphere. This implies that the evaporation of zinc is much more significant than that of the other heavy metals under a reducing atmosphere. In the leaching tests, the concentrations of nickel, copper, and zinc were below the detection limits in all the leachates. In terms of chromium, the total leaching concentration was highly related to Cr(VI). The clinkers produced under the oxidizing atmosphere had high leaching concentrations of chromium, and thus failed to meet the regulatory limit. In contrast, the reducing atmosphere was effective in decreasing the chromium leaching, and it therefore makes the resulting cement clinkers more environmentally sound.

Stabilization of residues obtained from the treatment of laboratory waste: Part 2--transformation of plasma vitrified slag into composites.

The Sustainable Environment Research Center of National Cheng Kung University in Taiwan has set up a treatment plant to dispose of laboratory waste. In the treatment process, the residue from the incineration system and the physical and chemical system is vitrified by a plasma melting system. Part 1 of this study described the treatment path of metals during vitrification. In Part 2, plasma vitrified slag is reused by using a molding technology. Unsaturated polyester resin and glass fiber were used as the molding material and additive, respectively, in the molding process. With an appropriate mixing ratio of unsaturated polyester resin, glass fiber, and slag, the physical properties of composites improved, and the ultimate tensile strength reached 17.6 MPa. However, an excess amount of slag reduced the strength and even retarded the production of composites. Differential thermal analysis and the water bathing test results show that the composite decomposed at 80 degrees C and that it vaporized at 187 degrees C. Although the unsaturated polyester resin decomposed, the metal encapsulated in the slag did not leach out. The results show that the reuse of slag using molding technology should be taken into consideration.

Stabilization of residues obtained from the treatment of laboratory waste. Part 1--Treatment path of metals in a plasma melting system.

The objective of this study is to investigate the treatment path of metals during the plasma vitrification of fly ash, bottom ash, sludge, and activated carbon collected from a laboratory waste treatment plant. Sampling, digestion, and analysis procedures that followed the standard methods of the Taiwan Environmental Protection Administration were used to determine the composition of the input and output materials. The microstructure was qualitatively examined using a scanning electron microscope. The results show that the vitrification process successfully vitrified the toxic input materials into a stable, glassy, amorphous slag. During vitrification, metals with low boiling points (As, Cd, Hg, Pb, and Zn) were vaporized into the flue gas. Metals with high boiling points and high specific weights went into the ingot, and the residual metals remained in the molten materials as the slag. The distribution of metals shows their behavior during vitrification and can provide a reference for vitrifying hazardous materials.

Reusing pretreated desulfurization slag to improve clinkerization and clinker grindability for energy conservation in cement manufacture.

The purpose of this study was to combine the physical pretreatments of grinding, sieving, and magnetic-separation processes to reclaim iron-rich materials from the desulfurization slag, and to use the remainder for cement clinker production. The iron-rich materials can be separated out efficiently by grinding for 30 min and sieving with a 0.3 mm mesh. The non-magnetic fraction of the particles smaller than 0.3 mm was in the majority, and proved to be suitable for use as a cement raw material. The raw mixes prepared with a pretreated desulfurization slag had a relatively high reactivity, and the temperature at which alite forms was significantly reduced during the clinkerization process. The clinkers produced with 10% desulfurization slag had a high level of alite and good grindability. Generally, the improvements in clinkerization and clinker grindability are beneficial to energy conservation in cement manufacture.

Inactivation of bacteria by a mixed argon and oxygen micro-plasma as a function of exposure time.

PURPOSE: A radio-frequency dielectric barrier discharge (DBD) was applied as a micro-plasma device for the inactivation of bacteria, e.g., Escherichia coli. MATERIALS AND METHODS: The cultured bacteria were placed on a polydimethyl siloxane (PDMS) film and placed inside the DBD cavity. The bacteria were exposed to micro-plasmas of varying oxygen/argon ratios for different exposure times. The survival of the bacteria was measured by determining bacterial growth using optical methods. RESULTS: The excited oxygen species increased with the increase in the oxygen to argon ratio as measured by optical emission spectroscopy (OES), but the increase of excited oxygen species in argon micro-plasma did not enhance the inactivation of bacteria. In contrast, increases in the time the bacteria were exposed to the micro-plasma were of importance. The results show that a continuous plasma flow containing energetic and reactive species may result in electro-physical interactions with bacteria exposed to the plasma leading to their inactivation. CONCLUSION: For currently-employed DBD device, addition of 0.5% oxygen to the argon micro-plasma for an exposure time of 30 sec was optimum for the inactivation of E. coli.

