Investigation on chemical species of arsenic, selenium and antimony in fly ash from coal fuel thermal power stations

Investigations of the existing chemical forms and the concentrations of arsenic (As), selenium (Se) and antimony (Sb) in samples of fly ash obtained from six coal-fired power stations in various countries were carried out. The concentration of As was found to vary from 5.4 to 22.3 mg kg(-1), and the most common mode of occurrence of As in the fly ashes is in association with carbonates or Fe-Mn oxides. The concentrations of Se and Sb ranged from 2.3-5.2 and 1.0-3.9 mg kg(-1), respectively. The dominant chemical forms of Se and Sb in the fly ashes were as extractable species. Also, water-soluble As, Se and Sb in the fly ashes were extracted, and the chemical species of As, Se and Sb in the extract determined using HPLC-ICP-MS. This was done as the potential release of soluble As, Se and Sb through leaching of fly ash is of environmental concern. The most abundant form of As in the extract was the low toxicity As(V). The main species of Se was Se(IV), although it was found that the ratio of Se(VI) to Se(IV) in acidic fly ashes is higher than in alkaline fly ash samples. Antimony was mostly present as Sb(III).     

Uranium oxide and other airborne particles deposited on cypress leaves close to a nuclear facility

Enhanced activity of actinides and some decay products has been reported for the leaves of cypress trees (Chamaecyparis nootkatensis) at the edge of the Malvési uranium-processing facility, southwestern France. The enhanced activity is due to the release of actinides via the smokestacks and from artificial ponds inside the facility. This study was conducted to characterize airborne particulate matter deposited on the leaf surfaces and to investigate whether or not radioactive particles may be identified. Air-dried leaf samples were examined by scanning electron microscopy, in combination with energy-dispersive X-ray spectrometry. The samples were scanned systematically in both secondary and backscattered electron modes. Particles ranging in size from <200 nm to ~40 μm were found on most portions of the adaxial leaf surface, but they are especially abundant at the boundary between facial and lateral leaves. The majority of the analyzed particles could be attributed to five principal classes: carbonates, silicates, sulfates, oxides/hydroxides, and halides. In addition, other types of particles were found, including Fe alloys; scheelite-group phases; phosphates; sulfides; and fly ash spheres. Similar particles were also observed on the surface of a wheat sample used for comparison. Of special interest are U-rich particles, which were observed on the cypress leaves only and which were identified as U oxides, except for one particle, which was a U-oxide-fluoride. These U-rich particles were released into the atmosphere by the nuclear facility prior to their deposition on the leaf surfaces. As most of the U-rich particles are <2.5 μm across, they are respirable. Once inhaled, particles containing alpha-emitting isotopes represent a potentially long-term source of ionizing radiation inside the lungs and thus, pose a threat to the health of people living nearby.     

乌鲁木齐冬季雾天可吸入颗粒物透射电子显微镜研究

利用透射电子显微镜(TEM)对乌鲁木齐冬季雾天采集的可吸入颗粒物(PM_2.5、PM_2.5~10)的形貌特征和集聚状态进行分析。将乌鲁木齐大气可吸入颗粒物分为烟尘集合体、飞灰、矿物颗粒、硫酸盐和有机颗粒等5种单颗粒类型,并讨论了其来源。TEM分析表明,PM_2.5中烟尘集合体占14%,飞灰占7.4%,矿物颗粒占24%,硫酸盐占16.7%,有机颗粒占20.4%;PM_2.5~10 中烟尘集合体没有观察到,飞灰占4.9%,矿物颗粒占26.8%,硫酸盐占12.2%,有机颗粒占58.5%。     

Characterization of individual aerosol particles in workroom air of aluminium smelter potrooms

Aerosol particles with aerodynamic diameters between 0.18 and 10 microm were collected in the workroom air of two aluminium smelter potrooms with different production processes (Soderberg and Prebake processes). Size, morphology and chemical composition of more than 2000 individual particles were determined by high resolution scanning electron microscopy and energy-dispersive X-ray microanalysis. Based on chemical composition and morphology, particles were classified into different groups. Particle groups with a relative abundance above 1%(by number) include aluminium oxides, cryolite, aluminium oxides-cryolite mixtures, soot, silicates and sea salt. In both production halls, mixtures of aluminium oxides and cryolite are the dominant particle group. Many particles have fluoride-containing surface coatings or show agglomerations of nanometer-sized fluoride-containing particles on their surface. The phase composition of approximately 100 particles was studied by transmission electron microscopy. According to selected area electron diffraction, sodium beta-alumina (NaAl(11)O(17)) is the dominant aluminium oxide and cryolite (Na(3)AlF(6)) the only sodium aluminium fluoride present. Implications of our findings for assessment of adverse health effects are discussed.     

