FACTORS INFLUENCING ACUTE TOXICfrY OF COAL ASH TO RAINBOW TROUT (SALMO GAIRDNERI) AND BLUEGILL SUNFISH (LEPOMIS MACROCHIRUS)1

ABSTRACT: The potentially toxic components in coal ash (ash particles, heavy metals) were evaluated in laboratory static, acute (96 hr) bioassays, both separately and in various combinations with extreme pH (5.0 and 8.5), using rainbow trout (Salmo gairdneri) and bluegifi sunfish (Lepomis macrochirus). Ash particle morphology and metal distribution anlaysis, using electron microscopy and surface-subsurface analysis by ion microscopy, showed that metals could be either clumped or evenly distributed on the surface of fly ash. Surface enrichment on fly ash particles from electrostatic precipitators, as measured by ion microscopy, was found for cadmium, copper, chromium, nickel, lead, mercury, titanium, arsenic, and selenium. Bottom (heavy) ash was not acutely toxic to either fish species at concentrations of up to 1500 mg/l total suspended solids (TSS) at pH 5.0, 7.5, or 8.5. Fly ash particles were not acutely toxic to blue-gill at levels up to 1360 mg/l TSS. Rainbow trout were highly sensitive to fly ash (25 to 60 percent mortality) at concentrations of 4.3 to 20.5 mg/I TSS when dissolved metal availability was high but were not sensitive at higher particulate concentrations (58 to 638 mg/I TSS) when dissolved metals were low. When metals were acid-leached from fly ash prior to testing, no rainbow trout mortality occurred at TSS concentrations of up to 2,350 mg/l TSS. When the percent of dissolved metal was high (e.g., 50–90 percent of the total), fish mortality was increased. Rainbow trout were nearly two orders of magnitude more sensitive than bluegill when subjected to a blend of cadmium, chromium, copper, nickel, lead, and zinc. The two species were similar in their acute sensitivity to acidic pH at levels at or below 4.0 and alkaline pH of 9.1. If the pH of coal ash effluent is contained within the range 6.0 to 9.0, acute toxicity to fish can be attributed to trace element availability from fly ash but not heavy ash. Control of holding pond and effluent pH and maximizing pond residence time are important strategies for minimizing effects of ash pond discharges on fish.     

粉煤灰在重金属废水处理中的应用

粉煤灰是一种可再资源化的工业固体废弃物。利用粉煤灰对重金属废水进行处理可谓是一种以废治废、变废为宝、实现废物综合利用的有效途径。综述了粉煤灰吸附法在重金属废水处理中的国内外研究现状,展望了该方法的应用前景。     

生活垃圾焚烧中重金属行为的研究进展

垃圾中的金属以氧化物、氮化物、碳化物及其它形态转移到焚烧产物如烟气、飞灰和底灰中，需严格控制焚烧过程中重金属的排放，故清楚了解金属在焚烧中的行为是很必要的。经研究发现，飞灰中重金属含量远远大于底灰中的含量，因此以垃圾焚烧飞灰中重金属的稳定化处理为目标，分析了目前国内外处理垃圾焚烧飞灰的方法和重金属在各种影响因素下的行为，并进行了比较，为飞灰的无害化和资源化处理提供参考。     

垃圾焚烧飞灰处置与资源化利用研究进展

随着生活垃圾焚烧处理方式的不断推广，焚烧飞灰的产生量也不断增加。按照我国固体废物分类方法，焚烧飞灰属于危险废物，必须进一步处置才能进入填埋场或资源化利用。本文分析了飞灰物理化学特性，论述了常规处置技术（水泥固化、化学药剂稳定化、酸溶剂提取和熔融固化等）存在的问题。将原始飞灰直接应用于水泥、混凝土或路基材料，飞灰中高含量的重金属和盐类会产生新的环境问题。飞灰水洗可以高效去除其中的可溶性盐类，水洗飞灰在焙烧后重金属的浸出浓度远低于原始飞灰烧结后的相应浓度，飞灰水洗-焙烧技术具有很好的应用前景。     

