RESUMEN
This study investigates a circulating fluidised bed (CFB) incineration plant to examine the concentrations and fingerprints of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) at five locations downstream of the post-combustion zone. Sampling encompassed both flue gas and ash, spanning from the high-temperature superheater to the outlet of the baghouse filter, thus covering a wide range of flue gas temperatures. The analysis reveals a continuous increase in PCDD/F and PCB concentrations in the flue gas from the superheater to the inlet of the air pollution control system (APCS). The maximum concentrations observed were 75.8 ng/Nm3 for PCDDs, 219 ng/Nm3 for PCDFs, and 763 ng/Nm3 for PCBs. These values represent 9.14, 11.5, and 6.37 times their respective concentrations at the outlet of the high-temperature superheater. Concurrently, the levels of PCDD/Fs and dioxin-like PCBs (dl-PCBs) in the ash steadily increased along the cooling path of the flue gas within the plant. Comparing dl-PCBs to the total amount of 209 PCB congeners, it was evident that dl-PCBs exhibited a trend more akin to that of PCDD/Fs. A robust linear correlation was observed between dl-PCBs and PCDD/Fs (R2 = 0.99, p < 0.001), surpassing that between PCBs and PCDD/Fs (R2 = 0.92, p < 0.01), suggesting that dl-PCBs share closer formation pathways with PCDD/Fs. Additionally, elemental composition analysis of fly ash samples aimed to explore potential links between fly ash characteristics and PCDD/F and PCB formation. The Cl/S ratio increased from 1.58 to 5.13 with decreasing flue gas temperature. Principal component analysis (PCA) was employed to visualise the concentrations of PCDD/Fs and PCBs in the flue gas alongside elemental contents in the fly ash. With the exception of PCBs in ash, all other PCDD/Fs and PCBs in fly ash exhibited positive correlations with both carbon (C) and chlorine (Cl). Furthermore, a positive relationship between C/Cl and PCDD/Fs-PCBs in fly ash implies that fly ash serves as the primary reaction surface for dioxin generation during low-temperature heterogeneous catalytic reactions.
Asunto(s)
Dioxinas , Bifenilos Policlorados , Dibenzodioxinas Policloradas , Dibenzodioxinas Policloradas/análisis , Bifenilos Policlorados/análisis , Residuos Sólidos/análisis , Ceniza del Carbón/análisis , Dioxinas/análisis , Dibenzofuranos/análisis , Dibenzofuranos Policlorados/análisis , IncineraciónRESUMEN
Short-chain chlorinated paraffins (SCCPs) are listed in Annex A (elimination) of the Stockholm Convention on persistent organic pollutants, and products containing SCCPs require detoxification. In the present study, the metal sodium (Na) dispersion method was applied to a wax sample containing SCCPs (58%, C10-C13 and Cl5-Cl9) to assess the dechlorination effect. Effective dechlorination of SCCPs was confirmed using 2-L and 20-L reaction systems. The initial concentrations of the wax (5, 10, 20, 30%), reaction time (10, 30, 60, 120, 180 min), and the ratios of the amount of Na dispersion and the initial amount of the wax containing SCCPs (Na/wax ratios; 3.9, 4.4, 5.2) were tested. The destruction efficiency of SCCPs was over 99.999% after 10 min of reaction at 90 °C under several conditions. The initial concentrations of the wax and the Na/wax ratios did not affect the results. The ultralow SCCP contents in exhaust gas from the reaction tank demonstrated a destruction removal efficiency of over 99.999999%. Trace levels of polychlorinated dibenzo-p-dioxins and furans, dioxin-like polychlorinated biphenyls, hexachlorobenzene, and pentachlorobenzene in the wax sample and treated materials (oil, water, and gas) met various regulatory values or exhibited the same levels as the environmental background. After dechlorination of the SCCPs, the main reaction products in the reaction liquid and final oil phase were identified as aliphatic compounds. The metal Na dispersion method was found to be an effective and decontaminated destruction technique for application to SCCPs in liquid-like samples with no formation of hazardous organic byproducts.
