Partitioning of elements in a entrained flow IGCC plant: Influence of selected operational conditions

The partitioning of trace elements and the influence of the feed conditions (50:50 coal/pet-coke feed blend and limestone addition) was investigated in this study. To this end feed fuel, fly ash and slag samples were collected under different operational conditions at the 335 MW Puertollano IGCC power plant (Spain) and subsequently analysed. The partitioning of elements in this IGCC plant may be summarised as follows: (a) high volatile elements (70->99% in gas phase): Hg, Br, I, Cl and S; (b) moderately volatile elements (up to 40% in gas phase and ?60% in fly ash): As, Sb, Se, B, F, Cd, Tl, Zn and Sn; (c) elements with high condensation potential: (>90% in fly ash): Pb, Ge, Ga and Bi; (d) elements enriched similarly in fly ash and slag 30-60% in fly ash: Cu, W, (P), Mo, Ni and Na; and (e) low volatile elements (>70% in slag): Cs, Rb, Co, K, Cr, V, Nb, Be, Hf, Ta, Fe, U, Ti, Al, Si, Y, Sr, Th, Zr, Mg, Ba, Mn, REEs, Ca and Li. The volatility of As, Sb, and Tl and the slagging of S, B, Cl, Cd and low volatile elements are highly influenced by the fuel geochemistry and limestone dosages, respectively.     

Enrichment of inorganic trace pollutants in re-circulated water streams from a wet limestone flue gas desulphurisation system in two coal power plants

The enrichment of inorganic trace pollutants in re-circulated water streams was studied at two power plants equipped with wet limestone Flue Gas Desulphurisation (FGD) system from the first re-circulation cycle of water up to the start of sampling campaigns. To elucidate the enrichment of inorganic trace pollutants as result of water re-circulation, a partial and total mass balances were undertaken. A t-Student analysis was performed to ascertain whether the mean contribution of filtered water affected the balance of elements and the enrichment of this water stream. The t-Student revealed the mean contribution of filtered water to total mass balance was statistically significant (p < 0.05) for Na, Mg, Cl, B, Mn, Se, Cd, Mo, and U at first plant, and Na, Cl, K, Mg, Hg, Li, B, F, Ni, Zn, Mn, Co Sc, Ge, Se, at the second one. High levels of inorganic trace pollutants in filtered water could be affected by limestone purity, electrostatic precipitator gas temperature, use of additives, fluoride and/or sulphate complexes, and the S/F and S/Cl ratios in the scrubber, which may reduce the gaseous retention efficiencies in FGD and increase the emission of metals by entraining and/or evaporation of droplets as particulate matter from gypsum slurry.     

Particulate emissions from large-scale medium-speed diesel engines: 2. Chemical composition

The effect of diesel fuel and operation mode on diesel particulate matter (PM) emissions was studied using a combination of a gravimetric impactor (DGI) and SEM/EDX analysis of PM particles from 0.005 to 2.5 μm aerodynamic size. Tests were made with heavy fuel oil (HFO) and light fuel oil (LFO) with medium speed (500 rpm), turbo-charged, power per cylinder ~1 MW, multivariable large-scale diesel engines. Diesel PM was sampled from diluted and cooled exhaust gases. The sampled PM was found to be primarily made of carbon and sulphur derived from the fuel and lube oil but contain several other chemical species as well. In this paper the submicron particle size range (0.2-0.5 μm and 0.5-1.0 μm) is discussed. The EDX analysis gave reasonably accurate quantitative results featuring the important elements present in the samples, namely, C, O, Mg, Si, S, Cl, Ca, V, Fe, Ni, Zn (and Al). The results indicate that the finest particles originate primarily from the fuel while the somewhat larger particles contain also significant amounts of elements derived from the lubrication oil. As expected, the concentrations of sulphur and certain metallic elements such as V, Ni, Ca, Zn, Fe, Mg are significantly higher in diesel PM from HFO firing than for LFO firing.     

