Ashes from fluidized bed combustion of residual forest biomass: recycling to soil as a viable management option

Although bottom ash (BA) [or mixtures of bottom and fly ash (FA)] from clean biomass fuels is currently used as liming agent, additive for compost, and fertilizer on agricultural and forest soils in certain European countries, in several other countries most of the ashes are currently disposed in landfills. This is due to both a lack of a proper classification of the materials and of regulatory barriers.Chemical characterization including analysis of an array of potentially toxic elements (PTEs) proved that over 100,000 tons of BA currently landfilled every year in Portugal actually complied with legal limits for PTEs for soil fertilizers applied in other countries. Pot experiments were conducted, testing three dosages of BA and FA (1, 2.5, and 5%, in weight) in three mining soils with different properties. Additions of ash materials to soils led to an increase in the pore water pH relative to control pots (0% of ash added) and had a clear impact on DOC and on the solubilization of both macro- and micronutrients (notably Cu).The results from the case study using BA and FA from a Portuguese biomass thermal power plant demonstrate that it is imperative to further develop a regulatory framework to alleviate technological and environmental barriers for biomass ash utilization as raw material for fertilizers and/or soil liming agent, in accordance with the goals of the circular economy. A more harmonized view on how to assess the merits and risks of the re-use of these materials is also needed.     

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.     

Wood pellet fly ash and bottom ash as an effective liming agent and nutrient source for rye grass (Lolium perenne L.) and oats (Avena sativa)

Fly ash (FA) and bottom ash (BA) from a softwood pellet boiler were characterized and evaluated as soil amendments. In a greenhouse study, two plant species (rye grass, Lolium perenne L. and oats, Avena sativa) were grown in three different treatments (1% FA, 1% BA, non-amended control) of a silty loam soil. Total concentrations of plant nutrients Ca, K, Mg, P and Zn in both ashes were elevated compared to conventional wood ash. Concentrations of Cd, Cr, Pb, Se and Zn were found to be elevated in the FA relative to BA and the non-amended soil. At 28 d, oat above-ground biomass was found to be significantly greater in soil amended with FA. Potassium and Mo plant tissue concentrations were significantly increased by addition of either ash, and FA significantly increased Zn tissue concentrations. Cadmium and Hg tissue concentrations were elevated in some cases. As soil amendments, either pellet ash is an effective liming agent and nutrient source, but high concentrations of Cd and Zn in FA may preclude its use as an agricultural soil amendment in some jurisdictions. Lower ash application rates than those used in this study (i.e. <1%) may still provide sufficient nutrients and effective neutralization of soil acidity.     

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.     

Filtration Properties of Fly Ash from Fluidized Bed Combustion

Some of the features of the fluidized-bed combustion (FBC) process have a direct bearing on the particulate properties that most strongly influence filtering pressure drop. A laboratory program was conducted to experimentally determine the relative pressure drop characteristics of ashes from the TVA-EPRI 20-MW bubbling bed, atmospheric pressure FBC (AFBC) pilot plant and six pulverized-coal combustion (PC) units. The combined influences of measured particle and dust cake properties on filtering pressure drop were estimated with existing filtration theories. These theories predict a higher pressure drop for a dust cake produced with the AFBC ash than for one consisting of any of the PC ashes. Laboratory measurements were made of the flow resistance of idealized, simulated dust cakes to confirm these predictions. Field operating data from the fabric filters collecting some of the tested ashes were available to validate the laboratory results. The laboratory and field data show relatively good agreement. The AFBC ash must be treated as a special case for fabric filters, and careful selection of cleaning method and fabric must be made to minimize the inherently high pressure drop characteristics of this ash.     

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.     

