Lead isotopic composition of fly ash and flue gas residues from municipal solid waste combustors in France: implications for atmospheric lead source tracing

Fly ash and flue gas residues from eight municipal solid waste combustors (MSWC) in France (1992--93 and 1998/ 2002) were analyzed for their Pb isotopic composition. Fly ashes are more representative of solid residual particles, whereas flue gas residues reflect mostly the composition of gas phases. Both sample types contain hundreds to thousands of micrograms of metals per gram. Leaching experiments showed that metals are present in condensed phases, probably as sulfates and chlorides, and suggest that Cd, Pb, and Zn are highly fractionated from one another during volatilization/condensation processes occurring during combustion. Although all the samples analyzed define a fairly restricted range in Pb isotopic compositions (206Pb/207Pb = 1.148-1.158 and 208Pb/206Pb = 2.101-2.114) compared to other environmental samples, some MSWC produce materials having distinct isotopic compositions, whereas others display very similar ones. Isotopic heterogeneity is also measured between samples from a single MSWC. This is interpreted as resulting from the heterogeneity of the waste source materials. The range of Pb isotopic composition of incinerator materials form a well-defined linear array in the 208Pb/206Pb versus 206Pb/207Pb diagram. This array is compatible with the previously reported European standard pollution (ESP) line and most probably represent the average lead isotopic composition of industrial atmospheric emissions in France, with the following ratios: 206Pb/207Pb = 1.154+/-0.003 and 208Pb/206Pb = 2.107+/-0.003 (1sigma).     

粉煤灰联产新型硅酸钙填料的研究进展

粉煤灰是燃煤在锅炉燃烧过程中产生的固体颗粒物,通过协同作用与联产技术利用粉煤灰制备新型硅酸盐填料的技术已经实现。本文主要综述了从粉煤灰提取生产的新型硅酸盐填料的方法,并对这种新型填料的研究进展和发展前景作出了综述。新型硅酸钙填料是一种多孔蜂窝状,具有质软、比表面积大、沉降体积高、相对密度小、磨耗值低和白度稳定性好等特征。研究表明,在对纸页强度损失很小的情况下新型硅酸钙填料的加填量能够达到30%以上。预计硅酸钙在文化印刷书写纸、低定量轻型化高加填纸、特种功能性纸张的生产领域具有广阔的应用前景,这为综合利用固体废弃物资源,降低生产成本开辟了新途径。     

Environmental tobacco smoke as a source of polycyclic aromatic hydrocarbons in settled household dust

Environmental tobacco smoke is a major contributor to indoor air pollution. Dust and surfaces may remain contaminated long after active smoking has ceased (called 'thirdhand' smoke). Polycyclic aromatic hydrocarbons (PAHs) are known carcinogenic components of tobacco smoke found in settled house dust (SHD). We investigated whether tobacco smoke is a source of PAHs in SHD. House dust was collected from 132 homes in urban areas of Southern California. Total PAHs were significantly higher in smoker homes than nonsmoker homes (by concentration: 990 ng/g vs 756 ng/g, p = 0.025; by loading: 1650 ng/m(2) vs 796 ng/m(2), p = 0.012). We also found significant linear correlations between nicotine and total PAH levels in SHD (concentration, R(2) = 0.105; loading, R(2) = 0.385). Dust collected per square meter (g/m(2)) was significantly greater in smoker homes and might dilute PAH concentration in SHD inconsistently. Therefore, dust PAH loading (ng PAH/m(2)) is a better indicator of PAH content in SHD. House dust PAH loadings in the bedroom and living room in the same home were significantly correlated (R(2) = 0.468, p < 0.001) suggesting PAHs are distributed by tobacco smoke throughout a home. In conclusion, tobacco smoke is a source of PAHs in SHD, and tobacco smoke generated PAHs are a component of thirdhand smoke.     

Alkali ash material: a novel fly ash-based cement

The United States generates 110 million t of coal ash annually. Approximately 70 million t of this coal ash is fly ash, of which 27% is recycled and the remaining 73% is landfilled. Disposal of such a huge quantity of ash poses a significant environmental problem. A new cementitious material has been developed, called alkali ash material (AAM), which is used to produce concrete for construction. AAM can be used to create a variety of concrete strengths and could revolutionize the concrete product manufacturing industry due to its economic advantage. AAM contains 40-95% Class F fly ash and is used as cement to bind sand, stone, and fibers creating concrete. AAM concrete has been tested for strength, durability, mechanical properties, and, most importantly, economic viability. AAM concrete is economically and technically viable for many construction applications. Some properties include rapid strength gain (90% of ultimate in 1 d), high ultimate strengths (110 MPa or 16,000 psi in 1 d), excellent acid resistance, and freeze-thaw durability. AAM's resistance to chemical attack, such as sulfuric (H2SO4), nitric (HNO3), hydrochloric (HCl), and organic acids, is far better than portland cement concrete. AAM is resistant to freeze-thaw attack based on ASTM C-666 specifications. Potential immediate applications of AAM are blocks, pipe, median barriers, sound barriers, and overlaying materials. Eventual markets are high strength construction products, bridge beams, prestressed members, concrete tanks, highway appurtenances, and other concrete products.     