Behaviour of elements and minerals during preparation and combustion of the Pernik coal,Bulgaria

The chemical and mineral composition, including major (Al, Ca, Fe, K, Mg, S, Si, Ti), minor (Na, P) and trace (Br, Cl, Co, Cr, Cu, Li, Mn, Ni, Pb, Rb, Sr, Zn) elements and different minerals, of the Pernik subbituminous coals and their preparation and combustion solid waste products were studied. Feed coals, upgraded coals (high-grade and low-grade coals) and their waste products, namely coal slimes and host rocks generated from the Pernik coal preparation plant, as well as combustion waste products such as bottom ashes, fly ashes and lagooned ashes resulted from the Republica coal-fired thermoelectric power station were characterized. The occurrence and behaviour (partitioning, volatilization, condensation, capture and retention) of the above-mentioned elements and various minerals during coal preparation and combustion are described. The results indicate some technological problems and possible environmental pollution of the air, water, soil and vegetation with certain elements in the areas surrounding both thermoelectric power station and coal preparation plant.     

Chemometric analysis of trace elements distribution in raw and thermally treated high sulphur coals

In the present study, chemometric analysis is applied as a tool to evaluate the release behaviour of trace elements (TEs) during coal utilization processes. Principal component analysis (PCA) and linear discriminant Analysis (LDA) were applied on the TE concentrations of raw and thermally treated coals. PCA and LDA successfully predicted the association of 21 trace elements (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, Te, Pb) contained in coal and their thermal behavior at various temperatures. Application of chemometric on thermally treated coals shows that at temperature 450 °C, elements like Na, P, K, Fe, Ca, Mg, Al and Si have affinity with mineral matter and therefore have low volatility. Elements like Te, Sb and Ti may form their chlorides, which enhance the volatilities of these elements, while Co and Pb may form sulfides like Co₂S₄ and PbS. In the temperature range of 600-850 °C, either coal undergones an intense degradation of its structure during pyrolysis and the elements released may be adsorbed on coal surface or be volatile. The elements Cr, Co, V, Ni may react with sulphurous gases evolved during pyrolysis. At temperature 1000 °C, wide dispersion in data elements interact with carbon and sulphur compounds of coals. The formation of compounds like Si carbide, bassanite, gehlenite, anarthite may also be responsible for low volatilities of the elements Si, Al and Ca at higher temperatures. Predictive capabilities of PCA and LDA were evaluated in terms of TEs volatilities at different temperatures. The results of chemometric analysis are not only in good agreement with volatilities of TEs present in coals at various temperatures but also with FTIR analysis.     

A three-step metal fractionation scheme for fly ashes collected in an Argentine thermal power plant

A new three-step fractionation scheme was applied to study the distribution of Al, As, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, S, Sb, Ti, V and Zn in fly ashes collected in the electrostatic precipitator of a thermal power plant in the city of San Nicolás (Argentina). Seven samples were collected during one week of operation in 2005. For the fractionation, the scheme applied consisted of extracting the elements in three fractions: (i) soluble and exchangeable elements, (ii) carbonates, oxides and reducible elements and (iii) residual elements. Metals and metalloids at μg g⁻¹ level were determined in each fraction by plasma based techniques namely, inductively coupled plasma optical emission spectrometry (ICP OES) and inductively coupled plasma mass spectrometry (ICP-MS). For validation, a certified reference materials NIST SRM 2711 (Montana soil) was subject to the same chemical sequential extraction procedure. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the major minerals present in the matrix. The predominant phases found in the total samples were mullite, quartz, iron oxides and lime. Total analyte concentration varied (in μg g⁻¹) from 1.54 for Cd to 30 600 for Al. The leachability of the 15 elements under study proved to be different. All the elements (except Cd and Pb) were detected in the soluble fraction in the order: Cu (0.10%) ∼ Mn (0.13%) < Ni (0.17%) ∼ Ti (0.19%) ∼ Fe (0.20%) ∼ As (0.21%) < Zn (0.86%) < Al (1.3%) < Cr (2.9%) < V (3.9%) < Sb (6.9%) < Mo (45.1%) < S (58.0%). Percentages higher than 20% of S (24.1%) < V (27.5%) < Mn (29.0%) were detected in the second fraction. Al, As, Cr, Cd, Cu, Fe, Ni, Pb, Sb and Zn were mostly associated to the residual fraction. Recoveries of the overall procedure varied between 106% (Mo) and 72% (Cr).     