Vitrification for reclaiming spent alkaline batteries.

The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification. Specimens were vitrified using an electrical heating furnace at 1400 degrees C and the output products included slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn, and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline batteries.

Stabilization of copper sludge by high-temperature CuFe2O4 synthesis process.

Copper sludge was stabilized by high-temperature CuFe(2)O(4) ferritization technique with different sintering temperature, isothermal time and Fe(3+)/M(2+) molar ratio. Copper is stabilized by inserting the copper ion into the stable CuFe(2)O(4) structure by ferritization. The result indicates that sintering temperature above 800 degrees C would be proper temperature range for CuFe(2)O(4) synthesis. When the Fe(3+)/M(2+) molar ratio of sludges are above the stoichiometric ratio of 2, copper ion in sludge would be stabilized and hence be kept from leaching out. From the result of relative XRD intensity ratio, the equilibrium of the ferritization reaction could be reached by prolonging the isothermal time to 10h. Judging by the TCLP results, the optimum ferritization parameters are Fe(3+)/M(2+) molar ratio equal to 3.5, sintering temperature at 800 degrees C and isothermal time above 10h.

An alternative approach for reusing slags from a plasma vitrification process.

Vitrification is widely applied to transform hazardous materials into inert slags. Raising the value of the recycled slag is an important issue from an economic point of view. In this study, an alternative approach for mixing a plasma slag with unsaturated polyester resin for making the dough-like molding composites is proposed. Physical properties, including ultimate tensile strength, Rockwell hardness, and the elongation at break, were measured to evaluate the characteristics of the composites. A scanning electron microscope and an X-ray diffractometer were used to examine the micro characteristics of the specimens. The chemical stability of the composites was estimated using the toxicity characteristic leaching procedure and a hot water bathing process. In an optimal slag loading (mass ratio of slag to unsaturated polyester resin) ranged from 0.1 to 0.2, the slag powder improved the physical properties of the composites. With an increased slag loading, excess slag powder weakened the structure of the resin, reducing the ultimate tensile strength and Rockwell hardness. The acid and water bathing tests indicated that the resin is decomposed in a hot environment. However, the slag was not destructed nor were the hazardous metals leached out. The results show that the molding method is an effective technology to recycle the slag.

Photocatalytic degradation of spill oils on TiO(2) nanotube thin films.

The nitrogen-doped TiO(2) nanotube (N-TNT) thin films were synthesized using ZnO nanorods as the template and doped with urea at 623K. Under ultraviolet (UV) and visible light irradiation, the efficiencies for photocatalytic degradation of methylene blue is as high as 30%. About 10% of toluene (representing aromatics in the spill oils) in sea water can be photocatalytically degraded under visible light radiation for 120 min. The aliphatic model compound (1-hexadecene) has, on the contrary, a less efficiency (8%) on the N-TNT photocatalyst. On the average, under visible light radiation, the effectnesses of the N-TNT for photocatalytic degradation of model compounds in the spill oils in sea water are 0.38 mg toluene/gN-TNTh and 0.25 mg 1-hexadecene/gN-TNTh. It is expected that spill oils in the harbors or seashores can be adsorbed and photocatalytically degraded on the N-TNT thin films that are coated onto levee at the sea water surface level.

Influence of start-up on PCDD/F emission of incinerators.

This study aims to evaluate the influence of start-up on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) concentration in the stack flue gas of incinerators and its contributing PCDD/F emission. The PCDD/F emission of the first sample among three consecutive stack flue gas samples of five intermittent incinerators, which sampled at a stable combustion condition after start-up, is 2-3 times higher than the mean of the others. For verifying the PCDD/F characteristics of incinerators during start-up, one continuous MSWI was investigated for two years. The elevated PCDD/F emissions of the MSWI during start-up could reach 96.9 ng I-TEQN m(-3) and still maintained a high PCDD/F emission (40 times higher than the Taiwan emission limit) even 18 h after the injection of activated carbon, indicating the memory effect. Taking the MSWI for example, which consists of four incinerators, the estimated annual PCDD/F emission from normal operational conditions was 0.112 g I-TEQ. However, one start-up procedure can generate approximately 60% of the PCDD/F emissions for one whole year of normal operations. And the PCDD/F emission, which is the result of the start-ups of four incinerators, was at least two times larger than that of a whole year's normal operations, without consideration for the PCDD/F emission contributed by the long lasting memory effect.