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Hidrocarburos Clorados , Bifenilos Policlorados , China , Monitoreo del Ambiente , Hidrocarburos Clorados/análisis , Parafina/análisis , Bifenilos Policlorados/análisis , SodioRESUMEN
Open burning of PVC-coated cables is a major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). In the present study, the formation characteristics of PCDD/F from burning of PVC-based samples with and without metallic copper were evaluated over the dioxin formation temperature window (200-500 °C). This temperature range also inevitably occurs under open burning conditions. The PCDD/F yield from PVC added with Cu increased by factors of 1390 (300 °C), 65 (400 °C) and 17 (500 °C) compared with that from PVC alone, confirming the stimulatory effect of metallic Cu on PCDD/F production. For the first time, a relatively complete isomer-specific analysis is established for PVC acting as source of PCDD/F. Formation pathways of PCDD/F and the reaction mechanisms were investigated using a combined analysis of PCDD/F isomer signatures, thermogravimetric results and Cl K-edge X-ray absorption spectra. De novo synthesis is the major pathway leading to massive production of PCDD/F. Copper extends the temperature range for the concurrence of de(hydro)chlorination of PVC with cross-linking and aromatisation of polyenes and then stimulates cracking of the chlorine-embedded carbon network. Together, these processes contribute to the strongly enhanced formation of PCDD/F via de novo synthesis.
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Benzofuranos , Dibenzodioxinas Policloradas , Dibenzofuranos , Dibenzofuranos Policlorados , Incineración , Cloruro de PoliviniloRESUMEN
Previous studies have suggested that unidentified compounds constitute a large proportion of extractable organochlorine (EOCl) and extractable organobromine (EOBr) in the crude extracts without fractionation; however, the proportion of unidentified EOX (X = chlorine, bromine) associated with high-/low-molecular-weight compounds is still unknown. In this study, we applied gel permeation chromatography to fractionate extracts from archived liver samples of high-trophic marine and terrestrial mammals (striped dolphins, cats, and raccoon dogs), for which concentrations of legacy organohalogen contaminants (polychlorinated biphenyls, organochlorine pesticides, and polybrominated diphenyl ethers [PBDEs]) had been previously reported. EOX in high- (>1000 g/mol) and low- (≤1000 g/mol) molecular-weight fractions (EOX-H and EOX-L) were determined by neutron activation analysis. Comparison of EOCl and EOBr enabled the characterization among species. Despite small differences in the concentrations and molecular-weight profiles of EOCl among species, the contribution of chlorine in identified compounds to EOCl-L varied from 1.5% (cats) to 79% (striped dolphins). Considerable species-specific variations were observed in the concentrations of EOBr: striped dolphins exhibited significantly greater concentrations of both EOBr-H and EOBr-L than cats and/or raccoon dogs. Moreover, the contribution of bromine in PBDEs to EOBr-L was >50% in two cats, while it was <6% in other specimens. This is the first report on EOBr mass balance in cetaceans and on EOX mass balance in terrestrial mammals living close to humans. These results suggest the need for analysis of unidentified chlorinated compounds in terrestrial mammals and unidentified brominated compounds in marine mammals.
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Hidrocarburos Clorados , Bifenilos Policlorados , Animales , Gatos , Monitoreo del Ambiente , Éteres Difenilos Halogenados , Hidrocarburos Clorados/análisis , Mamíferos , Bifenilos Policlorados/análisisRESUMEN
Brominated aromatic compounds are unintentionally generated during various thermal processes, including municipal solid waste incineration, electric-waste open burning, and secondary copper smelting. Copper (Cu) plays an important role in the formation of brominated aromatic compounds. In the present study, the thermochemical behaviors of Cu and Br in model samples, including copper bromide (CuBr2) and activated carbon, were studied using in situ X-ray absorption near-edge structure (XANES) and thermogravimetry. Quantification of polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) was also conducted by gas chromatograph-high resolution mass spectrometer. Three key reactions were identified: (i) the reduction of CuBr2 to CuBr (room temperature to 300 °C), (ii) the generation of Br bonded with aromatic carbon (150-350 °C), and (iii) the oxidation of copper (>350 °C). Maximum amounts of PBDD/Fs were found in residual solid phase after heating at 300 °C. The analytical results indicated the direct bromination of aromatic carbon by the debromination of copper bromides (I, II) and that CuBr and CuO acted as catalysts in the oxidation of the carbon matrix. The bromination mechanisms revealed in this study are essential to the de novo formation of PBDD/Fs and other brominated aromatic compounds.