Dioxin-like potencies and extractable organohalogens (EOX) in medical, municipal and domestic waste incinerator ashes in Japan

Ash samples collected from medical, municipal and small-scale domestic incinerators in Japan were tested for dioxin-like activity using bioassay technique (ethoxyresorufin-O-deethylase: EROD assay) and for extractable organohalogens (EOX) using instrumental neutron activation analysis in order to estimate potential toxicity and responsible chemicals in those samples. Crude extracts and fractions cleaned-up for dioxin analysis from the samples were used for the analysis. The ranges of dioxins in the ashes were between 2.23 and 12.29 ng TEQ/g (dry weight). Relative potency ranges estimated by EROD assay in the medical incinerator ashes were 3.8-17.6 times higher than the results of conventional chemical analysis. EOX analysis suggested that ash samples contained plenty of organochlorine compounds apart from chlorinated dioxins. In addition, medical waste incinerator ashes were considered to have relatively higher amount of organoiodine compounds. In the cleaned-up fractions, bioassay potency ranges were lower than those in the crude extracts. However, some samples still exhibited higher potency than expected from chemical analysis. Though some polycyclic aromatic hydrocarbons were found in the fractions, the amounts were relatively low (0.39-10.56 ng/g). The results imply that some bioactive organohalogens that cannot be detected in the conventional chemical analysis might have potential for dioxin-like toxicity, and contribute to higher bioassay activities. The combination of the chemical analysis with the bioassay and EOX provides rough figure of dioxin-like toxicity and suggests types of organohalogen compounds that should be identified as a part of dioxin analysis for control emission from an incineration plant.     

Fly and bottom ashes from biomass combustion as cement replacing components in mortars production: Rheological behaviour of the pastes and materials compression strength

In the present research mortar pastes obtained by replacing a commercial cement with the equivalent mass of 5, 10, 20 and 30 wt.% of fly ash or bottom ash from fir chips combustion, were prepared and rheologically characterized. It was observed that the presence of ash modifies their rheological behaviour with respect to the reference blend due to the presence, in the ashes, of KCl and K₂SO₄ which cause precipitation of gypsum and portlandite during the first hydration stages of the pastes. Hydrated materials containing 5 wt.% of ash display compression strength and absorption at 28 d of same magnitude as the reference composition; conversely, progressive increase of ash cause a continuous decline of materials performances. Conversely, samples tested after 180 d display a marked decline of compression strength, as a consequence of potassium elution and consequent alkali-silica reaction against materials under curing.     

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

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

A study for evaluation of contaminant transport characteristics through fine-grained soil.

Transport of soluble toxic substances through porous media lead to some significant geoenvironmental problems, for example, leachate migration from municipal and industrial solid waste resulting from unregulated disposal. Advection, dispersion, diffusion, and decay are reported to be the principal mechanisms in such phenomena. Geotechnical properties of the soil also play a significant role in this deterioration. In the present study, laboratory tests were conducted to formulate an appropriate method for assessment of migration of metal ions, such as nickel, through the soil. Relevant kinetic and process parameters, such as aquifer data, surface area, dielectric constant, pH of zero point charge (pHzpc), and permeability were also studied. One-dimensional mathematical modeling was used to describe the dynamics of the process. The present investigation was carried out at an ash pond site of a thermal power plant situated in West Bengal, India.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzo-furans in solid residues from wood combustion by HRGC/HRMS

PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.     

Investigation on organic pollutants from a domestic heating system using various solid biofuels

Various herbaceous biofuels (straw, whole plant cereals and set aside hay) and spruce wood were tested for their potential to form PCDD/F, PCPh, PCBz and PAH during combustion. The trials were conducted in an automatically charged multi-fuel furnace for domestic applications (50 kWth). Both, flue gas and the different ash fractions were analysed. CO-emission results show, that combustion conditions were relatively uniform (mean CO-level: 200 mg/m3 at 13% O2 in flue gas). Likewise, the TOC- and PAH-emissions in the fuel gas remained constantly on a relatively low level. However, for the PCDD/F, PCPh and PCBz increased emissions were detected when herbacious fuels were applied. This may be attributed to their higher chlorine concentration and the high ash content, which is responsible for increased dust emissions during combustion. Similar observations were also found for the PCDD/F-concentrations in the ashes. Combustion chamber ashes usually showed a drastically reduced contamination with highly toxical compounds, compared to the ash fraction from the heat exchanger ash or to chimney soot.     