Emission of polycyclic aromatic hydrocarbons (PAHs) from the liquid injection incineration of petrochemical industrial wastewater.

This study investigated the emission of polycyclic aromatic hydrocarbons (PAHs) from stack flue gas and air pollution control device (APCD) effluent of the liquid injection incinerator (LII) disposing the petrochemical industrial wastewater, and PAH removal efficiencies of wet electrostatic precipitator (WESP) and wet scrubber (WSB). The PAH carcinogenic potency were investigated with the benzo(a)pyrene equivalent concentration (BaP(eq)). The remarkably high total-BaP(eq) concentration (220 microgNm(-3)) in the stack flue gas was much higher than those of several published emission sources, and indicated the possible influence on its surrounding environment. The total-PAH emission factors of the WESP, WSB and stack flue gas were 78.9, 95.7 and 30,900 microgL(-1) wastewater, respectively. The removal efficiencies of total-PAHs were 0.254, 0.309 and 0.563% for WESP, WSB and overall, respectively, suggesting that the use of both WESP and WSB shows insignificant PAH removal efficiencies, and 99.4% of total-PAHs was directly emitted to the ambient air through the stack flue gas. This finding suggested that the better incineration efficiencies, and APCD removal efficiencies for disposing the petrochemical industrial wastewater are necessary in future.

Effects of CH4 and CO on the reduction of nitric oxide to nitrogen in a discharge reactor.

Additives are often added to enhance the efficiency of NO removal. This study uses a radio frequency (rf) discharge to consider the effect of added CH4 and CO to simulated NO/N2/O2/H2O mixtures on the elevation of NO conversion and the reduction of NO into N2. The enhancement levels of NO conversion when using various additives were found to be in this order: +CH4 > +CO > no additive. NO conversion reached 99.3%, 86.2%, and 77.6% when adding CH4, CO, and without additive, respectively, at inlet additive/NO molar ratio (R) = 5 and at 120 W. Moreover, the fraction of total N atoms converted from NO into N2 (FN2) was very high, reaching 99.4% and 99.5% when adding CH4 and CO, respectively, at R = 1 and at 120 W. The better operating conditions are using CH4 as the additive at R > or = 1 and a power of > 60 W to reach a higher NO conversion with a higher FN2. However, it should be noted that this rf plasma approach is not practical at this stage because of its relative low pressure.

Tracking of copper species in incineration fly ashes.

Speciation of copper in the incineration waste heat boiler (HB) and the down stream electrostatic precipitator (EP) fly ashes during the flue gas cooling down (1123-->473 K) has been studied by X-ray absorption near edge structural (XANES) spectroscopy in the present work. Copper species such as Cu(OH)(2) (59-67%), CuCl(2) (5-12%), CuO (24-26%), and a small amount of CuS (3-4%) in fly ashes were determined by semi-quantitative analyses of the XANES spectra. In the toxicity characteristics leaching procedure (TCLP) tests, about 83 and 20% of copper were leached from the EP and HB fly ashes, respectively. The relatively high leachability of copper for the EP fly ash might be due to the fact that CuCl(2) was enriched on the surfaces as observed by X-ray photoelectron spectroscopy (XPS). On the contrary, CuCl(2) was mainly encapsulated in the HB fly ashes.

