The leachability and chemical speciation of selected trace elements in fly ash from coal combustion and refuse incineration

A laboratory leaching test has been used to predict the potential mobility of As, Se, Pb and Cd in landfilled fly ash produced by coal combustion and refuse incineration. These waste residues also formed the basis of a speciation study in which the valency states of As and Se and the chemical forms of Pb and Cd have been determined. Selenium displayed the greatest leachability in each ash type, despite being present at relatively low concentrations in both materials. Substantial amounts of other trace elements were also leached, particularly Pb and Cd from refuse ash and As from coal ash. Chemical associations of Pb and Cd were examined by a sequential extraction procedure. In coal fly ash, both elements were mostly present in the residual fraction, while in refuse ash these elements were mainly associated with the exchangeable fraction. Water-soluble extracts of coal fly ash contained As exclusively as As(V); high background interference prevented the detection of water-soluble As in refuse ash. Selenium was present largely as Se(IV) in aqueous extracts of both ash types. The value of speciation techniques and leaching tests as predictors of environmental behaviour is discussed in conjunction with results of routine trace element determinations and plant uptake studies.     

城市生活垃圾焚烧飞灰水泥固化技术研究

用硫铝酸盐水泥对城市垃圾焚烧飞灰(简称飞灰)进行固化实验,研究了飞灰重金属浸出特性,分析了飞灰掺量、浸提剂pH值对重金属浸出特性以及飞灰掺量对不同龄期(3、7、28 d)飞灰固化体抗压强度的影响,并对飞灰及其固化体进行XRD分析。结果表明,在HJ/T 299-2007和HJ/T 300-2007两种不同浸出体系下,飞灰中Cu、Zn、Cd、Pb、Cr和Mn等重金属浸出浓度差别较大,建议应根据评价目标合理选择重金属浸出测量方法。其中,飞灰中Pb的浸出浓度超过《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3-2007)限值的3.35倍,因此被列为危险废物,应妥善处理。除飞灰掺量小于40%时的固化体Cd符合标准,其余飞灰固化体Pb和Cd的浸出浓度仍超过《生活垃圾填埋场污染控制标准》(GB 16889-2008)限值,故达不到卫生填埋的要求。固化体抗压强度随飞灰掺量增大而降低,重金属浸出浓度与之相反。飞灰掺量为40%时,固化体中重金属浸出浓度随浸提剂pH值降低而增大,但pH值大于5时,未测出重金属浸出。XRD结果表明:飞灰中可溶性盐参与水泥水化反应,重金属Cr以CrO42-的形式固化于钙矾石中。     

Edaphological characteristics of unweathered and weathered fly ashes from Gondwana and lignite coal

Naturally weathered and unweathered samples of fly ashes produced from Gondwana and lignite coals were characterized for their edaphological properties. The particle size distribution in these fly ashes varied widely, and the percentage of [Formula: see text] size particles governed their water holding capacity. All fly ashes were noncoherent in the dry state and had lower particle density than quartz and mulite. The fly ashes were low in available N, but were sufficient in available P, K, Ca, Mg, S, Cu, Fe, Mn, Zn and B. Among the fly ashes, unweathered lignite fly ash was the richest source of K, Ca, Mg, S and Fe, while weathered lignite fly ash had the highest amounts of Mn, Zn and B. The pH of the fly ashes was closely related to the ratio of exchangeable Ca to exchangeable Al. The fly ashes were high in soluble salt, but were poor in cation exchange capacity. As an amendment to correct soil pH, the fly ashes had a poor buffering capacity. Weathering decreased the total Fe, available S and exchangeable Na percentages, but increased the organic C content of the fly ashes. Invariably, an excess of soluble salts and exchangeable Na could limit plant growth on fly ash dumps. Toxic levels of B and Al existed in only some fly ashes.     

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.     