湿法预处理对垃圾焚烧飞灰中重金属的形态及风险影响研究

以某典型城市生活垃圾焚烧飞灰为研究对象,采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）和电感耦合等离子体光谱仪（ICP）测定了焚烧飞灰的主要成分、矿物学组成和重金属含量,探讨了湿法预处理工艺对飞灰的化学组成、矿物学形态、化学形态及风险水平的影响.结果表明,飞灰的主要化学组成为O、Ca、Cl、Na、K等,占飞灰总质量的93.54％,其次含有0.04％ ～0.68％的Zn、Pb、Cu、Cr等微量重金属元素;经过湿法预处理,飞灰中可溶性氯盐具有较好的去除效果,且几乎所有重金属元素的不稳定形态（弱酸提取态和可还原态）比例都有一定程度的减少,有效降低了重金属的毒性、生物有效性及环境风险水平.本研究有助于降低焚烧飞灰的环境风险和探寻其资源化的有效途径.     

垃圾焚烧飞灰中重金属的固化/稳定化处理实验研究

研究了城市生活垃圾焚烧-电灰的特性及飞灰中重金属的特性,对利用水泥作粘结剂进行飞灰固化/稳定化处理效果开展了系统的实验研究,分析了水泥固化/稳定化飞灰的工艺特点和最佳工艺参数,并讨论了粘结剂固化飞灰机理以及重金属浸出毒性,为进一步研究城市生活垃圾焚烧飞灰的无害化处理与利用提供了有重要价值的参考依据.     

Characterization of MSWI fly ash through mineralogy and water extraction

This paper investigates the mineralogical characteristics of fresh, aged and hot water extracted MSWI fly ash for providing the baseline information of minerals stability which controls the released heavy metals into the environment. Quantitative determination of bulk phase abundance in the fresh fly ash by the XRD Rietveld refinement method provided composition levels for amorphous and crystalline phases such as potassium tetrachlorozincate (K₂ZnCl₄), gehlenite, halite, quartz, anhydrite, and feldspar. The minerals association in the fly ash is clearly unstable and subject to mineralogical reactions. The phases of K₂ZnCl₄, halite and anhydrite in the fresh fly ash were involved in hydration and dissolution/precipitation processes to form new minerals such as the Zn-bearing mineral gordaite, syngenite, gypsum and hydrocalumite. The solubility-controlling phases and extractability of heavy metals were examined in a Soxhlet hot water-extractor. Here the soluble salts were simply removed from fly ash while Ca-, Al-, Si- and SO₄²⁻-bearing hydrate minerals were precipitated from the extraction solution. Furthermore, a low release of heavy metals Zn, Pb and Cd in hot water was noticed, indicating a strong retention of the trace metals in the mineral phases remaining in the insoluble fly ash residues.     

我国南方某城市垃圾焚烧飞灰特性及固化/稳定化处置实验

我国南方某城市主要采用焚烧法处理生活垃圾,已建7个焚烧厂日产生飞灰量为101.62 t/d。文章分析了各个垃圾焚烧厂飞灰的化学组成和重金属浸出毒性,其主要成分为CaO、SiO2、MgO、Al2O3、Fe2O3、Na2O、SO3和Cl,所有焚烧飞灰都有至少一种重金属浸出浓度超标,属于危险废物。在飞灰处置出路亟待解决的背景下,实验探讨了飞灰稳定化工艺,结果表明10%的水泥添加量可以使飞灰中超标重金属(Cd、Pb和Zn)的浸出浓度满足危险废物鉴别浓度限值和安全填埋场入场浓度限值。同时,通过人体健康风险评价分析了飞灰豁免管理的可行性,并对近期和远期该城市焚烧厂飞灰的处理处置及管理提出建议。     