Volatilisation of trace elements for coal–sewage sludge blends during their combustion☆

The influence of sewage sludge addition on the volatility of 37 trace elements (Ag, As, Au, B, Ba, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, Hf, Hg, La, Li, Mn, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Se, Sn, Sr, Ta, Te, Th, Tl, U, V, Y, Zn, Zr) during coal combustion was studied. For this purpose, a bituminous coal from the Asturian Central Basin and sewage sludge treated with Ca(OH)₂ and FeCl₃, as well as 10 and 50 wt% sludge–coal blends were used. Combustion experiments were performed in a laboratory electric furnace at 800, 900, 1000 and 1100 °C. The results have confirmed that the high Cl contents of the sludge can produce a pronounced effect on the volatilisation of some trace elements (Ag, Cd, Cs, Cu, Li, Pb, Rb and Tl) due to the probable formation of volatile chlorides, while the high CaO concentrations increase the retention of some elements in ash as As, Se and Te. The above opposite effects of Cl and CaO on trace element volatilisation were generally inappreciable for the 10 wt% blend, while they were more significant, but not as noticeable as expected, for the 50 wt% blend.     

Investigations on twenty Australian sewage sludges — their evaluation by means of chemical analysis

To evaluate twenty sludges from different places in Australia for disposal on arable land, these sludges were extracted with (a) HNO₃ to determine the ‘total’ contents of some heavy metals and other elements; (b) a solution containing DTPA to determine contents of ‘available’ heavy metals; and (c) with a CaCl₂-solution to determine contents of water-soluble heavy metals and some other elements. Measurements of the pH of the sludges, their electrolytic conductivity, NaHCO₃-extractable P, water-extractable Cl, and contents of ash and organic carbon were also made. The HNO₃-extractable Cd, Cu, Mn, Ni, Pb, and Zn in the sludges were compared with those in sludges from three other countries. High correlations between HNO₃-extractable and DTPA-extractable metals were found in the Australian sludges; therefore, the HNO₃ is equally good as the DTPA as an extractant of heavy metals in sewage sludges. The correlations between HNO₃- and CaCl₂-extractable Cd, Cu, Mn, and Zn were not significant. ‘Young’ and ‘aged’ sludges from the same treatment plants consistently differed in their Na and Cl contents, which were lower in the ‘aged’ sludges. A wheat experiment treated with high application rates of a saline and metalliferous sludge showed that the balance of nutrients and the amount of soluble salts in a sewage sludge are of greater direct importance to the growth of plants than the heavy metal content of that sludge.     

The fate of trace elements in fluidised bed combustion of sewage sludge and wood

Combustion tests have been carried out in a fluidised bed boiler to investigate the fate of trace elements during co-combustion of wood and municipal sewage sludge. The approach was to collect fuel and ash samples and to perform thermodynamic equilibrium calculations for gasification (reducing) and combustion (oxidising) conditions. Trace elements are found in the ash. Even most of the highly volatile Hg is captured in the bag filter ash. The bag filter ash offers higher surface area than the secondary cyclone ash and enhances the capture of Hg. There is no obvious correlation between capture and parameters investigated (sludge precipitation agent and lime addition). As, Cd, Hg, Pb, Se, Sb and Tl are predicted by equilibrium calculations to be volatile in the combustion chamber under oxidising conditions and Hg even at the filter temperature (150 °C). Reducing conditions promote, in some case more than others, the volatility of As, Cd, Pb, Sb, Se, Tl and Zn. The opposite effect was observed for Cu and Ni. Data points to the necessity of including bag filter in the gas cleaning system in order to achieve good removal of toxic trace elements.     