Adsorption–desorption of metolachlor and atrazine in Indian soils: effect of fly ash amendment

The effect of two fly ashes as soil amendment on the adsorption–desorption of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylphenyl)] and atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was studied in alluvial and laterite soils. The adsorption data for both the herbicides fitted well the Freundlich equation, and Freundlich adsorption coefficient (K _f) increased with an increase of fly ash amount. Both the fly ashes differed in their extent to increase herbicide sorption, and the effect was different in different soils. Atrazine was sorbed more in the soils/soils?+?fly ash mixtures than the metolachlor. The K _f values showed significant correlation with the amount of fly ash amendment (correlation coefficient, R?>?0.982). The desorption isotherms also fitted the Freundlich equation, and desorption showed hysteresis which increased with an increase in the content of fly ash amendment. The free energy change (ΔG) indicated that the sorption process is exothermic, spontaneous, and physical in nature. The study has shown that fly ash as soil amendment significantly increased the sorption of metolachlor and atrazine, but the effect is soil- and fly ash-specific.     

Ion chemistry and individual particle analysis of atmospheric aerosols over Mt. Bogda of eastern Tianshan Mountains, Central Asia

Aerosol samples were collected during the scientific expedition to Mt. Bogda in July-August, 2009. The major inorganic ions (Na(?+?), NH??, K(?+?), Mg(2?+?), Ca(2?+?), Cl(?-?), SO2??, and NO??) of the aerosols were determined by ion chromatography. SO2??, NO??, and Ca(2?+?) were the dominate ions, with the mean concentrations of 0.86, 0.56, and 0.28 μg m?3, respectively. These mean ion concentrations were generally comparable with the background conditions in remote site of Xinjiang, while much lower than those in ürümqi. Morphology and elemental compositions of 1,500 particles were determined by field emission scanning electron microscopy equipped with an energy dispersive X-ray spectrometer. Based on the morphology and elemental compositions, particles were classed into four major groups: soot (15.1%), fly ash (4.7%), mineral particles (78.9%), and little other matters (0.8% Fe-rich particles and 0.5% unrecognized particles). Presence of soot and fly ash particles indicated the influence of anthropogenic pollutions, while abundance mineral particles suggested that natural processes were the primary source of aerosols over this region, coinciding with the ionic analysis. Backward air mass trajectory analysis suggested that ürümqi may contribute some anthropogenic pollution to this region, while the arid and semi-arid regions of Central Asia were the primary source.     

Particle size distribution of aerosols and associated heavy metals in kitchen environments

Mass size distributions of total suspended particulate matter (TSPM) was measured from Sep 2002 to April 2003 in indoor kitchen environments of five locations in Jawaharlal Nehru University (JNU), New Delhi, with the help of a high volume cascade impactor. Particulate matters were separated in five different size ranges, i.e. >10.9 microm, 10.9-5.4 microm, 5.4-1.6 microm, 1.6-0.7 microm and <0.7 microm. The particle size distribution at various sites appears to follow uni-modal trend corresponding to fine particles i.e. size range <0.7 microm. The contributions of fine particles are estimated to be approximately 50% of TSPM and PM10.9, while PM10.9 comprises 80% of TSPM. Good correlations were observed between various size fractions. Regression results reveal that TSPM can adequately act as a surrogate for PM10.9 and fine particles, while PM10.9 can also act as surrogate for fine particles. The concentrations of heavy metals are found to be dominantly associated with fine particles. However, the concentration of some metals and their size distribution, to some extent is also site specific (fuel type used).     