Increasing bioavailability of phosphorus from fly ash through vermicomposting

Due to the environmental problems created by large-scale fly ash generation throughout the world, efforts are being made to recycle these materials. An important component of the recycling effort is using fly ash to improve low-fertility soils. Because availability of many nutrients is very low in fly ash, available ranges of such nutrients must be improved to increase the effectiveness of fly ash as a soil amendment. In the present study, we assessed the possibility of increasing P bioavailability in fly ash through vermicomposting in a yard experiment. Fly ash was mixed with organic matter in the form of cow (Bos taurus) dung at 1:3, 1:1, and 3:1 ratios and incubated with and without epigeic earthworm (Eisenia fetida) for 50 d. The concentration of phosphate-solubilizing bacteria (PSB) was found to increase many fold in the earthworm-treated series of fly ash and organic matter combinations compared with the series without earthworm. This helped to transform considerable amounts of insoluble P from fly ash into more soluble forms and thus resulted in increased bioavailability of the nutrients in the vermicomposted series. Among different combinations of fly ash and organic matter, P availability in fly ash due to vermicomposting was significantly higher in the 1:1 fly ash to cow dung treatment compared with the other treatments.     

Growth and elemental accumulation by canola on soil amended with coal fly ash

To explore the agronomic potential of an Australian coal fly ash, we conducted two glasshouse experiments in which we measured chlorophyll fluorescence, CO2 assimilation (A), transpiration, stomatal conductance, biomass accumulation, seed yield, and elemental uptake for canola (Brassica napus) grown on soil amended with an alkaline fly ash. In Experiment 1, application of up to 25 Mg/ha of fly ash increased A and plant weight early in the season before flowering and seed yield by up to 21%. However, at larger rates of ash application A, plant growth, chlorophyll concentration, and yield were all reduced. Increases in early vigor and seed yield were associated with enhanced uptake of phosphorus (P) by the plants treated with fly ash. Fly ash application did not influence accumulation of B, Cu, Mo, or Zn in the stems at any stage of plant growth or in the seed at harvest, except Mo concentration, which was elevated in the seed. Accumulation of these elements was mostly in the leaves, where concentrations of Cu and Mo increased with any amount of ash applied while that of B occurred only with ash applied at 625 Mg/ha. In Experiment 2, fly ash applied at 500 Mg/ha and mixed into the whole 30 cm soil core was detrimental to growth and yield of canola, compared with restricting mixing to 5 or 15 cm depth. In contrast, application of ash at 250 Mg/ha with increasing depth of mixing increased A and seed yield. We concluded that fly ash applied at not more than 25 Mg/ha and mixed into the top 10 to 15 cm of soil is sufficient to obtain yield benefits.     

Long-term evaluation of coal fly ash and mine tailings co-placement: A site-specific study

This study presents the results of a laboratory investigation conducted to evaluate the efficiency of coal fly ash to control the formation of acid mine drainage (AMD) from mine waste. Site-specific materials, coal fly ash from Atikokan Thermal Generating Station and mine tailings from Musselwhite mine, were mixed at different proportions for the investigation of the drainage chemistry and the optimal mix using static testing (acid–base accounting) and kinetic (column) testing. The acid–base accounting (ABA) results indicated that the fly ash possessed strong alkaline (neutralization) potential (NP) and could be used in the management of reactive mine tailings, thus ensuring prevention of AMD in the long-term. Column tests conducted in the laboratory to further investigate long-term performance of fly ash in the neutralization and prevention of acid mine drainage from tailings similarly showed that mixing fly ash with mine tailings reduces dissolution of many heavy metals from tailings by providing alkalinity to the system. It was found that a fly ash to tailings mass ratio equal to or greater than 15% can effectively prevent AMD generation from Musselwhite mine tailings in the co-placement approach.     