Heavy metal leaching from coal fly ash amended container substrates during Syngonium production

Coal fly ash has been proposed to be an alternative to lime amendment and a nutrient source of container substrates for ornamental plant production. A great concern over this proposed beneficial use, however, is the potential contamination of surface and ground water by heavy metals. In this study, three fly ashes collected from Florida, Michigan, and North Carolina and a commercial dolomite were amended in a basal substrate. The formulated substrates were used to produce Syngonium podophyllum Schott 'Berry Allusion' in 15-cm diameter containers in a shaded greenhouse. Leachates from the containers were collected during the entire six months of plant production and analyzed for heavy metal concentrations. There were no detectable As, Cr, Hg, Pb, and Se in the leachates; Cd and Mo were only detected in few leachate samples. The metals constantly detected were Cu, Mn, Ni, and Zn. The total amounts of Cu, Mn, Ni, and Zn leached during the six-month production period were 95, 210, 44, and 337 microg per container, indicating that such amounts in leachates may contribute little to contamination of surface and ground water. In addition, plant growth indices and fresh and dry weights of S. podophyllum 'Berry Allusion' produced from fly ash and dolomite-amended substrates were comparable except for the plants produced from the substrate amended with fly ash collected from Michigan which had reduced growth indices and fresh and dry weights. Thus, selected fly ashes can be alternatives to commercial dolomites as amendments to container substrates for ornamental plant production. The use of fly ashes as container substrate amendments should represent a new market for the beneficial use of this coal combustion byproduct.     

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.     

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.     

Trace elements in atmospheric particulate matter over a coal burning power production area of western Macedonia, Greece

Total suspended particle (TSP) concentrations were determined in the Eordea basin (western Macedonia, Greece), an area with intensive lignite burning for power generation. The study was conducted over a one-year period (November 2000–November 2001) at 10 sites located at variable distances from the power plants. Ambient TSP samples were analyzed for 27 major, minor and trace elements. Annual means of TSP concentrations ranged between 47 ± 33 μg m⁻³ and 110 ± 50 μg m⁻³ at 9 out of the 10 sites. Only the site closest to the power stations and the lignite conveyor belts exhibited annual TSP levels (210 ± 97 μg m⁻³) exceeding the European standard (150 μg m⁻³, 80/779/EEC). Concentrations of TSP and almost all elemental components exhibited significant spatial variations; however, the elemental profiles of TSP were quite similar among all sites suggesting that they are affected by similar source types. At all sites, statistical analysis indicated insignificant (P < 0.05) seasonal variation for TSP concentrations. Some elements (Cl, As, Pb, Br, Se, S, Cd) exhibited significantly higher concentrations at certain sites during the cold period suggesting more intense emissions from traffic, domestic heating and other combustion sources. On the contrary, concentrations significantly higher in the warm period were found at other sites mainly for crustal elements (Ti, Mn, K, P, Cr, etc.) suggesting stronger influence from soil resuspension and/or fly ash in the warm months. The most enriched elements against local soil or road dust were S, Cl, Cu, As, Se, Br, Cd and Pb, whereas negligible enrichment was found for Ti, Mn, Mg, Al, Si, P, Cr. At most sites, highest concentrations of TSP and elemental components were associated with low- to moderate-speed winds favoring accumulation of emissions from local sources. Influences from the power generation were likely at those sites located closest to the power plants and mining activities.     

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。     

城市生活垃圾焚烧飞灰与矿山废水共处置技术研究与工程应用

以城市生活垃圾焚烧飞灰和矿山酸性废水无害化处理为研究对象,设计了一条城市生活垃圾焚烧飞灰与矿山酸性废水共处置技术路线,利用焚烧飞灰和矿山酸性废水的酸碱性,加入重金属稳定化药剂,经处理可实现矿山酸性废水和垃圾焚烧飞灰中重金属的有效去除和稳定。矿山酸性废水的pH由2.33升至中性,废水中重金属Cu、Pb、Zn、Cd、Mn、Fe和As等浓度均有下降,可满足国家《污水综合排放标准》(GB 8978-1996)相关标准;垃圾焚烧飞灰中重金属Pb、Zn和Cd浸出浓度分别降低了92.1%、73.4%和95.2%,满足危险废物鉴别标准(GB 5085.3-2007)。     

Arsenic and copper stabilisation in a contaminated soil by coal fly ash and green waste compost