Comparisons of levels of polychlorinated dibenzo-p-dioxins/dibenzofurans in the surrounding environment and workplace of two municipal solid waste incinerators.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the surrounding environment (outdoor) and workplace air of two municipal solid waste incinerators (MSWIs, T and M) were characterized and compared. T and M represented two typical municipal solid waste incinerators in the north of Taiwan, which have different processes for controlling the PCDD/F emissions. The results of this study are summarized as follows. (1) The total PCDD/F and the total PCDD/F WHO-TEQ concentrations in the workplace air were 5-13 and 5-15 times higher than those in the outdoor air, respectively. Obviously, it is worthwhile to explore more on health risk assessment for exposure of PCDD/Fs emitted from MSWIs, particularly in the workplace air. (2) Mean total PCDD/F I-TEQ concentrations in the outdoor air ranged between 0.0216 and 0.155 pg I-TEQ/Nm(3) and averaged 0.0783 pg I-TEQ/Nm(3) (0.0828 pg WHO-TEQ/Nm(3)) during two seasons for two MSWIs, which were 6.5-fold higher than that of a remote site (0.0119 pg I-TEQ/Nm(3) or 0.0132 pg WHO-TEQ/Nm(3)) in Taiwan. However, the above outdoor air concentration levels in the MSWIs were still much lower than the air quality limitation of PCDD/Fs (0.6 pg I-TEQ/Nm(3)) in Japan []. (3) PCDFs were the primary toxicity distributors for PCDD/Fs in the outdoor air, since the ratios of PCDDs/PCDFs (I-TEQ) at all sampling sites ranged from 0.180 to 0.492 and were less than unity. (4) The OCDD, OCDF, 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-HpCDF were the four dominant species in both workplace and outdoor air near MSWIs. (5) By spraying water on and wetting both the fly and bottom ashes, the mean total PCDD/F I-TEQ concentration in the workplace air was reduced 86.9% in the T MSWI. The above results indicate an appropriate improving action did inhibit the fugitive emission of PCDD/Fs and reduce the health risk of workers during work handling ashes in MSWIs.

Bioremediation of polychlorinated-p-dioxins/dibenzofurans contaminated soil using simulated compost-amended landfill reactors under hypoxic conditions.

Compost-amended landfill reactors were developed to reduce polychlorinated-p-dioxins and dibenzofurans (PCDD/Fs) in contaminated soils. By periodically recirculating leachate and suppling oxygen, the online monitoring of the oxidation reduction potential confirmed that the reactors were maintained under hypoxic conditions, with redox levels constantly fluctuating between -400 and +80mV. The subsequent reactor operation demonstrated that PCDD/F degradation in soil could be facilitated by amending compost originating from the cow manure and waste sludge and that the degradation might be affected by the availability of easily degradable substrates in the soil and compost. The pyrosequencing analysis of V4/V5 regions of bacterial 16S rRNA genes suggested that species richness of the soil microbial community was increased by a factor of 1.37-1.61. Although the bacterial community varied with the compost origin and changed markedly during reactor operation, it was dominated by Alphaproteobacteria, Gammaproteobacteria, Actinobacteria, and Firmicutes. The aerotolerant anaerobic Sedimentibacter and Propionibacterium spp., and the uncultured Chloroflexi group could be temporarily induced to a high abundance by amending the cow manure compost; the bacterial growths were associated with the rapid degradation of PCDD/Fs. Overall, the novel bioremediation method for PCDD/F-contaminated soils using hypoxic conditions was effective, simple, energy saving, and thus easily practicable.

EXAFS study of adsorbed Cu(II) on fly ashes with different residual carbon contents.

This work studied the speciation of copper species adsorbed onto the surface of fly ash using X-ray absorption spectroscopy (XAS). Experimental results verified that the chemical bond between Cu(II) and the surface of the fly ash was Cu-O. The data set was optimally fitted into the two atomic shells: the first shell containing O atoms and the second shell containing Cu atoms. The extended X-ray absorption fine structure (EXAFS) data also show that, in the first shell, about 2.03-2.41 nearest oxygen atoms surround the center Cu atom with a Cu-O bond distance of 1.96-1.99 A. The results further demonstrated that the bond distance slightly increased with an increasing carbon content of the fly ash.

Leaching behavior and chemical stability of copper butyl xanthate complex under acidic conditions.

