Study of the use of coal fly ash as an additive to minimise fluoride leaching from FGD gypsum for its disposal

The use of coal fly ash as a fluoride retention additive has been studied as a way of treating flue gas desulphurisation (FGD) gypsum for its disposal in landfills. With this end leaching studies following the standard EN-12457-4 [Characterization of waste- Leaching-Compliance test for leaching of granular waste materials and sludges - Part 4: One stage batch test at a liquid to solid ratio of 10l/kg for materials with particle size below 10mm (without or with size reduction)] have been performed on FGD gypsum samples treated with different proportions of fly ash (0.1-100%). It was found that the fluoride leachable content in FGD gypsum was reduced in the range 1-55%, depending on the fly ash proportion added to FGD gypsum. High levels of fluoride leaching reduction (close to 40%) were achieved even at relatively low fly ash additions (5%). So, low fly ash incorporations assure the characterization of this by-product as a waste acceptable at landfills for non-hazardous wastes according to the Council Decision 2003/33/EC [Council Decision 2003/33/EC of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC] on waste disposal. Furthermore, the effectiveness of the proposed FGD gypsum stabilization method was also studied in column leaching systems, proving its good performance in simulated conditions of disposal. In such conditions a fluoride leaching reduction value slightly higher than 25% was displayed for a fly ash added amount of 5%.     

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.     

The Beginning of Survival

The majority of coal ash generated by electric utilities and power plants of industrial manufacturers is disposed of in landfills; the remainder is used primarily as admixtures in construction materials. Predictive computer models used to assess the environmental impact of disposal or utilization need quantitative information on ash composition and mineralogy. Typically, compositions are reported as elemental concentrations, but this data does not indicate the mineral or glass (amorphous) phases in which the elements are contained. Such phases affect the leaching mechanisms and rates. X-ray diffraction and scanning electron microscopy combined with energy dispersive X-ray spectrometry, common methods for qualitative mineral identification and particle characterization, were used to quantify coal ash mineral compositions. Samples of industrial coal ash from a stoker boiler and a fluidized bed combustion (FBC) system were analyzed and the results were compared to those for a standard sample of coal ash from the National Institute of Standards and Testing (NIST1633a). The results show that the stoker-boiler ash is similar in composition to the NIST sample. Mullite (AI₆Si₂O₁₃) dominates the composition of the crystalline fraction and silica (SiO₂,) dominates the composition of the amorphous fraction. The FBC ash contains the same minerals, but with large proportions of calcium-based phases: anhydrite (CaSO₄), lime (CaO), calcite (CaCO₃), and portlandite (Ga(OH)₂).     

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.     

Mineralogical study and leaching behavior of a stabilized harbor sediment with hydraulic binder

The environmental assessment of potential effects of contaminated harbor sediments stabilized with hydraulic binders and the determination of remediation endpoints require the determination of pollutants leaching potentials. Moreover, little information about the speciation and mobility of inorganic contaminants in these specific solid matrices is available in the literature. The objective of this paper is to investigate the relationship between mineralogy and leachability of contaminants (copper, lead, and zinc) present in a French harbor sediment stabilized with quicklime and Portland cement. Batch equilibrium leaching tests at various pH, chemical analysis of leachates, and mineralogical studies (X-ray diffraction, scanning electron microscopy–energy dispersive spectroscopy, and diffuse reflectance infrared Fourier transform) have been combined in the present investigation. The acid neutralization capacity of the stabilized matrix studied is first controlled by the dissolution of portlandite (pH?~12), followed by the dissolution of C–S–H (pH?~11) and the dissolution of ettringite (pH?~10). Finally, a very high buffering capacity of this stabilized sediment is observed for pH values around 6. This equilibrium is mainly controlled by the dissolution of iron sulfides and carbonate minerals. Consequently, the mobilization of inorganic contaminants as a function of pH remains very low (<0.1 wt%) for pH values above 6 and significantly increases for pH below these values. This research confirms the importance of a combined methodology for the intrinsic characterization of potential mobilization of contaminants in a stabilized sediment and for a better understanding of geochemical processes that affect contaminant fate, transformation, and transport in the subsurface environment.     

