Impact of the use of waste on trace element concentrations in cement and concrete.

The results of model calculations carried out to identify and quantify the input pathways of trace elements into cement and concrete and to estimate the extent to which trace element concentrations in cement may change due to waste utilization are presented. As expected, primary raw materials represented the most important input pathway for trace elements into cement, but the contribution from wastes was not negligible. The use of waste led to a slight increase of the concentrations of cadmium, antimony and zinc in cement. For cobalt, lead and vanadium, this increase was less distinct and for all other trace elements considered, the effect of the use of wastes on trace element concentrations in cement could not be demonstrated clearly. The trace element content of concrete was governed by the aggregates for most elements considered. However, for arsenic, cadmium, lead and zinc, both cement and the additive coal fly ash contributed noticeably to the total trace element concentration in the concrete.     

煤及煤矸石中砷的释放

研究了煤及煤矸石中砷的释放特征。采用XRD技术对煤样中的主要矿物成分进行了分析。表征结果显示,煤样中的主要矿物组成为碳酸盐矿物、硅酸盐矿物,以及一定量的SiO2、TiO2、硫化物矿物和硫酸盐矿物。实验结果表明：煤中砷的赋存形态主要以残渣态和硫化物结合态为主;在煤燃烧过程中,当燃烧温度为1 000 ℃时,1号矿井的煤样燃烧后灰渣中的砷含量为1.385 μg/g,砷的释放率为40.10%,2号矿井的煤样燃烧后灰渣中的砷含量为1.531 μg/g,砷的释放率为56.04%;在煤矸石的淋溶过程中,在淋溶液体积为100 mL的条件下,当淋溶液pH为5时淋出液中的ρ（砷）为19.27 μg/L,当淋溶液pH为7时淋出液中的ρ（砷）为7.78 μg/L。     

PHYSICO-CHEMICAL CHARACTERIZATION AND LEACHING OF DESULPHURIZATION COAL FLY ASH

Fly ash produced by coal combustion using two types of desulphurization process were studied: a conventional pulverized coal boiler equipped with lime injection (PCL ash), and a circulating fluidized bed combustion boiler with limestone injection (CFBC ash). The ashes were characterized completely: granulometry, morphology, mineralogy, chemical composition and behaviour to water contact. Both PCL ash and CFBC ash present similar features: fine granulometry, presence of anhydrite phase and sulphate content. However, PCL ash also shows lots of spherical particles, unlike CFBC ash, and a much higher lime content, due to the lower desulphurization rate in PC boilers. Unlike CFBC ash, most of the trace elements in PCL ash show an inverse concentration–particle size dependence. Leachates obtained from both samples are rich in soluble salts [CaSO₄and Ca(OH)₂] and arsenic and selenium are prevented from solubilizing by high lime content. In wetted PCL ash, the formation of ettringite crystals stabilizes calcium and sulphate ions. Simultaneously, arsenate, selenate and chromate anions are trapped in the crystal. CFBC ash does not really harden because the lime content is too low. However, the leached selenium concentration is cut down in wetted CFBC ash samples.     

Arsenic and thallium data in environmental samples: Fact or fiction?

Matrix effects may increasingly lead to erroneous environmental decisions as regulatory limits or risk‐based concentrations of concern for trace metals move lower toward the limits of analytical detection. A U.S. Environmental Protection Agency Office of Technical Standards Alert estimated that environmental data reported using inductively coupled plasma spectrometry (ICP‐AES) has a false‐positive rate for thallium of 99.9 percent and for arsenic of 25 to 50 percent. Although this does not seem to be widely known in the environmental community, using three case studies, this article presents data in environmental samples that demonstrate severe matrix effects on the accuracy of arsenic and thallium results. Case Study 1 involves soil results with concentrations that approached or exceeded the applicable regulatory soil cleanup objectives of 13 mg/kg for arsenic and 2 mg/kg for thallium. Reanalysis using ICP coupled with a mass spectrometer (ICP‐MS) confirmed all thallium results were false positives and all arsenic results were biased high, concluding no action was required for soil remediation. Case Study 2 involves groundwater results for thallium at a Superfund site, where thallium was detected in groundwater up to 21.6 μ g/L using ICP‐AES. Reanalysis by ICP‐MS reported thallium as nondetect below the applicable regulatory level in all samples. ICP‐MS is usually a more definitive and accurate method of analysis compared to ICP‐AES; however, this is not always the case, as we demonstrate in Case Study 3, using data from groundwater samples at an industrial site. Through a weight‐of‐evidence approach, it is demonstrated that although method quality control results were acceptable, interferences in some groundwater samples caused biased high results for arsenic using ICP‐MS, which were significantly lower when reanalyzed using hydride generation atomic fluorescence spectrometry. Causes of these interference effects and conclusions from the three case studies to obtain accurate metal data for site assessment, risk characterization, and remedy selection are discussed. © 2010 Wiley Periodicals, Inc.     