Speciation of nickel in Canadian subbituminous and bituminous feed coals, and their ash by-products

The nickel species in the feed coals and ash by-products from seven Canadian power plants (including one with a fluidized bed combuster) burning local subbituminous and bituminous coals with sulfur contents ranging from 0.22 to 3.6% have been examined using nickel XANES spectroscopy. XANES spectroscopy of Ni in coal and coal derived ash is complicated by a poor signal : noise ratio due to fluorescence of the much more abundant iron in the coal. Nevertheless, it has proved possible to show that the Ni environment in coals varies from largely oxidic species to mixtures of Ni-containing oxide and sulfide species. The nickel in one oxidized coal appears to be present as nickel sulfate. Nickel in all bottom and fly ash samples examined appears also to be present largely in oxygen anion environments. With the exception of one fly ash sample, for which the Ni exhibited spectral features similar to those for Ni(2+) in spinel or oxide phases, the nickel in the bottom and fly ash samples appears to exist largely as Ni(2+) in environments similar to those reported for Ni in silicate glasses. The data obtained indicate that the presence of potentially carcinogenic nickel sulfides in ash by-products from combustion of these coals is unlikely.     

桂林市细颗粒物部分典型排放源的粒径谱及成分分析

采用在线单颗粒气溶胶质谱技术源解析方法,对桂林市PM2.5典型排放源的粒径和化学成分进行质谱分析,采集燃煤/燃气源、工业工艺源、扬尘源、油烟源4类共计7个典型排放源。结果表明,桂林市4类排放源细颗粒物的粒径分布为0.25~1.25μm,80%以上的细颗粒分布在0.2~1.0μm的小粒径范围,峰值约0.68μm。细颗粒物离子成分含有Na~+、Mg~+、K~+、NH~+4、Fe~+、Pb~+、Cd~+、V~+、Mn~+、Li~+、Al~+、Ca~+、Cu~+、Zn~+、Cr~+、CN~-、PO_3~-、NO_2~-、NO_3~-、Cl~-、SO_4~(2-)、SiO_3~-等成分,桂林市细颗粒物为元素碳、有机碳元素碳、有机碳、富锰颗粒、富铁颗粒、富钾颗粒、矿物质、左旋葡聚糖以及其他金属等9类。     

Fractionation of elements by particle size of ashes ejected from Copahue Volcano,Argentina

The volcano Copahue, Neuquén province, Argentina has shown infrequent explosive eruptions since the 18th century. Recently, eruptive activity and seismicity were registered in the period July-October, 2000. As a consequence, ash clouds were dispersed by winds and affected Caviahue village located at about 9 km east of the volcano. Samples of deposited particles from this area were collected during this episode for their chemical analysis to determine elements of concern with respect to the health of the local population and its environment. Different techniques were used to evaluate the distribution of elements in four particle size ranges from 36 to 300 microm. X-ray powder diffraction (XRD) was selected to detect major components namely, minerals, silicate glass, fragments of rocks and sulfurs. Major and minor elements (Al, Ca, Cl, Fe, K, Mg, Mn, Na, S, Si and Ti), were detected by energy dispersive X ray analysis (EDAX). Trace element (As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, U, V and Zn) content was quantified by inductively coupled plasma-mass spectrometry (ICP-MS). Nuclear activation analysis (NAA) was employed for the determination of Ce, Co, Cs, Eu, Hf, La, Lu, Rb, Sc, Sm, Ta and Yb. An enrichment was observed in the smallest size fraction of volcanic ashes for four elements (As, Cd, Cu and Sb) of particular interest from the environmental and human health point of view.     

Occurrence of chlorinated and brominated polycyclic aromatic hydrocarbons in surface sediments in Shenzhen, South China and its relationship to urbanization