Effects of chlorine and sulphur on particle formation in wood combustion performed in a laboratory scale reactor

Fine particle formation in wood combustion was studied in a laboratory scale laminar flow reactor at various flue gas chlorine and sulphur concentrations. Aerosol samples were quenched at around 850 °C using a porous tube diluter. Fine particle number concentrations, mass concentrations, size distributions and chemical compositions were measured. In addition, flue gas composition, including SO₂ and HCl, was monitored. Experimental results were interpreted by thermodynamic equilibrium calculations.Addition of HCl clearly raised fine particle mass concentration (PM1.0) which was because of increased release of ash-forming material to fine particles. Especially the release of K, Na, Zn and Cd to fine particles increased. These species form chlorides which apparently increases their volatilization from the fuel. When a sufficient amount of SO₂ was supplied in a chlorine rich combustion (S/Cl molar ratio from 4.7 to 7.5), most of the HCl stayed in the gas phase, release of ash-forming elements decreased and also fine particle concentrations dropped significantly. The sulphation of alkali metals is suggested to play a key role in the observed decrease in the fine particle concentration. It seems that the formation of sulphates leads to alkali metal retention in the coarse particle fraction.     

Partitioning of trace inorganic elements in a coal-fired power plant equipped with a wet Flue Gas Desulphurisation system

The abatement capacity of trace inorganic elements was studied in a large Pulverized Coal Combustion (PCC) power plant equipped with a wet limestone Flue Gas Desulphurisation (FGD) system. High proportions of most elements were retained as fly ash as consequence of the efficiency of the electrostatic precipitator (ESP, 99.6% of fly ash) and slag (11%). The most volatile elements, such as S and F are retained by the FGD gypsum, and Cl by the filtered water; whereas the moderately volatile elements, As and B, are retained mainly by fly ash, reaching very high abatement efficiencies for these elements when considering the whole plant (>92%). Selenium and Hg are still retained by the whole system with relatively high proportions (89% and 67%); however a prominently proportion is emitted; Se (11%) and Hg (29%), attaining gaseous/PM rate at the emissions reaching 0.08 and 290, respectively. The gaseous emissions are below the limits according to the European directive 2001/80/EC for large combustion plants and the PRTR threshold values with the exception of Hg emissions and particulate Se, As, Zn, Cu, Ni, and Cr. Remediation actions to prevent and/or reduce the gaseous and PM emissions as well as the determination of leachable potential of trace inorganic pollutants retained in FGD gypsum, especially F in view of its disposal, are of significant relevance.     

Trace element behaviour in the Sasol-Lurgi MK IV FBDB gasifier. Part 2 - The semi-volatile elements: Cu, Mo, Ni and Zn

Gasification is a coal conversion process that could be considered to be more amenable with regards to environmental impact factors when compared to combustion, as it provides minimum direct emission to the atmosphere due to the opportunity to apply a series of gas cleaning processes. Emissions could be in the form of the well known trace elements labelled as toxic present in feed coal. Due to the minimal literature available on coal gasification when compared to coal combustion, a large amount of inference to coal combustion has been applied in discussing the partitioning behaviour of trace elements during coal utilization. Conducting mass balance calculations of trace elements around gasification processes have proven to be a challenging task. This is due to the limitation of the analytical techniques employed to quantify at the parts per million levels at which trace elements exist. The other challenge is analyzing for trace elements in all the different stream phases that occur after gasification. The availability of thermodynamic equilibrium packages i.e. Fact-Sage to perform high temperature calculations, at the same time handling all phases of material involved has simplified the challenges. Results obtained from such calculations have also proved to be close to reality, but have not been related to the fixed-bed counter-current gasification reactor operating on lump coal.The focus of this paper is to discuss more recent environmentally-focused research developments by Sasol, where trace element simulation and validation of model predictions have been undertaken for the gasification process. Fact-Sage thermodynamic equilibrium modelling was used to simulate the semi-volatile trace elements (Cu, Mo, Ni and Zn) gas phase and ash phase partitioning and speciation behaviour occurring in a fixed-bed pressurized gasifier. A Sasol-Lurgi Mark IV FBDB gasifier was mined via turn-out sampling in order to determine the trace element changes through the gasifier, results being used to validate the modelled results.The semi-volatile elements: Cu, Mo, Ni and Zn all showed limited (5% in the case of Zn) de-volatilization behaviour in the drying and pyrolysis zone of the fixed-bed gasifier. Predictions revealed that within the reduction zone of the fixed-bed gasifier that they are all highly volatile, producing gaseous species with an increase in temperature, varying in the order: Zn > Mo > Cu > Ni, which is contrary to what was found from the experimental results. This could imply that thermodynamic equilibrium conditions do not necessarily prevail in a fixed-bed gasifier operating on lump coal, since in reality mass and heat transfer limitations across coarse coal particles apply and the reactions are therefore more kinetically limited. Over-balances of Ni and Mo partitioning to the solid ash fraction, was found for the measured results. This anomaly was found to not be caused by erosion of the gasifier internals, but rather possibly be ascribed to accumulation and contamination caused by likely condensation and vaporisation of these species during the gasifier sampling campaign, as well as by the particle size reduction processes utilized prior to elemental analyses. Leaching tests conducted on the bottom ash collected from the gasifier have shown that the trace elements studied are firmly bound into the ash matrix and therefore would not be released during later disposal. The relative enrichment in trace element content observed for Ni and Mo within the gasifier should be further investigated.     