RESUMEN
Chromium is commonly found in the flue gases and ashes of Municipal Solid Waste Incineration. It has been reported as an active catalyst for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) during de novo tests, yet its specific mode of action has remained unclear. This study aims to identify the effects of chromium chloride on the formation of PCDD/F and other chloro-aromatics and to elucidate the underlying reaction mechanisms. A series of de novo tests, conducted over a wide range of temperature (from 250 to 550⯰C) and for four different oxygen contents (0, 5, 10, 20 %), confirmed the promoting effect of CrCl3 on the PCDD/F formation. In situ X-ray Absorption Fine Structure (XAFS) spectroscopy was applied to investigate the behavior of CrCl3 during heating, describing the entire picture of CrCl3-promoted formation pathways of dioxins. The effect of oxygen was studied by measuring XAFS spectra on samples heated at different oxygen concentrations. According to these spectra, chromium compounds play two key roles during dioxins formation: (a) chlorinating carbon, using chlorine derived from conversion of CrCl3 into Cr2O3, and further oxidation to Cr(VI), and (b) facilitating oxidative destruction of the carbon matrix, while reducing Cr(VI) to Cr2O3.
RESUMEN
Environmental pollution and human health issues due to unrestricted electronic waste (e-waste) recycling activities have been reported at a number of locations. Among different e-waste recycling techniques, open burning of e-waste releases diverse metal(loid)s into the environment, which has aroused concern worldwide. In human health risk assessments (HHRAs), oral ingestion of soil can be a major route of exposure to many immobile soil contaminants. In vitro assays are currently being developed and validated to avoid overestimation of pollutants absorbed by the human body when calculating total pollutant concentrations in HHRAs. In this study, Cu, As, Cd, Sb, and Pb bioaccessibility in polluted soils (nâ¯=â¯10) from e-waste open burning sites at Agbogbloshie in Accra, Ghana, was assessed using an in vitro assay, the physiologically based extraction test. A bioaccessibility-corrected HHRA was then conducted to estimate the potential health risks to local inhabitants. The in vitro results (%) varied greatly among the different metal(loid)s (Cu: 1.3-60, As: 1.3-40, Cd: 4.2-67, Sb: 0.7-85, Pb: 4.1-57), and also showed marked variance between the gastric phase and small intestinal phase. The particle sizes of soil samples and chemical forms of metal(loid)s also influenced bioaccessibility values. Using these bioaccessibility values, both the hazard index and carcinogenic risk were calculated. The hazard index was above the threshold value (>1) for 5/10 samples, indicating a potential health risk to local inhabitants.