One hundred and fourteen surface sediments were collected from the Maozhou River Watershed in Shenzhen, China from December 2009 to January 2010. Three individual chlorinated polycyclic aromatic hydrocarbons (ClPAHs), six individual brominated polycyclic aromatic hydrocarbons (BrPAHs), and five corresponding parent polycyclic aromatic hydrocarbons (PAHs) were determined. The concentration of 9-chlorophenanthrene was the highest ranging from 0.51-289 ng g(-1) (average, 16.5 ng g(-1)). For BrPAHs, the concentration of 2-bromofluorene was the highest ranging from 0.31-266 ng g(-1) (average, 35.3 ng g(-1)). No correlation was observed between the concentrations of ClPAHs and parent PAHs in surface sediments. In addition, there was no correlation between 1-bromopyrene, 7-bromobenz(a)anthracene and 9,10-dibromoanthracene, and corresponding parent PAHs. However, a significant correlation was found between 9-bromophenanthrene and phenanthrene (p < 0.01), between 9-bromoanthracene and anthracene (p < 0.05), and between 2-bromofluorene and fluorene (p < 0.05). Six fly ash samples collected from one of the municipal domestic waste incineration plants in Shenzhen were also analyzed for source identification. The concentration of 7-bromobenz(a)anthracene was the highest, ranging from 3.21-4.08 ng g(-1). In addition, 2-bromofluorene was not detected in all the fly ash samples. No correlation was found between the concentrations of Cl-/BrPAHs and corresponding parent PAHs in fly ashes. We also examined the relationship between the levels of Cl-/BrPAHs in surface sediments and the urbanization process. Our results suggested the levels of individual Cl-/BrPAHs congeners presented a similar increasing trend with the increasing urbanization level.     

The hygroscopic behaviour of individual aerosol particles in nickel refineries as investigated by environmental scanning electron microscopy

The hygroscopic properties of individual aerosol particles (1-35 microm equivalent projected area diameter) from the Roasting, Anode Casting and Electrorefining Departments of two Ni refineries were studied by environmental scanning electron microscopy (ESEM) and energy-dispersive X-ray microanalysis (EDX) at a relative humidity of 96-98% (at a temperature of 5 degrees C). In the Roasting and Anode Casting Departments, most particles (60-85% by number) showed no visible change in size or surface morphology when exposed to high relative humidity. Approximately 15-30% of the particles developed a thin water film (growth factors between 1.006 and 1.06) indicating the presence of thin surface coatings of sulfates. About 10% of the particles in the Roasting Department formed droplets (growth factors between 1.1 and 2.6) which always contained a large portion of insoluble material. In the Electrorefining Department, most particles (approximately 60%) were residues from the electrolysis bath solution. At a relative humidity of 96-98% these particles formed a solution which contained only small insoluble inclusions. About 30% of the particles in the Electrorefining Department developed thin water films. As only a small fraction of the particles increased substantially in size when exposed to high relative humidity, the deposition pattern of the total aerosol mass fraction will not be changed substantially by hygroscopic growth. The frequent occurrence of thin surface coatings of soluble material on insoluble Ni compounds has to be considered for health assessment purposes.     

Grain-size analysis of volcanic ash for the rapid assessment of respiratory health hazard

Volcanic ash has the potential to cause acute and chronic respiratory diseases if the particles are sufficiently fine to enter the respiratory system. Characterization of the grain-size distribution (GSD) of volcanic ash is, therefore, a critical first step in assessing its health hazard. Quantification of health-relevant size fractions is challenging without state-of-the-art technology, such as the laser diffractometer. Here, several methods for GSD characterization for health assessment are considered, the potential for low-cost measurements is investigated and the first database of health-pertinent GSD data is presented for a suite of ash samples from around the world. Methodologies for accurate measurement of the GSD of volcanic ash by laser diffraction are presented by experimental analysis of optimal refractive indices for different magmatic compositions. Techniques for representative sampling of small quantities of ash are also experimentally investigated. GSD results for health-pertinent fractions for a suite of 63 ash samples show that the fraction of respirable (<4 microm) material ranges from 0-17 vol%, with the variation reflecting factors such as the style of the eruption and the distance from the source. A strong correlation between the amount of <4 and <10 microm material is observed for all ash types. This relationship is stable at all distances from the volcano and with all eruption styles and can be applied to volcanic plume and ash fallout models. A weaker relationship between the <4 and <63 microm fractions provides a novel means of estimating the quantity of respirable material from data obtained by sieving.     

Determination and evaluation of hexavalent chromium in power plant coal combustion by-products and cost-effective environmental remediation solutions using acid mine drainage

The chromium species leaching from a coal combustion fly ash landfill has been characterized as well as a novel approach to treat leachates rich in hexavalent chromium, Cr(VI), by using another natural waste by-product, acid mine drainage (AMD), has been investigated during this study. It is observed that as much as 8% (approximately 10 microg g(-1) in fly ash) of total chromium is converted to the Cr(VI) species during oxidative combustion of coal and remains in the resulting ash as a stable species, however, it is significantly mobile in water based leaching. Approximately 1.23 +/- 0.01 microg g(-1) of Cr(VI) was found in the landfill leachate from permanent deposits of aged fly ash. This study also confirmed the use of AMD, which often is in close proximity to coal combustion by-product landfills, is an extremely effective and economical remediation option for the elimination of hexavalent chromium in fly ash generated leachate. Speciated isotope dilution mass spectrometry (SIDMS), as described in EPA Method 6800, was used to analytically evaluate and validate the field application of the ferrous iron and chromate chemistry in the remediation of Cr(VI) runoff.     