Size Distribution and Sources of Trace Metals in Ultrafine/Fine/Coarse Airborne Particles in the Atmosphere of Shanghai

Airborne particulate matter (PM) samples in 13 different size-fractions from 0.0283 to 9.92 μm were collected in winter of 2007 at three sites in Shanghai, China. The PM exhibited a bimodal distribution with a major mode in the fine particle size range (D_p = 0.2–1 μm) and a minor mode in the coarse range (D_p = 1–10 μm), suggesting that fine particle pollution is dominant in the Shanghai atmosphere. Trace metals in PM exhibited the following distribution patterns: (1) unimodal distribution in the fine fraction (Pb, Cd, Se, Sn, Bi, and Zn), (2) unimodal distribution in the coarse fraction (Mg, Al, Fe, Ca, Ba, Sr, Ge, Zr, U, and rare earth elements), (3) bimodal distribution, with one mode in the fine fraction and one in the coarse fraction (Cu, Mn, K, Ga, V, Rb, and Cs), and (4) multimodal distribution (Na, Ti, Cr, Co, As, Ni, Mo, Ag, W, Pt, Au, S, and Cl) throughout the entire aerosol size spectrum. In addition to these size distributions, Aitken modes due to local origins were also evident for Se, Sn, Cu, V, Ti, Cr, Co, As, Ag, Mo, and Pt, whose respective mass in the ultrafine particles (<0.1 μm) was 10, 23, 13, 19, 23, 14, 67, 32, 79, 40, and 21%, with submicron mass median aerodynamic diameters (MMADs) in PM_0.02-9.92 (except Pt). In particular, the MMADs for Co and Ag were <0.1 μm, which increase potential health issues. The measured distributions are believed to result from a combination of processes including local anthropogenic and natural sources, such as traffic, coal combustion, and the steel industry.     

Volatility and chemistry of trace elements in a coal combustor

The volatility of 16 trace elements (TEs) (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, Te, Tl, V, Zn) during coal combustion has been studied depending on the combustion conditions (reducing or oxidizing) and type of coal (high- or low-ash coal), together with their affinities for several active gaseous atoms: Cl, F, H, O, and S.

The elements can be divided into three groups according to their tendencies to appear either in the flue gases or in the fly ashes from a coal combustor:

Group 1: Hg and Tl, which are volatile and emitted almost totally in the vapor phase.

Group 2: As, Cd, Cu, Pb and Zn, which are vaporized at intermediate temperature and are emitted mostly in fly ashes.

Group 3: Co, Cr, Mn and V, which are hardly vaporized and so are equally distributed between bottom ashes and fly ashes. In addition, Sb, Sn, Se and Te may be located between Groups 1 and 2, and Ni between 2 and 3.

At 400 and 1200 K, the 16 TEs behave differently in competitive reactions with Cl, F, H, O and S in a coal combustor.     