Asunto(s)
Residuos Electrónicos , Metaloides/análisis , Medición de Riesgo , Contaminantes del Suelo/farmacocinética , Disponibilidad Biológica , Exposición Dietética/efectos adversos , Exposición Dietética/análisis , Exposición a Riesgos Ambientales/efectos adversos , Exposición a Riesgos Ambientales/análisis , Monitoreo del Ambiente , Ghana , Humanos , Concentración de Iones de Hidrógeno , Metaloides/farmacocinética , Metaloides/toxicidad , Metales/análisis , Metales/farmacocinética , Metales/toxicidad , Tamaño de la Partícula , Reciclaje , Suelo/química , Contaminantes del Suelo/análisis , Contaminantes del Suelo/toxicidadRESUMEN
The incineration of waste carbon nanomaterials will become an inevitable waste management strategy following the disposal of products containing carbon nanomaterials. We investigated the formation of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and polychlorinated biphenyls (PCBs) during the incineration of selected carbon nanomaterials [fullerene (C60), single-walled carbon nanotubes (SWNTs), and graphene], with sodium chloride and trace copper at 850⯰C in air using a laboratory-scale electric furnace. Most PCDD/Fs and PCBs were concentrated in particulate fly ash post-incineration, and in low-temperature zones in the furnace (54-670⯰C). Notably, C60 had a specific thermal behavior leading to the formation of high concentrations of high chlorinated PCDD/Fs and toxic 2,3,7,8-tetra-CDD/F (2,3,7,8-T4CDD/F). SWNTs had a lower potential to generate such compounds than C60, but had a higher potential than graphene and graphite. Temperature, solid/gas phases, chlorine sources, and the thermal stability of carbon nanomaterials were the key controlling factors. There is a need to consider the generation of PCDD/Fs and PCBs during the incineration of waste streams containing carbon nanomaterials.
RESUMEN
Open burning of electronic waste (E-waste) produces numerous organochlorine compounds (OCs). Although the presence of unidentified OCs has been suggested, the mass balance of identified and unidentified OCs in E-waste open burning soils (EOBSs) still remains unknown. In this study, the concentrations of Cl bonded with aromatic carbon (aromatic-Cl) and aliphatic carbon (aliphatic-Cl), and inorganic Cl in EOBSs were determined by focusing on chlorine (Cl) in water-insoluble fractions (insoluble Cl) and applying Cl K-edge X-ray absorption spectroscopy in conjunction with combustion ion chromatography. The concentrations of identified Cl (Cl in five individual OCs: polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, chlorinated polycyclic aromatic hydrocarbons and chlorinated benzenes) were calculated from the concentrations previously reported for the same samples. The proportions of identified Cl were less than 1% to aromatic-Cl, indicating the abundance of unidentified OCs. The concentrations of both aromatic-Cl and identified Cl were highest in the sample collected from the site in Vietnam (VN), where wires and cables were mainly burned, suggesting that unidentified aromatic-Cl were produced through pathways similar to those of identified OCs, and the pathway could be related to burning of wires and cables. Further, insoluble Cu (II) compound, Cu2(OH)3Cl were assumed to be present in EOBSs and the concentration was highest in VN, implying that insoluble inorganic chlorides could be related to the formation of aromatic-Cl and identified Cl.
Asunto(s)
Cloruros/análisis , Residuos Electrónicos/análisis , Hidrocarburos Clorados/análisis , Incineración , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes del Suelo/análisis , Incineración/métodos , Suelo/química , VietnamRESUMEN
We explored the effects of gas emission by mixtures undergoing alkali-activation of municipal solid waste incineration fly ash (MSWIFA) and pyrophyllite (the mixtures included dehydrated pyrophyllite, MSWIFA, 14â¯mol/L aqueous sodium hydroxide, and sodium silicate; curing proceed at 105⯰C for 24â¯h). We measured the compressive strengths of the derived solid composites. The causes of gas emission, and the physical and chemical properties of products created under controlled gas emission, were investigated. Hydrogen was emitted after mixing MSWIFA and alkali. The compressive strength of products prepared when gas emission was complete was 2-3.4-fold greater than that of products prepared when gas emission was incomplete. X-ray micro-tomography and mercury intrusion porosimetry showed that products formed during complete gas emission tended to have smaller pores. X-ray diffraction and nuclear magnetic resonance (27Al and 29Si) indicated that the aluminum substitution levels in tectosilicate differed under such conditions, although the minerals were identical. Thus, complete gas emission after mixing improved ultimate products.