Dust-particle migration around flotation tailings ponds: pine needles as passive samplers

The potential use of dust particles trapped on Scots pine needles for tracking dust migration around flotation tailings ponds in the Silesian-Krakowian ore district, Southern Poland was tested. 1-, 2- and 3-years old needles were studied using a scanning electron microscope and energy dispersive X-ray microanalysis. Particle sizes and morphologies, and the nature of the compounds hosting metals ions, were examined. A large majority of the particles examined are <10 microm in size. Almost 80% of particles represent respirable dust. All the components in the flotation wastes appear among the chemical compounds identified in particles on the pine needles. The quantity of the waste particles decreases with distance from the flotation tailings ponds. The analysis of dust particles on pine needles could be a useful method for estimating vectors and travel distances of suspended dust migrating around open flotation tailings ponds and around other point sources emitting dust particles with chemical compositions differing from the environmental background.     

Bioaccumulation of nutrient elements from fly ash-amended soil in Jatropha curcas L.: a biofuel crop

Fly ash (FA) from coal-burning industries may be a potential inorganic soil amendment; the insight of its nutrient release and supply to soil may enhance their agricultural use. The study was conducted to assess the ability of fly ash (a coal fired thermal plant waste) to reduce soil fertility depletion and to study bioaccumulation of mineral nutrients in Jatropha curcas grown on soils amended with fly ash. Fly ash was amended to field soil at six rates (0, 5, 10, 20, 40, and 70 % w/w) on which J. curcas was grown. After 8 months of growth, the height of jatropha plants was significantly increased at 5 and 10 % FA-amended soil, whereas, biomass significantly increased at 5, 10, and 20 % FA-amended soil compared to control soil (0 % FA). Leaf nutrients uptake, followed by stems and roots uptake were highly affected by fly ash amendment to soil. Most of nutrients accumulation were increased up to 20 % fly ash and decreased thereafter. The results of available nutrient analysis of soil revealed that availability of nitrogen, potassium, sulfur, copper, iron, mangnese, and zinc declined significantly at higher levels of fly ash amendments, whereas, availability of phosphorus increased at these levels. However, pH, organic carbon, and available boron were not influenced significantly by fly ash amendment to soil. Microbial biomass C, N, and ratio of microbial-C to organic C were significantly reduced at 20 % fly ash and higher amounts. This study revealed that J. curcas plants could gainfully utilize the nutrients available in fly ash by subsequently amending soil.     

新疆三地区总悬浮颗粒(TSP)中单颗粒的微观形貌特征

用扫描电镜/X射线衍射能谱(SEM/EDX)对喀什地区、乌鲁木齐市米东区、和田地区的总悬浮颗粒(TSP)的单个颗粒进行了形貌观察。经分析得出:喀什地区颗粒物无规则形为34%,片状为54%;和田地区的颗粒物片状为80%,球形为12%;乌鲁木齐市米东区的颗粒物均匀球形蜂窝聚集态为90%。对此作来源解析可以认为:乌鲁木齐市米东区的TSP主要来源是燃烧排放的飞灰及在大气中形成的二次粒子居多,而喀什地区及和田地区的TSP主要来源为土壤及矿物颗粒灰尘。     

Leachate of fly ash derived from refuse incineration

For highly urbanized cities where there is a scarcity of land available for landfilling, incineration of refuse is a feasible solution for solid waste disposal. After incineration, about 20% by weight of fly ash and other residues are produced and disposed of by landfill. Leachate tests carried out on samples of fly ash show that the heavy metal concentrations of the leachate are in excess of the permissible limits set by WHO. Lime and cement are used to stabilize the fly ash. The concentrations of heavy metals in the leachates of lime and cement treated fly ash are non-detectable. In additional to pollution control, the lime and cement treated fly ash significantly improves the properties of soft clay.