Determining the experimental leachability of copper, lead, and zinc in a harbor sediment and modeling

The potential leaching of pollutants present in harbor sediments has to be evaluated in order to choose the best practices for managing them. Little is known about the speciation and mobility of heavy metals in these specific solid materials. The objective of this paper is to determine and model the leachability of copper, lead, and zinc present in harbor sediments in order to obtain essential new data. The mobility of inorganic contaminants in a polluted harbor sediment collected in France was investigated as a function of physicochemical conditions. The investigation relied mainly on the use of leaching tests performed in combination with mineralogical analysis and thermodynamic modeling using PHREEQC. The modeling phase was dedicated to both confirm the hypothesis formulated to explain the experimental results and improve the determination of the main physico-chemical parameters governing mobility. The experimental results and modeling showed that the release of copper, lead, and zinc is very low with deionized water which is due to the stability of the associated solid phases (organic matter, carbonate minerals, and/or iron sulfides) at natural slightly basic conditions. However, increased mobilization is observed under pH values below 6.0 and above 10.0. This methodology helped to consistently obtain the geochemical parameters governing the mobility of the contaminants studied.     

Greenhouse gas emission potential of the municipal solid waste disposal sites in Thailand

Open dumping and landfilling are the prevalent solid waste disposal practices in Thailand. Surveys on the disposal sites revealed the presence of 95 landfills and 330 open dumps. Methane emission potential at these sites was estimated by three methods. Results of the Intergovernmental Panel on Climate Change (IPCC) method, Landfill Gas Emission model (LandGEM), and closed flux chamber technique were compared. The methane emission potential of 366 Gg/yr using the IPCC method was higher than the estimations of the LandGEM and closed flux chamber method of 115 Gg/yr and 103 Gg/yr, respectively. An understanding of the methane emission potential initiated the analysis of upgrading the open dumps into landfills, adding landfills to meet the future needs and utilization of landfill gases. Upgrading the open dumps to landfills increased the methane emission rates and their utilization potential. Approximately 20 additional landfills may be required to meet future demands. Landfill gas (LFG) utilization appears to be feasible in the large-scale landfills.     

固硫型煤渣烧制水泥熟料的研究初探

发展固硫型煤工业是治理煤烟型大气污染及减少二氧化硫对大气污染的有效途径。燃烧固硫型煤将产生大量固硫煤渣,对环境构成新的威胁。本文从实验探索的角度,研究开发利用固硫渣的途径。实验中对固硫渣做了化学全分析,用Ｘ－射线粉末衍射法（ＸＲＰＤ）对固硫渣及其加入一定量的添加剂后的煅烧产物进行物相鉴定,证实在一定的条件下固硫渣可以烧制成硫铝酸盐水泥熟料     

Dimension reduction and source identification for multispecies groundwater contamination

Assessment of chemical contamination at large industrial complexes with long and sometimes unknown histories of operation represents a challenging environmental problem. The spatial and temporal complexity of the contaminant may be due to changes in production processes, differences in the chemical transport, and the physical heterogeneity of the soil and aquifer materials. Traditional mapping techniques are of limited value for sites where dozens of chemicals with diverse transport characteristics may be scattered over large spatial areas without documentation of disposal histories. In this context, a site with a long and largely undocumented disposal history of shallow groundwater contamination is examined using principal component analysis (PCA). The dominant chemical groups and chemical "modes" at the site were identified. PCA results indicate that five primary and three transition chemical groups can be identified in the space of the first three eigenvectors of the correlation matrix, which account for 61% of the total variance of the data. These groups represent a significant reduction in the dimension of the original data (116 chemicals). It is shown that each group represents a class of chemicals with similar chemo-dynamic properties and/or environmental response. Finally, the groups are mapped back onto the site map to infer delineation of contaminant source areas for each class of compounds. The approach serves as a preliminary step in subsurface characterization, and a data reduction strategy for source identification, subsurface modeling and remediation planning.     