In situ metal stabilisation by amendments has been demonstrated as an appealing low-cost remediation strategy for contaminated soil. This study investigated the short-term leaching behaviour and long-term stability of As and Cu in soil amended with coal fly ash and/or green waste compost. Locally abundant inorganic (limestone and bentonite) and carbonaceous (lignite) resources were also studied for comparison. Column leaching experiments revealed that coal fly ash outperformed limestone and bentonite amendments for As stabilisation. It also maintained the As stability under continuous leaching of acidic solution, which was potentially attributed to high-affinity adsorption, co-precipitation, and pozzolanic reaction of coal fly ash. However, Cu leaching in the column experiments could not be mitigated by any of these inorganic amendments, suggesting the need for co-addition of carbonaceous materials that provides strong chelation with oxygen-containing functional groups for Cu stabilisation. Green waste compost suppressed the Cu leaching more effectively than lignite due to the difference in chemical composition and dissolved organic matter. After 9-month soil incubation, coal fly ash was able to minimise the concentrations of As and Cu in the soil solution without the addition of carbonaceous materials. Nevertheless, leachability tests suggested that the provision of green waste compost and lignite augmented the simultaneous reduction of As and Cu leachability in a fairly aggressive leaching environment. These results highlight the importance of assessing stability and remobilisation of sequestered metals under varying environmental conditions for ensuring a plausible and enduring soil stabilisation.     

Emission of heavy metals from animal carcass incinerators in Taiwan

The metal emissions from three incinerators burning different feedstock in Taiwan were characterized in this study. It was found that the Incinerators A and B, treating pig carcasses and animal (including pigs) carcasses, respectively, had much higher metal concentrations in stack flue gases than Incinerator C that combusted medical wastes. However, Incinerator A obtained relative lower metal contents in fly ash and bottom ash than the other two incinerators, mainly because the former used a much lower feedstock rate (although burning at a lower temperature) than the latter. For all the incinerators, (1) Fe, Ni, Pb, and Zn were dominant in both the fly ash and bottom ash while most of the Cd and Pb (more volatile) were present in the fly ash; (2) Fe emission factor was the highest and Zn/Pb/Ni/Cr emission factors were greater than those of Mn/Cd/Cu; (3) the Cu emission factors in bottom ash were relatively higher in comparison with those in fly ash; and (4) indicatory metals were the same (Fe, Zn, Pb, and Cu). The metal emission factors obtained from the livestock incinerators were much higher than those reported from MSW incinerators. Likewise, crematories that burn human cadavers must create similar pollution issues since metal supplements are part of human's normal diets. This causes an environmental concern and this work has important ramifications both in technical and regulatory decisions.     

Accumulation of nine metals and one metalloid in the tropical scallop Comptopallium radula from coral reefs in New Caledonia

Uptake of waterborne Cd, Co, Mn and Zn was determined in laboratory experiments using radiotracer techniques (109Cd, 57Co, 54Mn and 65Zn). Labelled Zn was mainly accumulated in the digestive gland (65%) and Co in kidneys (81%); Cd and Mn were similarly distributed in digestive gland and gills. In a complementary field study, Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, and Zn were analysed in scallops collected at two stations showing different contamination levels. Digestive gland and kidneys displayed the highest concentrations. Ag, As, Cd, and Fe differed in soft tissues from the two stations, suggesting that Comptopallium radula could be a valuable local biomonitor species for these elements. Low Mn and Zn concentrations found in kidneys suggest that their content in calcium-phosphate concretions differs from the other pectinids. Preliminary risk considerations suggest that As would be the only element potentially leading to exposure of concern for seafood consumers.     

Trace elements in vegetables grown in an industrial area in relation to soil and air particulate matter

The relationships between the trace element content of vegetables, agricultural soil and airborne particulate matter were investigated in the greater industrial area of Thessaloniki, northern Greece. Most elements were found at concentrations normally observed in vegetables grown in uncontaminated areas, however, elevated concentrations of Pb, Zn, Cr and Mn were found particularly in leafy vegetables. The trace element content of agricultural soil was low, despite the airborne particulate matter that was highly enriched with Zn, Cd, Pb and Mn. Multivariate statistical analysis indicated that the compositional patterns of the vegetables, the soil and the atmospheric particulates were largely different. The dominant pathway for most trace elements to vegetable roots was from the soil, while trace elements in vegetable leaves appeared to originate mostly from the atmosphere. High accumulation due to atmospheric deposition was found for Pb, Cr and Cd, especially in leafy vegetables. Root vegetables were found to accumulate soil Cd more efficiently than the other trace elements.     