Root penetration of sealing layers made of fly ash and sewage sludge

Fly ash and sewage sludge are suggested materials for constructing sealing layers covering mine tailings impoundments. Little is known, however, of their effect on vegetation or resistance to root penetration. We investigate: (i) the ability of different plant species to grow in sealing layers comprising fly ash and sewage sludge, (ii) the impact on plant growth of freshly hardened fly ash compared to aged and leached ash, and (iii) the plant stress response to fly ashes of different properties. A 6-mo greenhouse study using birch (Betula pendula Roth.), Scots pine (Pinus sylvestris L.), Kentucky bluegrass (Poa pratensis L.), and willow (Salix viminalis L.) demonstrated that no roots could grow into a compacted layer consisting only of ash, while a 6:4, ash-sludge mixture admitted roots into the upper part and a 1:9, ash-sludge mixture was totally penetrated (to 15 cm in depth) by roots of willow and Scots pine. Freshly hardened ash prevented root growth more effectively than aged ash did, as was observed in tests using reed canarygrass (Phalaris arundinacea L.) and pea (Pisum sativum L.). Furthermore, extracts of highly alkaline ash were more toxic to pea in a 48-h toxicity test than less alkaline ash was. However, stress responses to diluted ash extracts of lower pH, measured as enzyme capacities in dwarf bean (Phaseolus vulgaris L.), were more related to the metal and ion contents. Root penetration of sealing layers is most effectively prevented if little sewage sludge is added, and if ash of high alkalinity is chosen.     

Fly ash as a liming material for cotton

A field experiment was conducted to determine the effect of fly ash from a coal combustion electric power facility on soil acidity in a cotton (Gossypium hirsutum L.) field. Fresh fly ash was applied to a Bosket fine sandy loam (fine-loamy, mixed, thermic Mollic Hapludalf) soil with an initial soil pH(salt) of 4.8. The fly ash was equivalent to 42 g kg(-1) calcium carbonate with 97% passing through a 60 mesh (U.S. standard) sieve. Fly ash was applied one day before cotton planting in 1999 at 0, 3.4, 6.7, and 10.1 Mg ha(-1). No fly ash was applied in 2000. Within 60 d of fly ash application in 1999, all rates of fly ash significantly increased soil pH above 6.0. Manganese levels in cotton petioles were reduced significantly by 6.7 and 10.1 Mg ha(-1) of fly ash. Soil boron (B) and sodium (Na) concentrations were significantly increased with fly ash. In 1999, B in cotton leaves ranged from 72 to 84 mg kg(-1) in plots with fly ash applications. However, no visual symptoms of B toxicity in plants were observed. In 1999, cotton lint yield decreased on average 12 kg ha(-1) for each Mg of fly ash applied. In 2000, cotton yields were significantly greater for the residual 3.4 and 6.7 Mg fly ash ha(-1) plots than the untreated check. Due to the adverse yield effects measured in the first year following application, fly ash would not be a suitable soil amendment for cotton on this soil at this time.     

The reuse of municipal solid waste incinerator fly ash slag as a cement substitute

The results of the treatment of fly ash from a municipal solid waste incinerator (MSWI) by melting are described, and the safety and the effectiveness of using the slag produced by this melting treatment are studied. The properties of the MSWI fly ash slag were analyzed, to evaluate the feasibility of its reuse as a substitute for part of the cement required in mortar preparation. This MSWI fly ash slag was found to be comprised mainly of SiO₂ and CaO, which can be substituted for up to 20% of the cement content in mortar, without sacrificing the quality of the resultant concrete. In fact, the concrete thus produced has greater compressive strength, 10% higher than that without the substitution. The setting time of the fresh mortar becomes lengthens as increasing amounts of cement are replaced; while the spread flow value increases with the increasing percentage of cement substitution. X-ray diffraction analysis reveals that when the W/C=0.38 and the curing AGE=28 days, the crystal patterns in the mortar samples, prepared with different amounts of cement having been replaced by MSWI fly ash slag are similar. According to the results of the toxic characteristic leaching procedure analysis, MSWI fly ash slag should be classified as general non-hazardous industrial waste, that meets the effluent standard. Therefore, the reuse of MSWI fly ash slag is feasible, and will not result in pollution due to the leaching of heavy metals.     

