Trace Element Inputs from a Coal Burning Power Plant to Adjacent Terrestrial and Aquatic Environments

Inputs of trace elements derived from coal ash to terrestrial and aquatic environments were investigated near an 83 MW coal-burning power plant. Comparisons were made between terrestrial inputs of trace elements through aerial deposition during 23 years before installation of electrostatic precipitators and aquatic inputs from ash disposal basins after installation. A gaussian plume model was used to predict deposition patterns of 29 trace elements in coal ash about the power plant. Detectable increases of only Sr, As, Sb, and Be in surface soils within 3 km of the power plant were predicted. Concentrations measured in surface soils were largely consistent with these predictions. Measurements of aerial deposition of Cd, Pb, Cu, and Mn at a site 5.5 km distant were similar to those in other rural areas and indicated that little of the measured Cd, Cu, Mn, or Pb was derived from fly ash. Concentrations of 12 heavy metals in effluents from the basin receiving ash were comparable to those predicted in rainfall deposited nearest the plant. It is concluded that at other coal combustion facilities, basin disposal could be a more serious contamination threat to aquatic environments than aerial dispersal of ash.     

不同粒度飞灰中16种微量元素的含量分布

研究了不同粒级的燃煤飞灰中的Ｂａ、Ｂｅ、Ｃｄ、Ｃｒ、Ｃｕ、Ｈｇ、Ｌｉ、Ｍｎ、Ｎｉ、Ｐｂ、Ｓｒ、Ｔｉ、Ｖ、Ｚｎ、Ｚｒ元素的含量分布,煤中元素的含量比及富集因子。     

Modeling batch leaching behavior of arsenic and selenium from bituminous coal fly ashes

Correctly predicting the leaching potential of arsenic (As) and selenium (Se) is critical for assessing the environmental impact of coal fly ash. This study investigated the impacts of several key environmental factors, including pH, leaching time, and ash washing on the batch leaching behavior of As and Se from bituminous coal fly ashes. The experimental results demonstrated that As and Se leaching from fly ash increased beyond the minimal leaching pH ranges. Increasing leaching time increased As leaching but decreased Se leaching in the alkaline pH condition. A speciation-based adsorption model was used to quantify the batch leaching data, and determine the intrinsic leaching parameters including the total batch leachable mass and the adsorption constant of As or Se. The modeling approach was validated by correctly predicting the independent batch leaching data in a broad pH range and a different L/S condition. Experimental and modeling results also demonstrated that ash washing and ash aging (longer leaching time) did not change the adsorption constants of As and Se on the ash surface. However, ash washing could increase the availability of As and Se for leaching.     

Arsenic and heavy metal mobility in iron oxide-amended contaminated soils as evaluated by short- and long-term leaching tests

Several iron-bearing additives were evaluated for their effectiveness in the attenuation of arsenic (As) in various contaminated soils. These were selected for their known or potential ability to adsorb As anions, thus changing the speciation of As in a soil system. Three soils with different sources of As contamination were investigated (canal dredgings, coal fly ash deposits, and low-level alkali waste). The amendments used were goethite (alpha-FeOOH), iron grit, iron (II) and (III) sulphates (plus lime), and lime, applied to the soils at a rate of 1% w/w. A series of leachate extraction tests (UKEA, ASTM and modified Dutch column leaching test) were conducted on the equilibrated amended soils. These were used to firstly evaluate the potential of the amendments as immobilising agents, and secondly to compare the short- and long-term durability of their effects. Column tests demonstrated the efficiency of iron oxides over the longer time scale; these treatments significantly reduced concentrations of arsenic in leachates from all treated soils. Amended soils were also observed to contain higher levels of lead (Pb) and cadmium (Cd) in their leachates, signifying that certain Fe-oxides potentially increased heavy metal mobility in treated soils. The conclusions were that whilst Fe-oxides may be used as effective in situ amendments to attenuate As in soils, their effects on other trace elements, such as Pb and Cd, require careful consideration.     

Environmental impact of a coal combustion-desulphurisation plant: abatement capacity of desulphurisation process and environmental characterisation of combustion by-products

The fate of trace elements in a combustion power plant equipped with a wet limestone flue gas desulphurisation (FGD) installation was studied in order to evaluate its emission abatement capacity. With this aim representative samples of feed coal, boiler slag, fly ash, limestone, FGD gypsum and FGD process water and wastewater were analysed for major and trace elements using the following techniques: inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), ion chromatography (IC), ion selective electrode (ISE) and atomic absorption spectroscopy (AAS). Mass balances were established allowing to determine the element partitioning behaviour. It was found that, together with S, Hg, Cl, F, Se and As were those elements entering in the FGD plant primarily as gaseous species. The abatement capacity of the FGD plant for such elements offered values ranged from 96% to 100% for As, Cl, F, S and Se, and about 60% for Hg. The environmental characterisation of combustion by-products (boiler slag, fly ash and FGD gypsum) were also established according to the Council Decision 2003/33/EC on waste disposal. To this end, water leaching tests (EN-12457-4) were performed, analysing the elements with environmental concern by means of the aforementioned techniques. According to the leaching behaviour of combustion by-products studied, these could be disposed of in landfills for non-hazardous wastes.     