Asunto(s)
Silicatos de Aluminio/química , Ceniza del Carbón/química , Incineración/métodos , Industria del Petróleo y Gas/métodos , Residuos Sólidos/análisis , Carbono/químicaRESUMEN
This study investigated core samples from a landfill site for incinerator residue. The landfill site is one of the first monofill sites for municipal solid waste incinerator residue in the world. The concentrations of the heavy metals Cd, Cr, Cu, Pb, Zn, and Ni in the landfilled incinerator residues were 1-108, 41-926, 40-5498, 35-9806, 103-11453, and 25-719â¯mg/kg, respectively. Based on comparisons of heavy metal contents between raw incinerator fly ash and bottom ash reported in the literature, our samples comprised a mixture of incinerator fly ash and bottom ash. Rainfall had removed the dissolvable salts from the incinerator residues. The compositions of incinerator residues from different locations varied markedly. The vertical distribution showed a high heavy metal content in the waste layers, suggesting no vertical movement of heavy metals in this landfill site. A comparison between the experimental data and data calculated from historic records of the original metal compositions of the incinerator residues suggested high mobility of Zn, Cu, and Pb and low mobility of Cr and Cd. This trend was supported by a leaching test of waste layer samples. Zn and Cu were leached more readily at pH 9.0-10.0 and 10.5-11.5, respectively.
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There is an urgent need to dispose safely of the municipal solid waste incineration fly ash (MSWIFA) contaminated by cesium (Cs) released from the Fukushima Daiichi nuclear power plant accidents. This study investigated the relationship between quantitative Cs speciation and Cs immobilization in composite product from alkali-activated pyrophyllite and MSWIFA, with added stable cesium chloride and cesium carbonate. Cesium speciation was determined using X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS), while Cs immobilization was evaluated by a leaching method. Twenty-four composite products, with different Cs leaching properties, were prepared under various conditions. The XRD analysis of six composite products with different Cs leaching properties qualitatively identified a crystalline pollucite in the two products with the least Cs leaching. The quantitative speciation determined using XAFS revealed a strong negative correlation between the pollucite content in the 24 products and their Cs leaching ratio. Cesium species with a CsO bond were found in all products. These were at least two Cs species with different leaching properties. These results indicate that the change from a Cs species to pollucite in the product increased the Cs immobilization level in the system.
Asunto(s)
Cesio/química , Ceniza del Carbón/química , Incineración/métodos , Residuos Sólidos/análisis , Álcalis , Cesio/análisis , Eliminación de Residuos/métodos , Difracción de Rayos XRESUMEN
We measured bioaccessible lead (Pb) in simulated gastrointestinal fluids containing Pb-contaminated soil or dust from electronic waste (e-waste) recycling sites to assess the risk of Pb ingestion. The physiologically based extraction test (PBET) was used as in vitro bioaccessibility assay. Pb speciation was determined using X-ray absorption spectroscopy. The total Pb concentrations in dusts (n=8) and soils (n=4) were in the range of 1630-131,000 and 239-7800mg/kg, respectively. Metallic Pb, a common component of e-waste, was ubiquitous in the samples. We also found Pb adsorbed onto goethite and as oxides and carbonate, implying soil mixing and weathering influences. Pb phosphate and organic species were only found in the soil samples, suggesting that formation was soil-specific. We identified other Pb compounds in several samples, including Pb silicate, Pb chromate, and Pb(II) hydrogen phosphate. A correlation analysis indicated that metallic Pb decreased bioaccessibility in the stomach, while a Pb speciation analysis revealed a low bioaccessibility for Pb phosphates and high bioaccessibility for organic Pb species. The health risk based on bioaccessible Pb was estimated to be much lower than that of total Pb due to the lower concentrations.