铁尾矿路用对土壤环境质量影响及安全修复研究

为分析铁尾矿路用对道路沿线土壤环境质量影响的程度,对铁尾矿化学成分及有害物质进行测定,以秦巴山区的山地黄棕壤作为道路建设的耕土环境,把铁尾矿按70%~90%的推荐比例掺入,铁尾矿中的重金属按照最不利的全浸入式扩散进行分析,对黄棕壤中重金属含量超过限制要求的重金属进行安全修复,使铁尾矿道路沿线黄棕壤的重金属含量满足限制要求。结果表明:铁尾矿硫化物含量高达到2.89%,不满足配制混凝土的硫化物限量要求;铁尾矿路用的土壤中重金属Cr最大含量103.24 mg/kg、Cu最大含量116.4 mg/kg,国评标准污染等级均为Ⅱ级,其余重金属元素含量都在国家标准正常范围以内;高生物量的非超富集植物、细菌微生物、城市的污泥、工业粉煤灰(5%粉煤灰+50%尾矿砂+45%黄褐土)能够很好修复重金属Cr、Cu污染的土壤;含钙类物质的钝化剂处置重金属Cr、Cu污染效果好,腐殖酸、凹凸棒土、膨润土可以钝化土壤中的重金属Cu;高生物量非超富集植物、微生物钝化剂联合使用,具有更好的修复效果;当控制铁尾矿掺加比例不超过73%时,铁尾矿道路沿线的土壤重金属含量能够满足国家标准限值的要求。     

A study of the extraction of vanadium and nickel in oil-fired fly ash

Annual production of oil-fired fly ash in Taiwan is approximately 43 000 tons, of this approximately 13 000 tons is electrostatically precipitated, the rest is cyclonically collected. Structurewise, both consist of porous unburned carbon, vanadium and nickel oxide, and water-soluble sulfate. Electrostatically precipitated fly ash contains large amounts of ammonium sulfate. If these ashes are not properly disposed of, they become environmental problems, such as dusting, leakage of acid liquids, and pollution with heavy metals. This paper discusses the experimental extraction of vanadium and nickel from oil-fired fly ash. The results indicated that leaching of oil-fired fly ash in 0.5 N of sulfuric acid led to an extraction of 65% vanadium, 60% nickel, and 42% iron, along with an increase in the concentration of sulfuric acid. When leached in 2 N sodium hydroxide solution, the extraction of vanadium was 80%, and the extraction of nickel was negligible. If leached in an ammonia water, the extraction of nickel increased, along with an increase in the concentration of ammonia in water. When leached with 4 N ammonia water, the extraction of nickel was 60%, the extraction of vanadium was less than that obtainable from leaching in sulfuric acid solution or in sodium hydroxide solution. If electrostatically precipitated fly ash was leached in a solution of 0.25 N ammonia water and 2 N ammonium sulfate, it would yield an extraction of 60% nickel and 8% vanadium—leading to a selective extraction of nickel. This study has established an extraction flowsheet in which fly ash was first leached in an ammoniacal solution containing ammonium sulfate to recover nickel. The leached residues were then leached in an alkaline solution to recover vanadium.     

Utilization of washed MSWI fly ash as partial cement substitute with the addition of dithiocarbamic chelate

The management of the big amount of fly ash as hazardous waste from the municipal solid waste incinerator (MSWI) has encountered many problems in China. In this study, a feasibility research on MSWI fly ash utilization as partial cement substitute in cement mortars was therefore carried out. MSWI fly ash was subjected to washing process to reduce its chlorine content (from 10.16% to 1.28%). Consequently, it was used in cement mortars. Ten percent and 20% replacement of cement by washed ash showed acceptable strength properties. In TCLP and 180-day monolithic tests, the mortars with washed ash presented a little stronger heavy metal leachability, but this fell to the blank level (mortar without washed ash) with the addition of 0.25% chelate. Therefore, this method is proposed as an environment-friendly technology to achieve a satisfactory solution for MSWI fly ash management.     