Immobilization of heavy metals in polluted soils by the addition of zeolitic material synthesized from coal fly ash

The use of zeolitic material synthesized from coal fly ash for the immobilization of pollutants in contaminated soils was investigated in experimental plots in the Guadiamar Valley (SW Spain). This area was affected by a pyrite slurry spill in April 1998. Although reclamation activities were completed in a few months, residual pyrite slurry mixed with soil accounted for relatively high leachable levels of trace elements such as Zn, Pb, As, Cu, Sb, Co, Tl and Cd. Phytoremediation strategies were adopted for the final recovery of the polluted soils. The immobilization of metals had previously been undertaken to avoid leaching processes and the consequent groundwater pollution. To this end, 1100 kg of high NaP1 (Na6[(AlO2)6(SiO2)10] .15H2O) zeolitic material was synthesized using fly ash from the Teruel power plant (NE Spain), in a 10 m3 reactor. This zeolitic material was manually applied using different doses (10000-25000 kg per hectare), into the 25 cm topsoil. Another plot (control) was maintained without zeolite. Sampling was carried out 1 and 2 years after the zeolite addition. The results show that the zeolitic material considerably decreases the leaching of Cd, Co, Cu, Ni, and Zn. The sorption of metals in soil clay minerals (illite) proved to be the main cause contributing to the immobilization of these pollutants. This sorption could be a consequence of the rise in pH from 3.3 to 7.6 owing to the alkalinity of the zeolitic material added (caused by traces of free lime in the fly ash, or residual NaOH from synthesis).     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验,测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣,并为矿区重金属污染土壤的修复提供技术支持,采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理;通过浸出毒性实验对固化/稳定化处理效果进行综合分析,试图寻求一种最佳的稳定剂。结果表明,无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加,样品浸出液的pH都有升高,As、Cd的浸出浓度都有明显下降,而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中,粉煤灰混合堆肥化污泥的处理效果最好,浸出液的pH值达到7.82,As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳,同时具有以废治污的资源化生态效能。     

Adsorption of arsenic(V) onto fly ash: a speciation-based approach

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists in the world. The large volume of coal fly ash produced around the world is a potentially significant anthropogenic source of arsenic. Currently the leaching behavior of arsenic from fly ash is not well understood. Batch methods were used in this study to investigate arsenic leaching using a raw ash, and arsenic adsorption using a clean, washed ash. Experimental results indicated that pH had a significant effect on arsenic leaching or adsorption. Between pH 3 and 7, less arsenic was in the dissolved phase. When pH was less than 3 or greater than 7, increasing amounts of arsenic were leached or desorbed from fly ash. The leaching and adsorption behavior of arsenic was interpreted with the speciation of surface sites and arsenic. In a new approach, a speciation-based model was developed to quantify the arsenic adsorption as a function of pH and surface acidity parameters. This work is important in offering insight into the leaching mechanism of arsenic from coal fly ash, and providing a robust model based upon specific, measurable parameters to quantify arsenic adsorption by other solid media in addition to fly ash.     

Occurrence,speciation, and risks of trace metals in soils of greenhouse vegetable production from the vicinity of industrial areas in the Yangtze River Delta,China

The effect of industrial activities on trace metals in farmland of rapidly industrializing regions in developing countries has increasingly been a concern to the public. Here, soils were collected from 13 greenhouse vegetable production (GVP) farms or bases near industrial areas in the Yangtze River Delta of China to investigate the occurrence, speciation, and risks of Cr, Cu, Zn, Cd, Ni, and Pb in GVP soil. The results revealed that the main metal elements causing GVP soil pollution were Cd, Zn, Ni, and Cu, of which contamination levels were generally unpolluted to moderately polluted. Zinc pollution was mainly attributed to heavy fertilization, while Cd, Ni, and Cu pollution may be greatly ascribed to industrial effluents and coal combustion. Metal speciation studies showed that most of Cr, Ni, Cu, and Zn was present in residual fraction while more than half of Cd and Pb was present in non-residual fractions. Additionally, pollution of Cd, Cu, Ni, and Zn in GVP soil increased their corresponding mobile fractions. Risk assessment using potential ecological risk index and risk assessment code showed that Cd was the major risk contributor. Specifically, Cd generally posed moderate or considerable ecological risk as well as displayed medium or high mobility risk in GVP soil. Thus, great attention should be paid to the contribution of both industrial discharges and intensive farming to soil pollution by trace metals, especially Cd, because of its high mobility risk.