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Jugo Gástrico/química , Secreciones Intestinales/química , Plomo/química , Contaminantes del Suelo/química , Disponibilidad Biológica , Polvo/análisis , Residuos Electrónicos , Monitoreo del Ambiente , Plomo/análisis , Reciclaje , Contaminantes del Suelo/análisis , Espectroscopía de Absorción de Rayos XRESUMEN
Environmentally sound treatments are required to dispose of municipal solid waste incineration fly ash (MSWIFA) contaminated with radioactive cesium (Cs) from the Fukushima Daiichi nuclear power plant accident in Japan. This study focuses on the stabilization of Cs using an alkali-activated MSWIFA and pyophyllite-based system. Three composite solid products were synthesized after mixtures of raw materials (dehydrated pyrophyllite, MSWIFA, 14 mol/L aqueous sodium hydroxide, and sodium silicate solution) were cured at 105 °C for 24 h. Three types of MSWIFAs were prepared as raw fly ash, raw fly ash with 0.1% CsCl, and raw fly ash with 40% CsCl to understand the stabilization mechanism of Cs. Cs stabilization in two solid products was successful, with less than 6.9% leaching observed from two types tests, and was partly successful for the solid product with the highest concentration of Cs. X-ray diffraction showed that all of the solid products produced several crystalline phases, and that pollucite was formed in the highest Cs concentration product. The X-ray absorption fine structure and scanning electron microscopy with X-ray analysis suggested that most Cs species formed pollucite in the two solid products from MSWIFA with added CsCl. This system provides a technique for the direct stabilization of Cs in MSWIFA.
Asunto(s)
Radioisótopos de Cesio/química , Ceniza del Carbón/química , Incineración , Álcalis/química , Cesio , Cloruros , Japón , Residuos Sólidos , Difracción de Rayos XRESUMEN
This work focuses on the stabilization and speciation of lead (Pb) in a composite solid produced from an alkali-activated municipal solid waste incineration fly ash (MSWIFA)-pyophyllite-based system. The solid product was synthesized after mixtures of raw materials (dehydrated pyrophyllite, MSWIFA, 14 mol/L aqueous sodium hydroxide, and sodium silicate solution) were cured at 105 °C for 24 h. The product could reduce the leaching of Pb and the Pb concentration in the leachate was 7.0 × 10-3 using the Japanese leaching test and 9.7 × 10-4 mg/L using toxicity characteristics leaching procedure method, which satisfied the respective test criteria and successfully stabilized Pb in this system. The solid product had a compressive strength of 2 MPa and consisted mainly of crystalline phases. Scanning electron microscopy with X-ray analysis and X-ray absorption fine structure suggested that Pb was present along with Al, Si, and O, and that the atomic environment around the Pb was similar to that of PbSiO3. These results suggest that the alkali-activated MSWIFA-pyrophyllite-based system could be used to stabilize Pb in MSWIFA.
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Ceniza del Carbón , Incineración , Plomo , Eliminación de Residuos , Álcalis , Silicatos de Aluminio , Carbono , Metales Pesados , Material Particulado , Residuos SólidosRESUMEN
We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS.
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Residuos Electrónicos/análisis , Incineración , Hidrocarburos Policíclicos Aromáticos/toxicidad , Contaminantes del Suelo/toxicidad , Ceniza del Carbón/análisis , Contaminantes Ambientales/análisis , Halogenación , Japón , Hidrocarburos Policíclicos Aromáticos/análisis , República de Corea , Suelo/química , Contaminantes del Suelo/análisisRESUMEN
Nitrogen and sulfur (N/S)-containing compounds inhibit the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in thermal processes. However, few studies have examined the inhibition mechanisms of N/S-containing compounds. In the present study, we focused on thiourea [(NH2)2CS] as such a compound and investigated its inhibition effects and mechanisms. The production of PCDD/Fs, polychlorinated biphenyls (PCBs), and chlorobenzenes (CBzs) were inhibited by >99% in the model fly ash in the presence of 1.0% thiourea after heating at 300 °C. Experimental results using real fly ash series were indicative of the thermal destruction of these chlorinated aromatics by thiourea. Multielement characterization using K-edge X-ray absorption fine structures of copper, chlorine, sulfur, nitrogen, and carbon revealed three possible inhibition paths, namely, (a) sulfidization of the copper catalyst to CuS, Cu2S, and CuSO4; (b) blocking the chlorination of carbon via the reaction of chlorine with N-containing compounds to generate ammonium chloride and other minor compounds; and (c) changing the carbon frame involved in attacking the carbon matrix by sulfur and nitrogen. Thus, thiourea plays a role as a sulfur and nitrogen donor to achieve multiple and synergistic inhibition of chlorinated aromatics. Our results suggest that other N/S-containing inhibitors function based on similar mechanisms.