Emission Characteristics of Granulated Fuel Produced from Sewage Sludge and Coal Slime

Abstract

The neutralization of wastewater treatment residues is an issue for many countries. The European Union (EU) legal regulations have limited the use of the residues in agriculture and implemented a ban for their disposal. Therefore, urgent action should be taken to find solutions for the safe disposal of sewage sludge. The problem refers in particular to the new EU member countries, including Poland, where one can now observe an intensive development of sewage system networks and new sewage treatment plants. At the same time, these countries have few installations for thermal sewage sludge utilization (e.g., there is only one installation of that type in Poland). Simultaneously, there are many coal-fired mechanical stoker-fired boilers in some of these countries. This paper presents suggestions for the production of granulated fuel from sewage sludge and coal slime. Additionally, among others, lime was added to the fuel to decrease the sulfur compounds emission. Results are presented of research on fuel with two average grain diameters (～15 and 35 mm). The fuel with such diameters is adapted to the requirements of the combustion process taking place in a stokerfired boiler. The research was aimed at identifying the behavior of the burning fuel, with special attention paid to its emission properties (e.g., to the emissions of oxides of nitrogen [NO_x], sulfur dioxide [SO₂], and carbon mon-oxide [CO], among others). The concentration and emission values were compared with similar results obtained while burning hard coal. The combustion process was carried out in a laboratory stand where realization of the large-scale tests is possible. The laboratory stand used made simulation possible for a wide range of burning processes in mechanical stoker-fired boilers.     

Emission characteristics of granulated fuel produced from sewage sludge and coal slime

The neutralization of wastewater treatment residues is an issue for many countries. The European Union (EU) legal regulations have limited the use of the residues in agriculture and implemented a ban for their disposal. Therefore, urgent action should be taken to find solutions for the safe disposal of sewage sludge. The problem refers in particular to the new EU member countries, including Poland, where one can now observe an intensive development of sewage system networks and new sewage treatment plants. At the same time, these countries have few installations for thermal sewage sludge utilization (e.g., there is only one installation of that type in Poland). Simultaneously, there are many coal-fired mechanical stoker-fired boilers in some of these countries. This paper presents suggestions for the production of granulated fuel from sewage sludge and coal slime. Additionally, among others, lime was added to the fuel to decrease the sulfur compounds emission. Results are presented of research on fuel with two average grain diameters (approximately 15 and 35 mm). The fuel with such diameters is adapted to the requirements of the combustion process taking place in a stoker-fired boiler. The research was aimed at identifying the behavior of the burning fuel, with special attention paid to its emission properties (e.g., to the emissions of oxides of nitrogen [NO(x)], sulfur dioxide [SO2], and carbon monoxide [CO], among others). The concentration and emission values were compared with similar results obtained while burning hard coal. The combustion process was carried out in a laboratory stand where realization of the large-scale tests is possible. The laboratory stand used made simulation possible for a wide range of burning processes in mechanical stoker-fired boilers.     

Characterisation of dust material emitted during harbour operations (HADA Project)

Harbour activities such as loading, unloading and transport of dusty loose materials may be an important source of atmospheric particulate matter (PM). Depending on the materials, the type of operation and the meteorological scenarios, these activities may have an impact on the levels of ambient air PM around harbour areas. Moreover, air quality at harbours may be affected by nearby urban and industrial emissions. The aim of this work is to compile an inventory of the main characteristics (chemical, morphological, mineralogical and grain size parameters) of the bulk cargo materials and of the material emitted during different port operations for possible use as tracers of the fugitive PM emission sources. For all cases, the tracer characteristics determined for each bulk material were also identified in the corresponding PM material emitted. This inventory could assist the harbour authorities to identify the origin of high PM events recorded by air quality monitoring networks in harbour areas, and could also help modellers to predict the impact of harbour activities on ambient PM levels. The harbour of Tarragona (north-east Spain) was selected for this study given the high volume of solids in bulk handled. To this end, 12 handling operations of selected materials (clinker, phosphate, pyrite ash, Mn mineral, fine Si–Mn, coke (coal), bituminous coal, tapioca, soybean, alfalfa, corn, andalusite) were selected for the characterisation of suspended and deposited PM. In spite of the coarse grain size distribution of these bulk cargo materials, with a very low % in the fraction <10 μm, manipulation of these materials during harbour operations may result in high emissions of PM10 with relatively high levels of potential toxic elements. Furthermore, ambient PM10 in the area with the highest traffic density of the harbour was also sampled and characterised.     

