Halogenated polycyclic aromatic hydrocarbons in the environment

Halogenated polycyclic aromatic hydrocarbons (HPAHs) have been reported to occur in air, sediment, fly ash, and biota samples. This review summarized current existing data on the environmental occurrence, behavior, physicochemical properties, emission sources, and toxic equivalents of HPAHs. Firstly, the physicochemical properties of HPAHs were summarized. Then, an overview of environmental occurrence of HPAHs in ambient matrices including biological samples was reviewed. Meanwhile, the emission sources and possible formation mechanisms of HPAHs were discussed. Apart from that, the aryl hydrocarbon receptor (AhR)-mediated activities were summarized, which indicated that the position and number of halogen atoms on the parent PAHs molecule were important determinant factors affecting the AhR-mediated activity of individual HPAHs congeners. Finally, some research recommendations on HPAHs were given.     

Changes in PCDD/PCDF formation processes during instationary phases of combustor operation--exemplified by the use of Cl4DD isomer patterns

In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the change in PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively. Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found. To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from the fly ash, the Cl4DD isomer distributions are nearly the same in the different matrices. Surprisingly, the Cl4DD isomer distribution of the fly ash was more similar to the distributions found under transient combustion conditions.     

A case study of dioxin monitoring in and around an industrial waste incinerator in Korea

Many studies have been conducted that monitor and trace the sources of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) by comparing congener patterns of environmental samples with those of possible sources. In this study, we measured PCDD/F concentrations and compared congener patterns of samples of various media found in and around an industrial waste incinerator in Korea, including stack gas, fly ash, bottom ash, ambient air, soil, pine needle, and human blood. We obtained reliable data on the relationship between the PCDD/F distributions in these sources and the environment, and thus found indicators with which to assess the impact of such sources on the surrounding environment. In addition, the difference between the levels of PCDD/Fs in the blood of short-term workers and long-term workers demonstrates that these workers are exposed to the compounds produced by the indicator.     

Comparison of 2,4,6-trichlorophenol conversion to PCDD/ PCDF on a MSWI-fly ash and a model fly ash

We performed experiments on two different matrices with 2,4,6-trichlorophenol as precursor to Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD)/F. A municipal solid waste incinerators (MSWI) and a model fly ash were spiked in two different ways. The experiments demonstrated a three times higher formation potential of the trichlorophenol to PCDD on MSWI fly ash compared with the model fly ash used. For both fly ashes the PCDD yield was higher when gaseous trichlorophenol was fed continuously compared to mixing the fly ashes prior to the experiments with the total amount of the precursor. Despite dilution of the fly ashes tenfold with an inactive matrix the conversion of the chlorophenol was very high.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

垃圾焚烧飞灰综合利用研究进展

焚烧处理是解决日益增长生活垃圾的有效方法。垃圾焚烧产生的飞灰因含有大量的重金属等污染物而属危险废物 ,目前常采用的处理方法是填埋。本文就垃圾飞灰的综合利用研究现状进行了论述。从环境和技术的角度看 ,垃圾飞灰的预处理、水泥固化和玻璃化是目前飞灰综合利用的主要研究方向     

Fly ash surface formation and segregation during heating

The possible importance of various physical and chemical processes relevant to fly ash surface formation during coal combustion have been studied. Chemical segregation phenomena and crystal formation processes occurring on fly ash glass surfaces during heating in air and vacuum have been studied for extended periods and temperatures up to 1100°C. XPS, Auger and SIMS methods were used to obtain both relative surface elemental concentrations and depth profiles for major and minor components. Major differences were noted between samples heated in air and in vacuum environments. For the fly ash glass heated in air Fe, Ti and Mg become enriched on surfaces while heating in a vacuum leads to Si surface segregation. The results indicate two levels of surface enrichment; a thin (< 300 Å) layer and a thicker (1–2 μm) layer most evident for heating in air where an Fe-rich layer is formed. The formation of a crystalline granular structure concurrent with Fe enrichment is observed using scanning electron microscopy for heating in air at > 1000°C. The results indicate that the rates of surface segregation may not be sufficiently fast on the time scale of fly ash formation to result in equilibrium levels of surface segregation and that condensation processes during fly ash formation probably play a major role in the observed fly ash surface enrichments.     

地聚合材料固化处理垃圾焚烧飞灰

以垃圾焚烧飞灰和高岭土为主要原料,氢氧化钾为碱激活剂制备了地聚合材料,当焚烧飞灰的掺加量在70%时,其28 d抗压强度可达19.36 MPa。重金属浸出实验表明,地聚合物材料对垃圾焚烧飞灰中的重金属有明显的固化效果,在28 d时基本无溶出。SEM结果表明,地聚合材料的断面结构与力学性能和固化效果相关,XRD和FTIR的分析结果表明,焚烧飞灰和高岭土在碱的激发下生成新的硅铝酸盐聚合物,所得地聚合材料为无定形态。     

Source identification of PCDD/Fs in agricultural soils near to a Chinese MSWI plant through isomer-specific data analysis