Research Watch: Dioxins in fly ash

Chemistry.     

Spray irrigation of treated municipal wastewater as a potential source of atmospheric PBDEs

Spray irrigation facilities utilizing treated municipal wastewater are a potential source of polybrominated diphenyl ethers (PBDEs) to the atmosphere. PBDEs are used as flame retardants in many household items and have been found in wastewaters and biosolids. Evidence of PBDE release from spray irrigation facilities was discovered during a multiyear project to measure semivolatile organic chemical concentrations in air. Four BDE congeners (47, 99, 100, and 154) were monitored at three remote/ rural locations in Maryland and Delaware from 2001 to 2003. Average concentrations at two of the sites (BDE-47, 10-17 pg/m3; BDE-99, 5.3-7.7 pg/m3) reflect background levels. Average concentrations at the third location were 5-10 times higher (BDE-47, 175 pg/m3; BDE-99, 26 pg/m3) and were significantly correlated (p < 0.0001) with temperature indicating local source(s). Several spray irrigation facilities are located south and west of the third site, the prevailing wind direction during the spring and summer when most samples were collected. The fine mist released from the irrigation equipment may enhance release to the atmosphere via air-water gas exchange from water droplets. Temporal trends indicate that aerial concentrations of PBDEs in this area are increasing at an exponential rate; the atmospheric doubling times for the different congeners range from 1.1 to 1.7 yrs.     

Milwaukee, WI, as a source of atmospheric PCBs to Lake Michigan

A field study of atmospheric PCBs in Milwaukee, WI, U.S.A. was conducted on the shore of Lake Michigan. We believe this is the first report of atmospheric PCBs in Milwaukee, although PCBs are well-known to contaminate the sediments of the Milwaukee River and Outer Harbor. Concentrations of PCBs collected during the June 2001 study are similar to concentrations in other urban-industrial areas and higher than PCBs in background air. The average sigmaPCB (sum of 88 congener groups) gas-phase concentration in Milwaukee was 1.9 ng m(-3)+/-standard deviation 0.78 ng m(-3). The average and standard deviation for the particulate-associated PCBs are 0.05+/-0.02 ng m(-3). Particulate-phase PCBs account for less than 5% of the total atmospheric concentration. PCBs in Milwaukee air are a source of PCBs to Lake Michigan. Calculated net gas exchange fluxes predicted forthe Milwaukee sampling period ranged from -60 to -400 ng m(-2) d(-1), where net deposition is indicated by the negative sign. Calculated particle-associated PCB deposition ranged from 80 to 500 ng m(-2) d(-1). Most of the particle-phase deposition flux is a result of coarse particle deposition and decreases rapidly with distance from shore. Under typical meteorological conditions, particle-associated PCBs depositional flux to the lake surface decreases by 90% within 40 km. For net gas-exchange, the flux reaches zero at about the same distance. At greater distances, particle-phase PCB deposition is negligible, and PCBs are volatilizing at a higher rate than they are being deposited. We calculated that Milwaukee air contributes about 120 kg of PCBs to Lake Michigan each year. This is about 10 times larger than the discharge of PCBs from the Milwaukee River.     

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.     

Characterizing the metal adsorption capability of a class F coal fly ash

The surface physical-chemical characteristics of a class F coal fly ash were studied in an effort to establish a quantitative understanding of metal adsorption. The ash surface acidity (acid site density and acidity constant), surface electrical characteristics, and adsorption constants for selected heavy metal ions were determined using a batch titration method, an electrophoretic method, and a batch equilibrium metal adsorption method, respectively. Results showed that the fly ash has a pHzpc value of 6.2. Its surface contains three types of acid sites. The densities of these acid sites are 2.1 x 10(-4), 1.8 x 10(-5), and 5.3 x 10(-5) mol/g, with acidity constants (pK(H)) of 2.7, 7.8, and 11.0, respectively. Metal adsorption results indicated that, of the three types of acid sites on surface, only the acid site with 7.8 pK(H) is responsible for metal adsorption. The adsorption constants (log K(S)) of Cd(II), Cr(III), Cu(II), Ni(II), and Pb(II) are 4.8, 7.0, 6.4, 4.9, and 8.6, respectively. Adsorption results indicated that the metal adsorption is in the linear range of the Langmuir isotherm if the total metal in the system is less than 10% of the total metal binding site. Results also showed that the presence of anionic metal ions does not affect the adsorption of cationic metal ions by the fly ash.