RESUMEN
Open burning of electronic waste (e-waste) releases various metals and organohalogen compounds in the environment. Here we investigated the interplay of metals (Cu, Pb, Zn, Fe, Co, and Sr) and bromine (Br) in the formation of dioxin-related compounds (DRCs), including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs), as well as non-regulated DRCs such as polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and their monobrominated PCDD/Fs in soils sampled from open burning e-waste sites at Agbogbloshie in Accra, Ghana. The predominant DRCs were PBDFs, PCDFs, PCDDs, and DL-PCBs. Statistical analyzes, X-ray absorption spectroscopy, and the PCDF/PCDD ratio suggested possible formation paths of PCDD/Fs and DL-PCBs by catalytic behaviors of copper chlorides (CuCl, CuCl2, and Cu2(OH)3Cl) and thermal breakdown of polyvinyl chloride. Predominant formation of brominated furans may be derived from electron transfer from intermediates of PBDE to copper, Cu(II) â Cu(I). Lead chloride also contributed to generate DRCs and may become highly bioaccessible through the open burning of e-waste. The main zinc species (ZnCl2 and ZnS) suggested a possible relationship to generate DRCs and specific zinc source such as tire burning. Cu, Pb, Zn, and Br contained in various e-wastes, wires/cables, plastics, and tires strongly influenced generation of many DRCs.
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Bromo/análisis , Dioxinas/química , Residuos Electrónicos/análisis , Metales/análisis , Contaminantes del Suelo/química , Electrónica , Monitoreo del Ambiente , GhanaRESUMEN
This study investigates the emission of nitrous oxide (N2O) and discusses the reduction of N2O emissions during the 24-h combustion of cattle manure using a pilot-scale fluidized bed incinerator under various experimental conditions. The results of these experiments were then validated against previously reported data. In addition, the characteristics of cattle manure incineration ash and their changes under different combustion conditions were estimated. In incineration experiments with composted cattle manure, N2O concentrations using multi-stage combustion were 75% lower than the concentrations resulting from normal combustion without additional auxiliary fuel, since N2O could be decomposed in the high-temperature zone formed by the inlet of the secondary combustion air. The N2O emission factor under normal combustion conditions (800°C) was 6.0% g-N2O-N/g-N. This result is similar to the values found in previous studies at the same temperature. The N2O emission factor was decreased to 1.6% g-N2O-N/g-N using a multi-stage combustion procedure. The current Japanese N2O emission factor of 0.1% g-N2O-N/g-N is an underestimate for some conditions and should be uniquely specified for each condition. Finally, cattle manure ash contains ample fertilizer elements, little Fe, Al and Zn, but abundant Cl. Therefore if Cl could be removed by some kind of pretreatment, cattle manure ash could be used as a favourable fertilizer.
RESUMEN
The chemical behavior of Cs in waste incineration processes is important to consider when disposing of radionuclide-contaminated waste from the Fukushima Daiichi nuclear power plant accident in Japan. To determine the speciation of Cs, we attempted the direct speciation of trace amounts of stable Cs in the dust from municipal solid waste incineration (MSWI) and sewage sludge incineration (SSI) by micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) at the SPring-8 facility. The µ-XRF results revealed that locally produced Cs was present in MSWI and SSI dust within the cluster size range of 2-10 µm. The µ-XAFS analysis confirmed that the speciation of Cs in MSWI dust was similar to that of CsCl, while in SSI dusts it was similar to pollucite. The solubility of Cs was considered to be influenced by the exact Cs species present in incineration residue.