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

Heavy metal content in soil reclaimed from a municipal solid waste landfill

Residues reclaimed from a municipal solid waste (MSW) landfill were characterized for the concentrations of a number of heavy metals. The residue fractions analyzed included a fine fraction (<0.425 mm), an intermediate fraction (>0.425 and <6.3 mm) and a fraction consisting of paper products that could ultimately degrade to a smaller size. The intermediate fraction appeared to be organic in nature, while the fine fraction was more soil-like. In general, the metal concentrations were greatest in the intermediate fraction and lowest in the fine fraction. The effect of sample age on the elemental content was also investigated. The concentrations of several elements were greater in older samples (sample approximately 8 years in age) when compared to newer samples (sample approximately 3 years in age). Limitations associated with the land application of residual soil (composed of the fine and intermediate fractions) were assessed by comparing measured concentrations to regulatory threshold values. In general, most metal concentrations were below regulatory thresholds for use in unrestricted settings. At the concentrations measured, however, several elements might limit reuse options, depending on which regulatory threshold serves as a benchmark. Elevated concentrations of arsenic presented the greatest limitation with respect to common US thresholds while elevated cadmium concentrations presented the greatest limitation when compared to UK thresholds. The source of the arsenic was determined to be the waste, not the cover soil.     

Chemical changes in different types of coal ash during prolonged,large scale,contact with seawater

In this study, we followed the chemical changes occurring in coal ash exposed to prolonged (300 days), large scale, contact with running seawater. Four major components (Al, Ca, Mg, Fe) and seven minor and trace elements (Cd, Cr, Cu, Mn, Zn, Pb, Hg) were measured in four coal ash types: fly and bottom ash freshly obtained from coal-fired power plant, and old ash (crushed and blocks) recovered from the sea after 3-5 years contact with seawater. Changes occurred in the chemical composition of the coal ash along the experiment: Fe increased in fresh ash, Al increased in old ash and Ca increased in all ash types except old ash blocks. Cu and Hg decreased in fresh fly ash while Cr increased, Cd decreased in all ash types except bottom ash, and Mn decreased in bottom ash. Most of the changes occurred in the fresh fly ash, and not in the old ash, indicating equilibrium after prior exposure to seawater. In addition, more changes occurred in fresh fly ash than in bottom ash, emphasizing the differences between the two ash types. While the changes in the concentrations of the major elements may be an indication of the integrity of the ash matrix, the only elements of environmental significance released to the environment were Hg and Cd. However, calculated seawater concentrations were much lower than seawater quality criteria and therefore the coal ash was considered suitable for marine applications concerning seawater quality.     

Characterization of air emissions and residual ash from open burning of electronic wastes during simulated rudimentary recycling operations