Hydrometallurgical recovery of zinc from ashes of automobile tire wastes

Study has been performed on the investigation of metal leaching behavior for fly and bottom ashes from automobile tire wastes using acid and alkaline solutions from both viewpoints of environmental protection and resource utilization. The two ashes were found to contain substantial amounts of zinc and iron along with small quantities of cobalt, manganese, magnesium, copper, titanium and aluminum. The fly ash contained a much larger amount of zinc than the bottom ash, and seems to be a promising secondary source for the metal. Effects of such experimental parameters as temperature, time and solid-liquid ratio on the leaching behavior were investigated. Using three mineral acids and citric acid, selective leaching of zinc was successfully attained; the concentration of zinc in the leach liquors from the fly ash reached as high as 20 g l(-1) while the iron leaching was much suppressed. Selective separation of zinc was also attained in the leaching with alkaline solutions, though the percent leaching was lower than that in the acid leaching. Moreover, solvent extraction and precipitation were applied to the metal-loaded leach liquors as downstream processing to evaluate the feasibility of zinc recovery.     

Comparative assessment of coal tars obtained from 10 former manufactured gas plant sites in the eastern United States

A comparative analysis was performed on eleven coal tars obtained from former manufactured gas plant sites in the eastern United States. Bulk properties analyzed included percent ash, Karl Fisher water content, viscosity and average molecular weight. Chemical properties included monocyclic- and polycyclic-aromatic hydrocarbon (PAH) concentrations, alkylated aromatic concentrations, and concentrations of aliphatic and aromatic fractions. It was found that there was at least an order-of-magnitude variation in all properties measured between the eleven coal tars. Additionally, two coal tars obtained from the same manufactured gas plant site had very different properties, highlighting that there can be wide variations in coal tar properties from different samples obtained from the same site. Similarities were also observed between the coal tars. The relative chemical distributions were similar for all coal tars, and the coal tars predominantly consisted of PAHs, with naphthalene being the single-most prevalent compound. The C(9-22) aromatic fraction, an indicator of all PAHs up to a molecular weight of approximately 276 gmole(-1), showed a strong power-law relationship with the coal tar average molecular weight (MW (ct)). And the concentrations of individual PAHs decreased linearly as MW (ct) increased up to ca. 1000 gmole(-1), above which they remained low and variable. Implications of these properties and their variation with MW (ct) on groundwater quality are discussed. Ultimately, while these similarities do allow generalities to be made about coal tars, the wide range of coal tar bulk and chemical properties reported here highlights the complex nature of coal tars.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

Effects of water washing on removing organic residues in bottom ashes of municipal solid waste incinerators

Due to their potential toxicity and odourous nature, the residual organics in municipal solid waste incinerators are recently gaining attention as an important issue of resources recovery apart from their complex mixture of organic counterpart. Studies of the organic fractions in municipal solid waste incinerator residues have been limited. In this study, extended solid-phase extraction of the water-washed bottom ash and liquid-phase extraction of the washing water were carried out with regard to bottom ash samples from three mass-burning incinerators in Taipei County (Taiwan) during four consecutive seasons of year 2008-2009. Supercritical fluid extraction and Soxtec extraction techniques along with GC-MS were successfully used to characterize the residual organics in weathered and washed bottom ashes. Supercritical fluid extraction provided the quantification of aliphatics and aromatic compounds such as hexanoic acid and benzaldehyde, respectively. Soxtec extraction was useful for qualitative analysis of aromatic and aliphatic groups in the ashes and many of which were odourous and toxic compounds. By mixing one unit weight (g) bottom ash with two unit volume (mL) water for 15 min, total organic carbon in the bottom ash was greatly reduced (e.g., from 4.1 to 1.8 wt.%). Among the removed were foul odour-causing compounds such as pyridine and quinoline derivatives, while some aromatic compounds such as 4-hydroxybenzaldehyde and low-molecular-weight aliphatics such as hexanoic acid remained. The results here suggest that washing with water can be an effective pre-treatment step for removing odour-causing and environmental concerned organics.     