     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

高温堆肥与蚯蚓堆肥对城市污泥重金属形态的影响

采用高温堆肥和蚯蚓堆肥工艺,研究了城市污泥与锯末、粉煤灰或磷矿粉按不同比例混合堆肥前后重金属（Cu、Pb、Zn、Cd和As）交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态和残留态的变化。研究表明：高温堆肥和蚯蚓堆肥前后各试验污泥的重金属形态和含量呈现出不同的变化,都可以降低污泥中交换态Cu、Pb、Zn、Cd和As的含量;对于Cu和Pb,高温堆肥优于蚯蚓堆肥;对于Zn、Cd和As,蚯蚓堆肥优于高温堆肥。2种堆肥方式中,粉煤灰用量为10%的钝化效果优于20%,磷矿粉的钝化效果同粉煤灰一样。     

Leaching characteristics of stabilized/solidified fly ash generated from ash-melting plant

This study was designed to elucidate the leaching characteristics of stabilized/solidified (S/S) fly ash generated by ash-melting. For this study, pH-dependent leaching tests, sequential extraction procedures, and column leaching tests were carried out. The pH-dependent leaching test results for Pb, Cu, and Zn showed that the heavy metal concentrations in the high-pH range were lower than the predicted values for hydroxide and carbonate. During sequential extraction, Cu and Pb were principally distributed in the S/S ashes' organic matter fraction in the chelating agent, suggesting that metals bind to the chelating agent. The percentage of the water-soluble fraction for Pb and Cu was low (<0.2 %). The fly ashes treated with a chelating agent and cement had low leachability potential for metals in the high-pH range. Column tests for S/S fly ashes showed that two leaching stages were distinguishable: one for short time, corresponding to faster metal leaching, and another for the leaching rate. Kinetic speciation was then applied to data obtained from column leaching tests. The first-order reaction/diffusion model showed a better fit for Ca, Pb, and Cu, suggesting that the initial dissolution of soluble compounds, such as metal chloride, was controlled by the first-order reaction (surface wash off). Subsequently, insoluble compounds such as hydroxide or carbonate might penetrate into the porous matrix by diffusion.     

油页岩循环流化床锅炉底渣和飞灰中重金属元素浸出毒性研究

为了研究我国桦甸油页岩65 t/h循环流化床锅炉的底渣和飞灰中重金属元素Cr、Cu、Pb和Zn的赋存状态及不同酸度条件下的浸出特性,分别进行了逐级提取实验和分批浸出的淋滤实验。逐级提取实验结果表明,这4种元素在底渣和飞灰中具有基本相当的赋存状态。硫化物结合态和稳定的残渣态是各元素的主要赋存状态,元素的潜在浸出能力大小表现为:PbCrCuZn,飞灰中各元素的潜在浸出能力大于底渣中的。浸出实验结果表明,元素的赋存状态决定了其浸提能力,浸提液的pH值对各元素浸出能力的影响不尽相同,各元素的浸出能力随浸提时间的延长都会趋于平衡,Cr和Pb的浸出浓度都高于地表水和饮用水的国家标准。     

Time-resolved leaching of cadmium and manganese from lignite and incinerator fly ash

Fly ashes from a lignite fired power plant and a municipal incinerator were leached for 3 hours using 0.1N HC1. Leachate was analyzed for Cd and Mn and plots of concentration versus time for these elements show Cd, a surface adsorbed element in the combustion process, to be rapidly removed from the ash particles in the initial four or five minutes of leaching. Manganese, a fly ash matrix element, is leached at a more constant rate as the ash praticles are dissolved. Total Cd and Mn concentrations in the incinerator fly ash are greater than total concentrations of these elements in the lignite fly ash.     

Utilization of coal fly ash as a slow-release granular medium for soil improvement

This work proposes a new potential application of waste coal fly ash as a K fertilizer support. Fly ash was reacted with KOH to facilitate the impregnation of K as well as to enhance the bonding force. In particular, the applied process resulted in a significant slow-releasing characteristic of fertilizer elements. To examine the effect of K impregnation, a few detailed leaching tests were carried out in terms of process variables such as reaction time and temperature, sintering time and temperature, and KOH concentration. The current experiment presented an optimum preparation condition that is competitive with conventional commercial fertilizers. The manufactured ash fertilizers inhibited release of the K elements. It was also found through the continuous leaching test with pure water that the ash fertilizer had excellent moisture absorbability. However, the effects of some trace elements in fly ash on soil health and crop productivity as well as environmental considerations need to be established with long-term studies.     