Air emissions and residual ash samples were collected and analyzed during experiments of open, uncontrolled combustion of electronic waste (e-waste), simulating practices associated with rudimentary e-waste recycling operations. Circuit boards and insulated wires were handled separately to simulate processes associated with metal recovery. The average emissions of polychlorinated dibenzodioxins and dibenzofurans (PCDD/PCDFs) were 92 ng toxic equivalency (TEQ)/kg [n = 2, relative standard deviation (RSD) = 98%] and 11 900 ng TEQ/kg (n = 3, RSD = 50%) of the initial mass of the circuit boards and insulated wire, respectively. The value for the insulated wire is about 100 times higher than that for backyard barrel burning of domestic waste. The emission concentrations of polybrominated dibenzodioxins and dibenzofurans (PBDD/PBDFs) from the combustion of circuit boards were 100 times higher than for their polychlorinated counterparts. Particulate matter (PM) sampling of the fly ash emissions indicated PM emission factors of approximately 15 and 17 g/kg of the initial mass for the circuit boards and insulated wire, respectively. Fly ash samples from both types of e-waste contained considerable amounts of several metallic elements and halogens; lead concentrations were more than 200 times the United States regulatory limits for municipal waste combustors and 20 times those for secondary lead smelters. Leaching tests of the residual bottom ash showed that lead concentrations exceeded U.S. Environmental Protection Agency landfill limits, designating this ash as a hazardous waste.     

Evaluation of bioaccessible arsenic in fly ash by an in vitro method and influence of particle-size fraction on arsenic distribution

A huge amount of fly ash is produced by coal-fired power plants every year in China and leads to increasing environmental problems associated with disposal and treatment. It will be very helpful for the study of management and disposal of solid waste to understand the bioaccessibility and environmental behaviors of arsenic in fly ash. In this paper, an in vitro physiologically-based extraction test was applied to estimate the solubility and bioaccessibility of arsenic in fly ash in the human gastrointestinal tract. The fly ash samples were sieved into different fractions with different particle sizes (100–60, 60–10, 10–2.5, <2.5 μm). The influence of particle size on both total and bioaccessible arsenic was also investigated. The results demonstrated that arsenic concentrations in fly ash were significantly correlated with particle size. The proportion of bioaccessible arsenic (gastric and intestinal arsenic) accounting for the total arsenic was in the range of 36–67 %. The statistic analysis indicated that total arsenic in fly ash was linearly correlated with bioaccessible arsenic. The results illustrated that bioaccessible arsenic was dominated by total arsenic.     

Metal Contamination of the Natural Environment in Norway from Long Range Atmospheric Transport

Long range atmospheric transport is the most important sourceof contamination to the natural environment in Norway with manyheavy metals. Investigations based on aerosol studies, bulkdeposition measurements and moss analysis show that airborne transport from other parts of Europe is the major mode for supplyof vanadium, zinc, arsenic, selenium, molybdenum, cadmium, tin,antimony, tellurium, thallium, lead, and bismuth, whereas metalssuch as chromium, nickel, and copper are mainly derived from point sources within Norway and in northwestern Russia close tothe Norwegian border. Elements associated with long range transport show substantial enrichment in the humus horizon of natural soils in southern Norway, sometimes to levels suspected to cause effects on soil microbial processes. E.g. lead concentration values of 150–200 ppm are observed in the mostcontaminated areas in the south as compared to about 5 ppm inthe far north. Elements such as lead and cadmium also show enrichment in some terrestrial food chains. These elements alsoshow considerably elevated levels over background concentrationsin the water and sediment of small lakes in the southern part ofthe country. Retrospective studies based on ombrogenous peatcores indicate that long range transport has been a significantsource of heavy metal contamination in southern Norway for thelast couple of centuries. The deposition of most heavy metals inNorway has been considerably reduced over the last 20 yr, withthe exception of contributions in the north from Russian smelters.     

Behavior of As,Cd, Co,Cr, Cu,Pb, Ni,and Zn at the soil/plant interface around an uncontrolled landfill (Casablanca,Morocco)

The present work undertaken in the environmental context aims to study the distribution of heavy metals in plants that grow naturally around uncontrolled landfills. The study's goal was to identify plants that can be used to remediate contaminated soils. For this purpose, 14 plants species and their rhizospheric soil samples were collected and analyzed for arsenic, cadmium, cobalt, chromium, copper, lead, nickel, and zinc by inductively coupled plasma‐atomic emission spectrometry. The results showed the presence of elevated metal concentrations in soil, many exceeding the regulatory values, and that many species exhibited an ability to accumulate multiple metals in their shoots and roots without sustaining toxicity. This was confirmed by bioconcentration and translocation factors generally higher than 1.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.     