Comparative study of elemental mass size distributions in urban atmospheric aerosol

Elemental mass size distributions in aerosols collected at four different urban sites with gradually increasing overall aerosol mass concentration are presented, compared and discussed in the present paper. The aerosol samples were collected with cascade impactor and stacked filter unit samplers, and were analyzed by particle-induced X-ray emission spectrometry and instrumental neutron activation analysis. Typical coarse-mode elements, i.e., Na, Mg, Al, Si, P, Ca, Ti, Fe, Ga, Sr, Zr, Mo and Ba, exhibited unimodal size distributions at all four urban locations studied, and the mass median aerodynamic diameters were increased with aerosol pollution level. Elements typically related to high-temperature or anthropogenic sources, i.e., S, Cl, K, V, Cr, Mn, Ni, Cu, Zn, Ge, As, Se, Br, Rb and Pb, either had a unimodal size distribution with most or their mass in the fine size fraction or clearly showed a bimodal size distribution at the urban background site. However, significant differences between the size distributions of four sampling sites were noted. There was a clear tendency for the accumulation mode to decrease and for the coarse mode to increase with increasing total aerosol mass concentration. A pronounced resuspension of the soil and roadway dust associated with the fine aerosol particles that were deposited on the ground surface previously, and the condensation process of volatile precursor gases on the already existing aerosol particles can explain the observed tendencies. The elemental mass size distributions derived for the polluted urban environments differ from those typically observed for industrial, combustion or automotive sources. A consequence of the diversity in the size distributions on the PM_2.5 speciation concept is also presented.     

Influence of woody biomass (cedar chip) addition on the emissions of PM10 from pulverised coal combustion

Co-combustion of pulverised coal with a woody biomass, cedar chip was conducted in a lab-scale drop-tube furnace (DTF) to investigate the synergetic interaction between the inorganic elements of different fuels and the emissions of sub-micron particles (particles smaller than 1.0 μm in size, PM₁) and super-micron particles (particles in the size range of 1.0-10 μm, PM₁₊) during co-firing. The mass fraction of cedar chip in fuel blend ranged from 10% to 50%. All the fuels were burnt in air at two furnace temperatures, 1200 and 1450 °C. The results indicate that, under an identical calorific input, combustion of cedar chip alone favored the emission of sub-micron PM₁, which is dominated by volatile elements including K, Ca, Fe, Na and P. A large fraction of K and Na were most probably present as gaseous vapors in the furnace. The other metals mainly condensed into nano-scale nuclei which subsequently coagulated into a variety of sizes in flue gas. Coal combustion alone favored the release of super-micron particles rich in Al and Si. Emission of PM upon co-firing was a function of both cedar chip share and furnace temperature. At a small mass fraction for cedar chip in fuel blend, e.g. 10% tested here, interaction between the inorganic elements of single fuels was insignificant at either furnace temperature. Accordingly, the quantities of PM₁ and PM₁₊ emitted from co-firing at 10% cedar chip were slightly higher than from the combustion of coal alone, due to the contribution of cedar chip. Significant interaction between the inorganic elements of single fuels was observed for co-firing of coal with >10% cedar chip at the furnace temperature of 1450 °C. As has been confirmed, adding 20-30% cedar chip to coal resulted in the shift of approximately 90% of PM₁ and 50% PM₁₊ into coarse ash particles. For the cedar chip-derived alkali vapors and nano-scale/sub-micron particles, the rates of their shift into larger particles were influenced by two competing routes, homogeneous coagulation and surface reaction with coal-derived kaolin. In contrast, the shift of super-micron particles was primarily determined by their collision probability with the coal-derived mineral grains in bulk gas. A sticky surface for particles is also essential. The shift of individual metals into coarse ash differed distinctly from one another.     

X射线荧光光谱法测定土壤样品中C和N等30个主次痕量元素

采用PVC环的粉末样品压片制样,用RIGAKU ZSX Primus Ⅱ型X射线荧光光谱仪对土壤样品中的C、N、Na2O、MgO、Al2O3、SiO2、P、S、Cl、K2O、CaO、Ti、V、Cr、Mn、TFe2O3、Co、Ni、Cu、Zn、Ga、Nb、Zr、Y、Sr、Rb、Pb、Th、Ba和Br等30个组分进行测定.重点研究了C、N、Cl、S等元素的测定条件、痕量元素的背景选择和谱线重叠校正问题.使用经验系数法和康普顿散射线、背景散射线作内标校正基体效应.经国家一级标准物质校验,方法的检出限、精密度和准确度,满足多目标地球化学调查样品的分析要求.     