Isomer-specific data were investigated in order to identify the sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in agricultural soils, including Fluvo-aquic and paddy soils, in the vicinity of a Chinese municipal solid waste incineration (MSWI) plant. Homologue and isomer profiles of PCDD/Fs in soils were compared with those of potential sources, including combustion sources, i.e., MSWI flue gas and fly ash; and the impurities in agrochemicals, such as the pentachlorophenol (PCP), sodium pentachlorophenate (PCP-Na) and 1,3,5-trichloro-2-(4-nitrophenoxy) benzene (CNP). The results showed that the PCDD/F isomer profiles of combustion sources and agricultural soils were very similar, especially for PCDFs, although their homologue profiles varied, indicating that all the isomers within each homologue behave identically in the air and soil. Moreover, factor analysis of the isomer compositions among 33 soil samples revealed that the contamination of PCDD/Fs in agricultural soils near the MSWI plant were primarily influenced by the combustion sources, followed by the PCP/PCP-Na and CNP sources. This implication is consistent with our previous findings based on chemometric analysis of homologue profiles of soil and flue gas samples, and identifies PCP/PCP-Na as an additional important source of PCDD/Fs in the local area. This makes the similarities and differences of isomer profiles between Fluvo-aquic and paddy soils more explainable. It is, therefore, advisable to use isomer-specific data for PCDD/F source identifications where possible.     

Speciation and mobility of cadmium in straw and wood combustion fly ash

Two fly ashes from biomass combustion have been analysed regarding cadmium speciation and mobility. A fly ash from straw combustion contained 10 mg Cd/kg dry matter, and around 50% of the cadmium was leachable in water. The possible main speciation of cadmium in this fly ash was CdCl2. When adding this fly ash to agricultural soil a threat for groundwater contamination and plant uptake is existing. A fly ash from wood chip combustion had 28.6 mg Cd/kg dry matter. In this fly ash, the cadmium was bound more heavily, with only small amounts of cadmium leached in mild extractants. A possible speciation of cadmium in this fly ash was as oxide or as CdSiO3. Long-term effects and accumulation of cadmium could be a problem when adding this fly ash to agricultural or forest soils.     

Formation of dioxins (PCDDs/PCDFs) by dioxin-free fly ash as a catalyst and relation with several chlorine-sources

Simplified thermal formation experiments have been conducted using dioxin-free fly ash as a catalyst with many kinds of combustible samples such as newspaper, kerosene, paraffin, PE (polyethylene), PP (polypropylene) and PVC. Chlorine sources were PVC, NaCl and HCl. The combustion of samples containing chlorine in the absence of dioxin-free fly ash produced dioxins at a low level although HCl was present in the gas stream. On the other hand, the combustion of samples without chlorine with dioxin-free fly ash increased dioxins formation to a level around 10 times higher than that upon heating dioxin-free fly ash alone. This result is considered to be due to the presence of metal chloride in the fly ash and hydrocarbons in the gas stream. The combustion of samples containing either an organic or inorganic chlorine source or using a HCl stream with dioxin-free fly ash increased dioxin level dramatically.     

Fly Ash from Electrostatic Precipitators: Characterization of Large Spheres

The body of information contained in this paper is directed towards individuals concerned with the toxicology and physical state of airborne effluents from pulverized coal-fired stationary sources. A flotation/sedimentation technique was used to separate fly ash from power plant clean-up devices into light, medium, and high density fractions. Large spherical particles were selected from each fraction and examined by optical and scanning electron microscopy. Attempts were made to identify pleurospheres (filled hollow spheres) by crushing the spheres in situ under the optical microscope. In no cases were filled spheres observed, suggesting that they are not a common structure in fly ash. Several phenomena which generate hollow spheres are discussed.     

粉煤灰资源化的现状

本文检索了国内外综合利用粉煤灰的有关文献 ,由粉煤灰特性入手 ,介绍了它在农业、建筑、环保等行业的资源化现状。指出粉煤灰作为二次资源的重要意义 ,并对粉煤灰资源化提出了一些设想     

粉煤灰技术在污水处理中的应用研究及存在问题讨论

对国内外污水处理中应用粉煤灰技术的现状进行了文献综述 ,并从环境保护与市场机制这个视角对粉煤灰在污水处理中的应用及存在问题进行了分析讨论。粉煤灰具有一定的吸附性能以及细微粒径特征 ,在污水处理中可以获得较好效果。但是同时会产生数倍的污泥增量 ,有些污泥甚至是有毒的 ,会产生二次污染。通过对历史事件的回顾认为以粉煤灰为原料制备混凝剂等 ,尽管在技术上可行 ,但是从市场经济角度看是不可取的     

粉煤灰的改性及其在垃圾渗滤液深度处理中的应用研究

实验采用物理方法和化学方法对粉煤灰进行改性,并用改性粉煤灰深度处理垃圾渗滤液。通过扫描电镜和X-射线衍射对改性前后粉煤灰的表面结构和主要晶相组成进行分析,同时考察其在垃圾渗滤液深度处理中的吸附效果。结果表明,改性后粉煤灰的比表面积和孔隙度增大,吸附能力增强。通过比较,吸附能力最强的改性粉煤灰是将引发剂A与粉煤灰以质量比为1∶9的比例混合,在800℃下恒温焙烧2 h所制得的改性粉煤灰,该改性粉煤灰对垃圾渗滤液中COD和色度的去除率可达到67.3%和87.3%,相对于改性前去除率提高了96.0%和57.8%。     