Deposition and Fate of Lead in a Forested Catchment, Lesni Potok, Central Czech Republic

The deposition of trace elements and their fate in a forest ecosystemhas been monitored at the experimental site, Lesni Potok catchment (LP), with granite bedrock. The catchment is located 30 km ESE from Prague. Annual bulk Pb-deposition flux F_Pb was 3.41 kg km^-2 a^-1 in 1994 and gradually decreased to 0.49 kg km^-2 a^-1 in 2001. The decrease is comparable with those observed in Germany and in the U.S.A. in the 1970s and 1980s. The total sales ban of leaded gasoline in the Czech Republic since January 2001 was accompanied by a pronounced decrease of F_Pb in a single year. The residual Pb-deposition flux is assigned to both the long-range transport of fine-grained vehicular lead aerosol (with a long residence time in the atmosphere) and to theemissions from power plant boilers burning lignite mined in the Czech northwest coal basin. The F_Pb of lead correlates stronglywith those of As, Cd, Cu, Zn and Be, the typical metals in coal fly ash, at two monitored sites. Topsoil horizons contain elevated concentrations of Pb (53–67 mg kg^-1), which are of anthropogenicorigin. Soils in the riparian areas contain increased concentrations of Pb when compared to soils on the hillslope areas. Significant amounts of Pb were found on a stream substrate and Fe-precipitate sampled from the stream. Low concentrations of Pb in bark and bole wood suggest that the uptake of Pb by vegetation is negligible. The very small surface water outputs (average of 0.002 kg km^-2 a^-1) compared to inputs (average of 1.890 kg km^-2 a^-1) from the LP catchment indicate an ongoing accumulation of Pb in a forested landscape.     

Stabilization/solidification of ashes in clays used in the manufacturing of ceramic bricks.

This paper presents the results of the lixiviation of metals from different mixtures of fly and bottom ashes that have been stabilized and solidified in clays used in the manufacture of bricks. The ashes used for this study were obtained from a Hoffmann-type brick furnace adapted for the incineration of municipal solid waste during the manufacturing of ceramic bricks. The ashes were stabilized in clay in different proportions of clay:ash mix (99:1, 95:5, 90:10, 80:20 and 60:40). Such mixes were used to manufacture bricks that were calcined at a temperature ranging from 50 to 1100 degrees C. The clay, ashes and manufactured bricks were characterized using X-ray diffraction, fluorescent X-ray, thermogravimetry, differential thermal analysis, atomic absorption spectroscopy and scanning electronic microscopy. In addition, toxicity characteristic leaching procedure lixiviation tests were performed according to the EPA 1311 method for the determination of heavy metals. The results showed an affinity between clay and ash, and also that the bricks manufactured with these mixtures present low lixiviation levels. The tests also showed the highest decrease in the concentration of arsenic, nickel, chromium, zinc and silver for 99:1 mixtures. The 95:5 mixture was found to be the most favourable for the stabilization (greater concentration decrease) of lead and cadmium. Selenium was the metal with the lowest concentration change whereas arsenic, nickel, chromium, zinc and cadmium showed the greatest concentration change in all mixtures, with the exception of cadmium in the mixture 99:1.     

Release Of Some Trace Elements From Sluiced Fly Ash On Acidic Soils With Particular Reference To Boron

The purpose of this study was to examine the relationship between the concentration of boron (B) and some other selected trace elements in soil solution as effected by hydrogen ion activity within the normal pH range for acidic soils commonly amended with agricultural limestone and, alternatively, alkaline fly ash. Sluiced alkaline fly ash was applied to an acidic, clay textured soil at rates equivalent to 0, 42, 84, 125 and 167 tonne ha^-1 based on the soil lime requirement. After wheat was grown and harvested the soil-ash mixtures were maintained at field capacity moisture content for an additional 4 months before pore water samples were extracted by immiscible displacement. The total concentrations of Co, Cr, Fe, V and Zn in the ash treated soils increased by < 10% at the highest application rate of ash, the content of Cu was increased by 13% and B by 38%. Only the concentration of boron increased appreciably in the pore water extracts. Release of B from the ash was correlated with the solubility behaviour of Ca and Mg, and not with the dissolution of glass phases in the ash. Speciation and adsorption calculations for the extracts were carried out using the program MINTEQ. Common Ca, Mg and Na borate minerals were undersaturated with respect to the equilibrated solutions. Application of the constant capacitance model to the adsorption of B on mineral surfaces suggested that adsorption had little effect on total dissolved B at pH values below 6.0. Predicted concentrations of B in solutions, equilibrated with calcite in a subsurface horizon, were up to 10.6 mg dm^-3; more than double the recommended maximum concentration for B (5mg dm^-3) in potable water in Ontario.     