The composition of size-fractionated pulverised coal and the trace element associations

Major and trace element analyses have been performed on size fractions of a pulverised coal from Eggborough Power Station (UK). Minerals are concentrated in the fractions less than 10 μm in size and there is relative enrichment of pyrite in the fractions greater than 50 μm. Because of the compositional variation with size it is possible to proportion statistically the elements between, in this case, organic matter, silicates and pyrite. Germanium, Br and V are dominantly organic associated and Cr, Cu, Ni, Zn, Sr, Ba and Pb are also present in the organic matter, although concentrations are lower than in other fractions of the coal. These elements are either in the organic structures or contained within pore fluids. Chromium, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Sm, Th and U are dominantly associated with the silicate fraction, as are V, Ni and Zn, but other coal fractions contribute more to the total coal composition. Concentrated in pyrite are Mo, Se, As, Pb, Sb, and to a lesser extent Ni, Cu and Zn in that these elements are sufficiently concentrated in other fractions that pyrite is not the major location in the coal. Validation for the method is achieved by summing element concentrations in the three fractions and comparing with the bulk composition. Previous calculations on a related coal have been extended and close agreement observed for the composition of the three fractions. The calculated values for the fractions apply specifically to one coalfield, although some of the values may have more general application.     

Screening the possibility for removing cadmium and other heavy metals from wastewater sludge and bio-ashes by an electrodialytic method

Both wastewater sludge and fly ash from combustion of biomass (bio-ash) have traditionally been applied to agricultural land in Denmark. However, Cd concentrations often exceed limiting values. The present study is a preliminary investigation of the possibility for reducing the Cd concentration in wastewater sludge and bio-ashes (straw and wood) using an electrodialytic method. The waste products were treated as stirred suspensions. During the remediation the suspension was acidified from water splitting at the anion exchange membrane and the acidification mobilized Cd that was removed to the electrode compartments. Even though the matrices were very different the remediation was successful in all cases. After treatment the Cd concentration in the ashes allowed for spreading at agricultural land and the limiting concentration of 0.8 mg Cd/kg for the wastewater sludge was almost reached (0.84 and 0.88 mg Cd/kg). The main differences of the waste products influencing the remediation process were: the sludges had a high content of organic particles that were mobilized by electrophoresis and fouled the anion exchange membrane; the straw-ash contained a lot of chloride, which formed anionic complexes with Cd, and the wood ash had a high initial pH (13.3). The mass of wastewater sludge and bio-ashes decreased during treatment but the concentration of other heavy metals (Pb, Ni, Cu and Zn) was not increased to exceed limiting values in remediated matrix.     

Content, mobility and transfer behavior of heavy metals in MSWI bottom ash in Zhejiang province, China

Municipal solid waste incinerator (MSWI) bottom ash samples were taken from six cities of Zhejiang province, where 1/4 incinerators of China were located. The samples were instrumentally analyzed to detect the content of heavy metals. Sequential extraction procedure (SEP) was adopted to characterize the mobility and environmental impact of heavy metals. And the transfer coefficients of heavy metals from the input MSW to the bottom ash during the incineration were also calculated. It showed that the average content of Zn, Mn, Cu, Pb and Cr in the bottom ash exceeded 300 mg/kg, which was much higher than that in the soils. SEP results showed that although the residue fraction was the primary fraction of the heavy metals in the bottom ash, there were still 1.84 mg of Cd, 86.21 mg of Cu, 83.46 mg of Pb and 939.46 mg of Zn in 1 kg bottom ash having the potential of leaching, which indicated a great threat to the surrounding environment. The result of coefficients calculation revealed that almost all the Cu, Cr, Mn and Ni in the input MSW were transferred to the bottom ash during the incineration. Bottom ash was also the main destination of Cd, Co, As, Mo, Pb and Zn though considerable amounts of those metals were transferred to the raw gas.