Remediation of metal-contaminated soils with the addition of materials--part I: characterization and viability studies for the selection of non-hazardous waste materials and silicates

Contamination episodes in soils require interventions to attenuate their impact. These actions are often based on the addition of materials to increase contaminant retention in the soil and to dilute the contaminant concentration. Here, non-hazardous wastes (such as sugar foam, fly ash and a material produced by the zeolitization of fly ash) and silicates (including bentonites) were tested and fully characterized in the laboratory to select suitable materials for remediating metal-contaminated soils. Data from X-ray fluorescence (XRF), N₂ adsorption/desorption isotherms, X-ray diffraction (XRD) and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) analyses revealed the chemical composition, specific surface area and the phases appearing in the materials. A pH titration test allowed the calculation of their acid neutralization capacity (ANC). The metal sorption and desorption capacities of the waste materials and silicates were also estimated. Sugar foam, fly ash and the zeolitic material were the best candidate materials. Sugar foam was selected because of its high ANC (17 000 meq kg⁻¹), and the others were selected because of their larger distribution coefficients and lower sorption reversibilities than those predicted in the contaminated soils.     

The behavior of PCDD and PCDF during thermal treatment of waste incineration ash

The polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) content of three fly ash samples with different elemental compositions from different municipal waste incinerators were analyzed before and after thermal treatment at 300 °C or 500 °C. Gas phase emissions during the treatments were also collected and analyzed. Substantial reductions in the total PCCD/F content of the ashes were observed after treatment at 500 °C, seemingly due to degradation rather than dechlorination. Treatment at 300 °C resulted in an increase in the PCDD/F content of the three ashes. Initial concentration of PCDD/F in the untreated ashes did not reflect the outcome of the treatment at the different temperatures. In addition, the composition of the ash was found to influence the rate of decomposition and formation of PCDD and PCDF during thermal treatment; the results showed that Cu, Fe, Ca and S play important roles in these processes.     

Rice and wheat straw ashes: Characterization and modeling of pretilachlor sorption kinetics and adsorption isotherm

The rice straw ash (RSA) and wheat straw ash (WSA) were explored as low cost adsorbent for pretilachlor removal from water. The ashes were characterized and sorption behavior of pretilachlor was evaluated. Kinetics study suggested that the modified Elovich model best explained the pretilachlor sorption on both the ashes. The adsorption data were analyzed using 2-, 3- and 4-parameter models and nine error functions were used to compute the best fit isotherm by nonlinear regression analysis. The pretilachlor was more sorbed onto the RSA (22.0–92.2%) than the WSA (11.4–61.4%) and percent adsorption decreased with increase in the herbicide concentration in solution. Isotherm model optimization analysis suggested that the Freundlich and the Temkin isotherms were the best models to predict the pretilachlor adsorption onto the RSA and the WSA. The error analysis suggested that the reciprocal of the observed squared (ROS) and the reciprocal of the predicted squared (RPS) error functions provided the best determination of the adsorption constants for the Freundlich and the Temkin isotherms, respectively. The RSA, which exhibited higher pretilachlor sorption potential, can be utilized as low cost adsorbent for pesticide removal from contaminated water.     

Removal of hydrogen sulfide gas and landfill leachate treatment using coal bottom ash.

Coal bottom ashes produced from three thermal power plants were used in column and batch experiments to investigate the adsorption capacity of the coal ash. Hydrogen sulfide and leachates collected from three sanitary landfill sites were used as adsorbate gas and solutions, respectively. Experimental results showed that coal bottom ash could remove H2S from waste gas or reduce the concentrations of various pollutants in the leachate. Each gram of bottom ash could remove up to 10.5 mg of H2S. In treating the landfill leachate, increasing ash dosage increased the removal efficiency but decreased the adsorption amount per unit mass of ash. For these tested ashes, the removal efficiencies of chemical oxygen demand (COD), NH3-N, total Kjeldhal nitrogen (TKN), P, Fe3+, Mn2+, and Zn2+ were 36.4-50, 24.2-39.4, 27.0-31.1, 82.2-92.9, 93.8-96.5, 93.7-95.4, and 80.5-82.2%, respectively; the highest adsorption capacities for those parameters were 3.5-5.6, 0.22-0.63, 0.36-0.45, 0.027-0.034, 0.050-0.053, 0.029-0.032, and 0.006 mg/g of bottom ash, respectively. The adsorption of pollutants in the leachate conformed to Freundlich's adsorption model.