Although xanthate addition can be used for treating copper-containing wastewater, a better understanding of the leaching toxicity and the stability characteristics of the copper xanthate complexes formed is essential. This work was undertaken to evaluate the leaching behavior of copper xanthate complex precipitates by means of toxicity characteristics leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) using 1 N acetic acid solution as the leachant. Also, the chemical stability of the copper xanthate complex during extraction has been examined with the studying of variation of chemical structure using UV-vis, Fourier transform infrared and X-ray photoelectron spectroscopies (XPS). Both TCLP and SDLT results showed that a negligible amount of copper ion was leached out from the copper xanthate complex precipitate, indicating that the complex exhibited a high degree of copper leaching stability under acidic conditions. Nevertheless, chemical structure of the copper xanthate complex precipitate varied during the leaching tests. XPS data suggested that the copper xanthate complex initially contained both cupric and cuprous xanthate, but the unstable cupric xanthate change to the cuprous form after acid extraction, indicating the cuprous xanthate to be the final stabilizing structure. Despite that, the changes of chemical structure did not induce the rapid leaching of copper from the copper xanthate complex.

Integrated copper-containing wastewater treatment using xanthate process.

Although, the xanthate process has been shown to be an effective method for heavy metal removal from contaminated water, a heavy metal contaminated residual sludge is produced by the treatment process and the metal-xanthate sludge must be handled in accordance with the Taiwan EPA's waste disposal requirements. This work employed potassium ethyl xanthate (KEX) to remove copper ions from wastewater. The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) were used to determine the leaching potential and stability characteristics of the residual copper xanthate (Cu-EX) complexes. Results from metal removal experiments showed that KEX was suitable for the treatment of copper-containing wastewater over a wide copper concentration range (50, 100, 500, and 1000 mg/l) to the level that meets the Taiwan EPA's effluent regulations (3mg/l). The TCLP results of the residual Cu-EX complexes could meet the current regulations and thus the Cu-EX complexes could be treated as a non-hazardous material. Besides, the results of SDLT indicated that the complexes exhibited an excellent performance for stabilizing metals under acidic conditions, even slight chemical changes of the complexes occurred during extraction. The xanthate process, mixing KEX with copper-bearing solution to form Cu-EX precipitates, offered a comprehensive strategy for solving both copper-containing wastewater problems and subsequent sludge disposal requirements.

Speciation of copper in the incineration fly ash of a municipal solid waste.

The speciation of copper and zinc in the incineration fly ash of a municipal solid waste in Taiwan was investigated in the present work. By the least-squares fitted X-ray absorption near edge structural (XANES) spectroscopy, we found that CuCO3, CuOH2, and CuO (fractions of 0.09, 0.39 and 0.51, respectively) were the main copper species in the fly ash. Quantitative analysis of the extended X-ray absorption fine structural (EXAFS) spectra indicated that the bond distance of Cu-O in the fly ash was 1.96 A with a coordination number (CN) of 3.9 in the first shell of copper. In the second shell, the bond distance and CN of Cu-(O)-Cu were 2.91 A and 2.7, respectively. In addition, speciation of Zn was also examined in the same X-ray absorption energy (8780-9970 eV). The bond distance of Zn-O and Zn-O-Zn were 1.97 and 2.94 A, respectively. However, the Zn-O-Cu structure was not found because of the physically unreasonable sigma(2) (Debye-Waller factor) values in the EXAFS data fitting process.

Pyrosequencing analysis reveals high population dynamics of the soil microcosm degrading octachlorodibenzofuran.

A deeper understanding of the microbial community structure is very important in bioremediation for polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs). However, this has been insufficiently addressed in previous studies. To obtain more information, we pyrosequenced the V4/V5 regions of the 16S rRNA genes of bacterial communities transited from polluted soil to batch microcosms that rapidly degraded high concentrations of octachlorodibenzofuran (OCDF). The analysis results contained an average of 11,842 reads per sample, providing the first detailed description of bacterial communities associated with PCDD/Fs. The community composition markedly changed to be concomitant with the degradation of OCDF, indicating that a distinctive population structure developed rapidly in the microcosm. Although oxygen gas was provided weekly to the microcosm, the growth of potential degraders, Sphingomonas, Pseudomonas, Rhodococcus, and Clostridium, was observed, but in consistently low quantities. While anaerobic Sedimentibacter initially emerged as an abundant pioneer, several aerobic participants, such as the genera Brevundimonas, Pseudoxanthomonas, and Lysobacter, exhibited a large increase in their 16S rRNA gene copies within the timeframe, which showed a temporal population dynamic, and indicated their collaborative contributions to the degradation of OCDF under hypoxic conditions. These results have provided a deeper insight into the microbial community structure and population dynamics of the OCDF-degrading microcosm.