Element immobilization in refuse incinerator ashes by solidification in glass, ceramic or cement

Incineration of municipal refuse results in the production of massive quantities of fly ash and bottom ash. Toxic elements in the original refuse may be concentrated up to 40-fold in the resultant ash. There is concern that burial of such ash in landfills could result in leaching of these elements downward into groundwater. In this study, refuse ashes were incorporated into glass, ceramic and cement composites to immobilize such toxic elements. The EP Toxicity Test (1986) was used to show that extraction of such elements by simulated acid rain is effectively blocked in these new solid materials.     

Arrested municipal solid waste incinerator fly ash as a source of heavy metals to the UK environment

Arrested fly ash samples from most currently operating municipal solid waste (MSW) incinerators in the UK have been analysed for a range of elements. Some of the more important heavy metals ranged in concentration as follows: Cd, 21-4646 (median = 271) mg kg(-1); Cu, 296-1307 (642) mg kg(-1); Cr, 44-1328 (574) mg kg(-1); Ni, 45-2204 (74) mg kg(-1); Pb, 447-9704 (4337) mg kg(-1); and Zn, 2285-13,500 (9232) mg kg(-1). These concentrations represent considerable enrichments relative to median UK soil concentrations. Enrichment ratios (defined as median fly ash: median UK soil) were as follows: Mn 1.6; Co 2.6; Ni 3.3; Ba 11; Sr 11; Cr 15; Cu 35; Pb 108; Zn 113; Cd 387. It is estimated that MSW incinerator ash contributes c. 15 t Cd and 241 t Pb to UK landfill sites per annum. These figures compare with previous studies by Hutton & Symon (Hutton, M. & Symon, C. (1986). The quantities of cadmium, lead, mercury and arsenic entering the UK environment from human activities. Sci. Total Environ., 57, 129-50.) which estimated that annual inputs to UK landfills from coal fly ash are c. 60 t Cd and 1270 t Pb. However, it is argued that metals associated with MSW ashes are potentially of greater environmental significance than in coal ashes, because they are much more available and present at much higher concentrations.     

Species- and stage-specific differences in trace element tissue concentrations in amphibians: implications for the disposal of coal-combustion wastes

Information on species- and stage-specific patterns of contaminant accumulation is generally lacking for amphibians, yet such information could provide valuable knowledge on how amphibians interact with contaminants. We assessed concentrations of As, Cd, Cu, Ni, Pb, Se, Sr, and Zn in whole bodies of larval, recently metamorphosed, and adult life stages in Bufo terrestris and Rana sphenocephala from a site that currently receives coal combustion waste (CCW) discharge, a site where CCW was formerly discharged that has undergone natural attenuation for 30 years, and a nearby reference site. For the majority of elements (As, Cd, Cu, Ni, Pb, Zn), concentrations were highest in larvae, but Se and Sr concentrations remained elevated in later life stages, likely because these elements are S and Ca analogs, respectively, and are thus retained throughout structural changes during metamorphosis. Element concentrations were generally higher in B. terrestris than in R. sphenocephala. Concentrations of As, Se, and Sr were up to 11-35 times higher in metamorphs emigrating from CCW-polluted wetlands compared to unpolluted wetlands, suggesting metamorphosed amphibians can transport trace elements from aquatic disposal basins to nearby uncontaminated terrestrial habitats. In addition, anurans utilizing naturally revegetated sites up to 30 years after CCW disposal ceases are exposed to trace elements, although to a lesser degree than sites where CCW is currently discharged.     

SGA对垃圾焚烧飞灰中重金属的固化性能研究

根据EPA1311、HJ／T299—2007、HJ／T300—2007和HJ557—2009等国内外不同标准,研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性,探讨了六硫代胍基甲酸（sixthioguanidineacid,SGA）、二甲基二硫代氨基甲酸盐（sodiumdimethyldithiocarbamate,SDD）和Ca（OH）2浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明,随着浸提液pH的降低,该厂焚烧飞灰中大部分金属元素的浸出量增大,焚烧飞灰浸出液中的cd、Ni、Ph和zn浓度分别超过国家危险废物鉴别标准（GB5085．3—2007）规定值的4．75倍、1．47倍、6．72倍和2．20倍,属于危险废弃物,必须进行稳定化处理。当固化剂SGA加入量为0．1mol／kg时,稳定化后的重金属浸出浓度已经低于危险废物鉴别标准,且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）2;当固化剂SGA、SDD和Ca（OH）2加入量为0．5mol／kg时,稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB5085．3-2007）中的规定值。与SDD和Ca（OH）：相比,SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。