The distribution of metals in the forest floor of aged conifer stands at a plantation in Northern England

The distribution of the elements Cd, Cr, Cu, Mn, Ni, Pb, Sr, V and Zn has been examined in the horizons of soils under aged Sitka spruce (Picea sitchensis (Bong.) Carr.) stands at a plantation in Northern England. The stands are under first-generation cultivation and are up to 33 years old. Cadmium, Mn, Pb and Zn concentrations were consistently higher in the organic layers than in the underlying mineral soil. This contrasted with the situation for Sr and V. Cadmium, Pb and Zn all showed an increase in concentration in the L + F horizons with stand age and a corresponding increase in the difference between L + F horizon concentrations. Soil pH declined with increasing stand age. Cadmium, Cr, Pb and Zn were all present at higher concentrations in the F horizon than in any other, while Cu and Ni were relatively constant through all the horizons studied. For all nine elements, the H horizon was the largest store of the three organic layers. Calculated rates of accumulation of Cd, Pb and Zn in the L + F horizons gave good agreement with estimated regional atmospheric deposition rates. In comparison to atmospheric deposition, biological mobilisation and deposition of Cd, Pb and Zn make a relatively minor contribution to the surface soil metal burden. Cadmium appeared to be the most readily leached of these three metals from the forest floor, although some transfer of atmospherically-derived Pb to the H+ soil horizons was indicated.     

再生铝飞灰重金属的浸出毒性特征及其控制

采用再生铝飞灰为研究样品,研究了飞灰重金属浸出毒性水平以及飞灰浸出毒性特征,同时探讨了飞灰的处理处置工艺。结果表明：飞灰中Pb、Cd和Zn浸出浓度超标,超标率为100%,属于具有浸出毒性的危险废物,必须对其进行稳定和固化;再生铝飞灰中锌的浸出浓度所占比例最大,铅的浸出浓度次之,两者之和占总量的98%以上,再生铝飞灰中主要有害重金属为Zn和Pb;并结合当前飞灰的处理处置工艺,提出的可能的控制方法为水泥固化和药剂稳定法,为同类研究提供参考。     

钝化材料复配对土壤Cd生物有效性的影响

为了得到效果好的复配钝化材料,采用正交设计,通过培养实验探讨生物炭、粉煤灰、汉白玉3种钝化材料不同复配方式对土壤pH的影响和对镉（Cd）的钝化效果,从中筛选出6种效果较好的复配方式,并以小白菜为供试植物,通过盆栽实验和大田实验探讨了钝化材料复配 对土壤Cd生物有效性的影响。结果表明：3种钝化材料不同复配方式均能显著提高土壤pH,降低土壤有效Cd含量,统计分析发现钝化材料复配过程中对Cd降幅的影响表现为汉白玉>粉煤灰>生物炭。钝化材料添加后,盆栽和大田条件下小白菜可食部位Cd含量均显著降低,综合2种实验条件下小白菜生物量和可食部位Cd含量的变化,1.5%生物炭+1.5%粉煤灰+0.5%汉白玉、1%生物炭+0.5%粉煤灰+1%汉白玉2种复配方式效果最好。     

Comparison of trace element concentrations in livers of diseased, emaciated and non-diseased southern sea otters from the California coast

Infectious diseases have been implicated as a cause of high rates of adult mortality in southern sea otters. Exposure to environmental contaminants can compromise the immuno-competence of animals, predisposing them to infectious diseases. In addition to organic pollutants, certain trace elements can modulate the immune system in marine mammals. Nevertheless, reports of occurrence of trace elements, including toxic heavy metals, in sea otters are not available. In this study, concentrations of 20 trace elements (V, Cr, Mn, Co, Cu, Zn, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb, and Bi) were measured in livers of southern sea otters found dead along the central California coast (n = 80) from 1992 to 2002. Hepatic concentrations of trace elements were compared among sea otters that died from infectious diseases (n = 27), those that died from non-infectious causes (n = 26), and otters that died in emaciated condition with no evidence of another cause of death (n = 27). Concentrations of essential elements in sea otters varied within an order of magnitude, whereas concentrations of non-essential elements varied by two to five orders of magnitude. Hepatic concentrations of Cu and Cd were 10- to 100-fold higher in the sea otters in this study than concentrations reported for any other marine mammal species. Concentrations of Mn, Co, Zn, and Cd were elevated in the diseased and emaciated sea otters relative to the non-diseased sea otters. Elevated concentrations of essential elements such as Mn, Zn, and Co in the diseased/emaciated sea otters suggest that induction of synthesis of metallothionein and superoxide dismutase (SOD) enzyme is occurring in these animals, as a means of protecting the cells from oxidative stress-related injuries. Trace element profiles in diseased and emaciated sea otters suggest that oxidative stress mediates the perturbation of essential-element concentrations. Elevated concentrations of toxic metals such as Cd, in addition to several other organic pollutants, may contribute to oxidative stress-meditated effects in sea otters.     

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.