Enrichment of elements in industrial waste incineration bottom ashes obtained from three different types of incinerators,as studied by ICP-AES and ICP-MS

The elemental composition of the industrial waste incineration bottom ash (IWIBA) samples collected from three different types of incinerator with different kinds of wastes were compared. The major-to-ultratrace elements in the IWIBA samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from milligrams per gram to submicrograms per gram could be determined with relative standard deviations of less than 5%. The IWIBA sample from petrochemical wastes contained lower concentrations of the elements, because fewer mineral constituents were contained in the input waste materials. On the contrary, the elemental concentrations in the IWIBA sample from industrial solid wastes provided the highest values for most elements, while the elemental compositions of the IWIBA sample from food wastes were similar to those of municipal solid waste incineration bottom ash. In addition, it was found from the analytical results that the levels of various heavy metals such as Cr, Mn, Fe, Ni, Cu, As, Zr, Mo, Sb, Ba, and Pb were higher in the IWIBA samples than in municipal solid waste incineration bottom ash. The enrichment factors of the elements in the IWIBA samples were estimated from the analytical results to compare the elemental distributions in incineration bottom ashes in relation to their mining influence factors, which are the indices for human use of the elements.     

Bio fuel ash in a road construction: impact on soil solution chemistry

Limited natural resources and landfill space, as well as increasing amounts of ash produced from incineration of bio fuel and municipal solid waste, have created a demand for useful applications of ash, of which road construction is one application. Along national road 90, situated about 20 km west of Sollefteå in the middle of Sweden, an experiment road was constructed with a 40 cm bio fuel ash layer. The environmental impact of the ash layer was evaluated from soil solutions obtained by centrifugation of soil samples taken on four occasions during 2001–2003. Soil samples were taken in the ash layer, below the ash layer at two depths in the road and in the ditch. In the soil solutions, pH, conductivity, dissolved organic carbon (DOC) and the total concentration of cations (metals) and anions were determined. Two years after the application of the ash layers in the test road, the concentrations in the ash layer of K, SO₄, Zn, and Hg had increased significantly while the concentration of Se, Mo and Cd had decreased significantly. Below the ash layer in the road an initial increase of pH was observed and the concentrations of K, SO₄, Se, Mo and Cd increased significantly, while the concentrations of Cu and Hg decreased significantly in the road and also in the ditch. Cd was the element showing a potential risk of contamination of the groundwater. The concentrations of Ca in the ash layer indicated an ongoing hardening, which is important for the leaching rate and the strength of the road construction.     

Leaching behavior of some demolition wastes

Demolition wastes may be used in different civil engineering applications as road constructions, concrete, and embankments or landfill. Regardless its application, leaching tests of the waste should be carried out to assess concentrations of pollutants. Concrete, brick and mixture of concrete, bricks, tiles and ceramics wastes were subject to percolation test—CEN/TS 14405, and batch test—SR EN 12457. The leachates were analyzed with respect to concentration of inorganic elements—arsenic, barium, cadmium, chromium, copper, mercury, molybdenum, nickel, lead, selenium, zinc, fluoride, chloride and sulfate, and organic compounds (phenol index). The concentrations of elements in leachates were compared with the limit values of European regulation for the acceptance of inert wastes at landfills. Generally, the releases of inorganic species in leachates were below limits values. Some waste leachates obtained by percolation and batch test had high values for phenol index.     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N₂ atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb₂OCl₂ or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb₂OCl₂ were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.