Properties of several fly ash materials in relation to use as soil amendments

Fly ash samples from five power stations in Western Australia and Queensland, and two soils used for horticulture in Western Australia, were evaluated for a series of physical and chemical properties. Soils were comprised primarily of coarse sand-sized particles, whereas most of the fly ashes were primarily fine sand- and silt-sized particles. Hydraulic conductivities in the fly ashes were 105- to 248-fold slower than in the soils. The water-holding capacities of fly ashes at "field capacity" were three times higher than those of the soils. Extractable P in the fly ashes (except Tarong and Callide) were 20- to 88-fold higher than in the soils. The pH showed considerable variation among the different sources of fly ash, with samples from Muja being the most acidic (pH = 3.8; 1:5 in CaCl2 extract) and from Gladstone the most alkaline (pH = 9.9). The toxicity characteristic leaching procedure (TCLP) values indicate that the potential for release of trace elements from the fly ashes was well below regulatory levels. When applied at sufficient rates (e.g., to achieve 10% w/w in surface layers) to sandy soils, fly ash altered texture and increased water-holding capacity. Depending on the source of fly ash used, such amendments could also provide P and aid nutrient retention by increasing the phosphorus retention index (PRI) and/or cation exchange capacity (CEC). The considerable variability in physical and chemical properties among the fly ash samples evaluated in the present study supports the notion that field trials are essential to the future development of soil amendment strategies making use of any particular source of fly ash.     

Testing the Indicative Value of Magnetic Susceptibility Measurements for Concluding on Site Potentials and Risks Provoked by Fly Ash Deposition

The article presents results of testing the indicative value of magnetic susceptibility for fly ash deposition and its effects on forest site properties. Base saturation and concentrations of Ca and Mg were used as indicators for nutrient pools resulting from fly ash deposition. Concentrations of Fe, Al, Mn, Cd and Black Carbon were used as indicators for risks of leaching. The correlation of magnetic susceptibility with concentrations of nutrient, acidic cations, heavy metals, base saturation and Black Carbon was calculated. Additionally, we tested the suitability of magnetic susceptibility as a parameter in a linear regression based model to predict the concentrations of Ca, Mg, Fe, Al, Mn, Cd and Black Carbon. We were able to show a positive correlation between magnetic susceptibility and the selected indicators. In contrast to previous studies, we were also able to demonstrate the suitability of magnetic susceptibility to predict the size of fly ash deposition influenced nutrient pools mainly for humus layers, especially for Oa horizons. The spatial distribution of magnetic susceptibility showed also a positive correlation with regionalized base saturation. However, because of the data base and other factors impacting the measurement and modeling results, some shortcomings of using a linear regression model must be noted. From these results, we concluded that magnetic susceptibility might be a valuable parameter in a multiple regression based approach, but should not be used alone for predicting effects of fly ash deposition.     

PHOSPHATE IN WATERS: I. REDUCTION USING NORTHERN LIGNITE FLY ASH1

Fly ashes fiom lignite coal fixed steam electric plants contain appreciable amounts of materials that can, in principle, decrease the phosphorus concentration in surface waters. Typical samples of un-weathered fly ash were used to test efficacies of removal of phosphorus from standard phosphate solutions and actual lake water samples. The effects of changing parameters such as contact time, pH, fly ash/water ratios, and solution temperature are presented. Water soluble and insoluble factors in the ash both appear to be reactive constituents. Trials with municipal waste waters showed near quantitative removal of ortho-phosphate.