添加垃圾焚烧飞灰冷固小球的工业烧结实验

将垃圾焚烧飞灰添加进烧结冷固球团配料进行造球,对冷固小球的成分及强度进行分析,结果表明,添加垃圾焚烧飞灰冷固小球化学组成稳定,重金属浸出毒性远低于危险废物鉴别标准,落下强度较基准期略微降低,但符合运输、贮存的要求.并对添加了飞灰的冷固小球对其后续烧结、冶炼工序的影响进行分析,结果表明,用添加飞灰的冷固小球进行烧结所得烧结矿的转鼓强度、落下强度及常规化学成分较基准期没有太大变化,添加飞灰进行造球、烧结,对其后续冶炼工序的顺行几乎没有影响,所带来的额外的环境污染微乎其微.     

铁屑粉煤灰组合处理含磷废水

实验研究了铁屑粉煤灰组合处理含磷废水的除磷效果.通过单因素实验,考查了铁屑粉煤灰质量比、反应时间、pH值和投加量对除磷效果的影响.实验结果表明,该法除磷的最优条件为铁屑和粉煤灰的质量比为2∶1,反应时间为20 min,pH值为6,投加量为20 g/L.在最优实验条件下磷的去除率达到了97.5％.对比了该法和粉煤灰吸附法与传统铁屑法的除磷效果.与单一粉煤灰吸附法和传统铁屑法除磷的结果相比较,铁屑粉煤灰组合除磷的方法具有明显优势.     

Source apportionment of PM10 in six cities of northern China

Ambient PM₁₀ was sampled in six northern China cities (Urumqi, Yinchuan, Taiyuan, Anyang, Tianjin and Jinan) from December 1999 to July 2002, and analyzed for 16 chemical elements, two water-soluble ions, total carbon, and organic carbon. In addition, chemical source profiles consisting of the same particulate components were obtained from a number of naturally occurring geological sources (soil dust from exposed lands) and sources of atmospheric particulates resulting from human activities (resuspended dust, cement, coal combustion fly ash, vehicle exhaust, and secondary particles). Ambient and source data were used in a chemical mass balance (CMB) receptor model to determine the major source of PM₁₀ in these six cities. Results of CMB modeling showed that the major source of ambient PM₁₀ in all the cities was resuspended dust. Significant contributions from coal fly ash were also found in all six cities.     

Aerosol laser ablation mass spectrometry of suspended powders from PM sources and its implications to receptor modeling

Primary sources of particulate matter (PM) were analyzed by suspending powdered samples into an aerosol laser ablation mass spectrometer (LAMS). PM sources studied included vehicle exhaust particulates, dust from a non-ferrous smelter, cement powder, incinerator fly ash, two coal fly ash samples, and two soils. Marker peaks signified certain PM source sectors: construction particles could be distinguished by abundant Ca and Ca compounds, fuel combustion was marked by elemental carbon clusters, and nonferrous industrial particles showed inorganic As, Cu, Pb, Zn, and SOx. In addition to the distinction between particles from these different source sectors, mass spectral results also showed that for a single source, different particle types existed, and among different sources within a sector, similar spectra were present. The aerosol LAMS results show the difficulty in differentiating among separate fly ash sources as well as among different soil samples. A particle class balance receptor model that measures the amount of specific particle types rather than the amount of a chemical component is suggested as a means of source apportionment when particle spectra with overlapping source possibilities occur. The assumptions and limitations of receptor modeling aerosol LAMS data are also described. In particular, methods need to be developed to account for the contribution of secondary sources.     

A new method to assess mercury emissions: a study of three coal-fired electric-generating power station configurations

U.S. Environmental Protection Agency (EPA) Method 7473 for the analysis of mercury (Hg) by thermal decomposition, amalgamation, and atomic absorption spectroscopy has proved successful for use in Hg assessment at coal-fired power stations. In an analysis time of approximately 5 min per sample, this instrumental methodology can directly analyze total Hg--with no discrete sample preparation--in the solid matrices associated with a coal-fired power plant, including coal, fly ash, bottom ash, and flue gas desulfurization (FGD) material. This analysis technique was used to investigate Hg capture by coal combustion byproducts (CCBs) in three different coal-fired power plant configurations. Hg capture and associated emissions were estimated by partial mass balance. The station equipped with an FGD system demonstrated 68% capture on FGD material and an emissions estimate of 18% (11 kg/yr) of total Hg input. The power plant equipped with low oxides of nitrogen burners and an electrostatic precipitator (ESP) retained 43% on the fly ash and emitted 57% (51 kg/yr). The station equipped with conventional burners and an ESP retained less than 1% on the fly ash, emitting an estimated 99% (88 kg/yr) of Hg. Estimated Hg emissions demonstrate good agreement with EPA data for the power stations investigated.