村镇小型生活垃圾热处理炉底渣的理化特性

小型垃圾热处理设备可实现就地处置,节约运输成本,目前在中国山区、丘陵地带的村镇得到广泛应用.为了解村镇小型生活垃圾热处理炉底渣的理化特性及其影响因素,对中国云南、贵州、安徽村镇实际运行的小型生活垃圾热处理设备产生的底渣进行取样,分析其热灼减率、物理组成、化学组成、晶相组成、重金属含量和浸出特性,探讨处理工艺、地域及季节...     

Enrichment of trace elements in the clay size fraction of mining soils

Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps.     

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.     

Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site

In this paper the results of a recent characterization of Rio Piscinas (SW of Sardinia, Italy) hydrological basin are reported. In such area (about 50 km2), previous mining activities caused a serious heavy metal contamination of surface waters, groundwater, soils and biota. Acid mine drainage phenomena were observed in the area. The main sources of contamination are the tailings stored in mine tunnels and abandoned along fluvial banks. A methodological approach was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments samples were collected. XRD analyses were performed for mineralogical characterization, while acid digestion was carried out for determining metal contents. Batch sequential leaching tests were performed in order to assess metal mobility. Also groundwater and stream water were sampled in specific locations and suitably characterized. All information collected allowed the understanding of the effect of tailings on water contamination, thus contributing to the qualitative prediction of pollution evolution on the basis of metal mobility. Finally, a potential remediation strategy of stream water is proposed.     

Stabilization of FGD gypsum for its disposal in landfills using amorphous aluminium oxide as a fluoride retention additive

The applicability of amorphous aluminium oxide as a fluoride retention additive to flue gas desulphurisation (FGD) gypsum was studied as a way of stabilizing this by-product for its disposal in landfills. Using a batch method the sorption behaviour of amorphous aluminium oxide was evaluated at the pH (about 6.5) and background electrolyte conditions (high chloride and sulphate concentrations) found in FGD gypsum leachates. It was found that fluoride sorption on amorphous aluminium oxide was a very fast process with equilibrium attained within the first half an hour of interaction. The sorption process was well described by the Langmuir model, offering a maximum fluoride sorption capacity of 61.7 mg g(-1). Fluoride sorption was unaffected by chloride co-existing ions, while slightly decreased (about 20%) by competing sulphate ions. The use of amorphous aluminium oxide in the stabilization of FGD gypsum proved to greatly decreased its fluoride leachable content (in the range 5-75% for amorphous aluminium oxide doses of 0.1-2%, as determined by the European standard EN 12457-4 [EN-12457-4 Characterization of waste-leaching-compliance test for leaching of granular waste materials and sludges-Part 4: one stage batch test at a liquid to solid ratio of 10 l/kg for materials with particle size below 10mm (without or with size reduction)]), assuring the characterization of this by-product as a waste acceptable at landfills of non-hazardous wastes according to the Council Decision 2003/33/EC [Council Decision 2003/33/EC of 19 December 2002. Establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC] on landfill of wastes. Furthermore, as derived from column leaching studies, the proposed stabilization system proved to be highly effective in simulated conditions of disposal, displaying a fluoride leaching reduction value about 81% for an amorphous aluminium oxide added amount of 2%.     

Mobility of heavy metals associated with the natural weathering of coal mine spoils

Knowledge of chemical mobility of heavy metals is fundamental to understanding their toxicity, bioavailability, and geochemical behavior. In this paper, two different methods, i.e. mineralogical means and sequential extractions, were employed to analyze the total contents, existing states, and chemical forms of heavy metals in coal mine spoils. The results demonstrate that the mobility of heavy metals in coal mine spoils depends not only on their existing states and the stability of their host minerals but also on the properties of the coal mine spoils. In the process of coal mine spoils-water interaction, sulfides that contain heavy metals first break down and release metals, which are then adsorbed and complexed by the iron oxyhydroxide colloid resulting from pyrite oxidization and organic matter. During the natural weathering of coal mine spoils, only a small fraction of these metals are released to the environment, and most of them still remains in the residual material.     

Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium

The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium.