Partitioning behavior of trace elements during pilot-scale fluidized bed combustion of high ash content lignite

This study describes the partitioning of 20 trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and eight major and minor elements (Al, Ca, Fe, K, Mg, Na, Si, Ti) during the combustion of high ash content lignite. The experiments were carried out in the 0.3 MW(t) Middle East Technical University (METU) atmospheric bubbling fluidized bed combustor (ABFBC) test rig with and without limestone addition. Inert bed material utilized in the experiments was bed ash obtained previously from the combustion of the same lignite without limestone addition in the same test rig. Concentrations of trace elements in coal, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Cr, Hg, Li, Mo, Ni, Sn, V, Zn) are recovered in fly ash. Limestone addition shifts the partitioning of Ba, Cr, Mo, Ni, Sn, V, Zn from bottom ash to fly ash.     

Trace elements partitioning during co-firing biomass with lignite in a pilot-scale fluidized bed combustor

This study describes the partitioning of 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and 9 major and minor elements (Al, Ca, Fe, K, Mg, Na, S, Si, Ti) during co-firing of olive residue, hazelnut shell and cotton residue with high sulfur and ash content lignite in 0.3 MW(t) Middle East Technical University (METU) Atmospheric Bubbling Fluidized Bed Combustor (ABFBC) test rig with limestone addition. Concentrations of trace elements in coal, biomass, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission and mass spectroscopy (ICP-OES and ICP-MS). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Tl, V and Zn) are recovered in fly ash when firing lignite only. Co-firing lignite with biomass enhances partitioning of these elements to fly ash. Co-firing also shifts the partitioning of Cd, P, Sb and Sn from bottom to fly ash.     

Use of sequential leaching, mineralogy, morphology and multivariate statistical technique for quantifying metal pollution in highly polluted aquatic sediments--a case study: Brahmani and Nandira Rivers, India

The particle size distribution, geochemical composition and sequential leaching of metals (Fe, Mn, Ni, Cu, Co, Cr, Pb, Zn and Cd) are carried out in core sediments (<88 microm) from the Brahmani and Nandira Rivers, India. To confirm the contamination of downstream sediments by fly ash, mineralogical and morphological characterizations were carried out. High environmental risk of Co, Pb and Ni is due to their higher availability in exchangeable fraction. The metals like Zn, Cu and Mn represent an appreciable portion in the carbonate phase. Metals such as Zn, Pb, Cd, Co and Ni are associated with reducible phase may be due to adsorption. The organic bound Cu, Zn, and Pb seem to be second dominant fraction among non-lithogenous in Nandira sediments. Factor analysis data reveals that textural parameters, Fe-Mn oxy/hydroxides, organic precipitation and coal fly ash disposals, are individually responsible for the enrichment of heavy metals. The relationships among the stations are highlighted by cluster analysis to identify the contamination levels.     

Decontamination and/or revegetation of fly ash dykes through naturally growing plants

Present study is focused on the decontamination and/or revegetation of fly ash dykes through naturally growing plants, namely Calotropis procera, Cassia tora, Chenopodium album, Sida cardifolia, Blumea lacera. The results of sequential extraction study showed that maximum amount of metals (Na, K, Fe, Mn, Cr, Pb, Ni, Cd) were associated with residual and Fe-Mn fractions. Diethylenetriamine penta acetic acid (DTPA)-triethanolamine (TEA) extraction assessed the bioavailability of the metals. The total metal accumulation in tested plants was found in the order; C. album>S. cardifolia>C. tora>C. procera>B. lacera. The maximum bioconcentration factor (BCF) was recorded in S. cardifolia for the metals (Na, Fe, Zn, Cd), in C. procera for the metals (Mn, Cu, Ni, Cr) and in C. album for the metals (Co, Pb). However, the translocation factor (TF) of most of the metals was found more in S. cardifolia followed by C. album than other plants. Among all the plants, C. album have shown high BCF and low TF values for toxic metals (Pb, Cd) and suitable for phytostabilization of these metals. Principal component analysis was used to predict translocation behavior of the metals in different parts of the plants which was found similar for the metals (Cu, Zn, Mn, Cr). All examined plants are suitable for revegetation (naturally grows on fly ash dykes) and S. cardifolia and C. album may be used for decontamination purposes.     

Preparation of xylenol orange functionalized silica gel as a selective solid phase extractor and its application for preconcentration--separation of mercury from waters

A new selective solid phase extractor was prepared from silica gel modified with xylenol orange (SGMXO). The solid phase extractor is stable in 6molL(-1) HCl, common organic solvents, and pH 1.0-9.0 buffer solutions. In the batch experiments, Hg(II) can be adsorbed on SGMXO at pH 1.0 with 90.0% retention, whereas the retention of other common coexisting metal ions such as Cd(II), Pb(II), Cu(II), Ni(II), Co(II), Mn(II), Zn(II), and Fe(III) is less than 4.1%.. The adsorption equilibration for Hg(II) was achieved within 3min. At optimum conditions, the adsorption capacity of the extractor is 18.26micromolg(-1) of dry modified silica gel, and the preconcentration factor is as high as 333. The recovery is still higher than 95% for the preconcentration of 10ngmL(-1) Hg(II). The new solid phase extractor has been used for the preconcentration of low level of Hg(II) in surface water, tap water in chemistry laboratory and student's dormitory and a simulated sea water samples, recoveries of 98.2-100.6% were obtained. It is showed that low level of Hg(II) can be effectively preconcentrated by this new selective solid phase extractor.     

Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines

Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation.     

Assessment of trace element levels in Rhododendron honeys of Black Sea Region, Turkey

Rhododendron and multi-flower honeys obtained from Black Sea Region of Turkey (12 Rhododendron and 8 multi-flower honeys) were studied to determine the presence of the 14 trace elements such as Cu, Cd, Pb, Co, Cr, Ni, Al, Se, Zn, Mn, Fe, K, Ca and Mg. Trace element determination was performed by atomic absorption spectrometry (AAS) after microwave digestion. The results revealed that Rhododendron honeys exhibited higher concentrations of Cu, Co, Cr, Ni, Se, Zn, Ca and Mg but lower concentrations of Al, Mn, Fe and K than in the multi-flower honeys. Trace element levels in analyzed honey samples were generally lower than literature values.     

Comparative study of adsorption properties of Turkish fly ashes. I. The case of nickel(II), copper(II) and zinc(II)

The objective of this study was to compare two different Turkish fly ashes (Afsin-Elbistan and Seyitomer) for their ability to remove nickel [Ni(II)], copper [Cu(II)] and zinc [Zn(II)] from an aqueous solution. The effect of contact time, pH, initial metal concentration and fly ash origin on the adsorption process at 20+/-2 degrees C were studied. Batch kinetic studies showed that an equilibrium time of 2h was required for the adsorption of Ni(II), Cu(II) and Zn(II) on both the fly ashes. The maximum metal removal was found to be dependent on solution pH (7.0-8.0 for Ni(II), 5.0-6.0 for Cu(II) and 6.0-7.0 for Zn(II)) for each type of fly ash. With an increase in the concentrations of these metals, the adsorption of Ni(II) and Zn(II) increased while the Cu(II) adsorption decreased on both the fly ashes. Adsorption densities for the metal ions were Zn(II)>Cu(II)>Ni(II) for both the fly ashes. The effectiveness of fly ash as an adsorbent improved with increasing calcium (CaO) content. Adsorption data in the range of pH values (3.0-8.0) using Ni(II) and Cu(II) concentrations of 25+/-2mg/l and Zn(II) concentration of 30+/-2mg/l in solution were correlated using the linear forms of the Langmuir and Freundlich equations. The adsorption data were better fitted to the Langmuir isotherm since the correlation coefficients for the Langmuir isotherm were higher than that for the Freundlich isotherm. The fly ash with high calcium content (Afsin-Elbistan) was found to be a metal adsorbent as effective as activated carbon and, therefore, there are good prospects for the adsorptions of these metals on fly ash with high calcium content in practical applications in Turkey.     

Preparation of the diphenylcarbazone-functionalized silica gel and its application to on-line selective solid-phase extraction and determination of mercury by flow-injection spectrophotometry

A new solid-phase extractor, diphenylcarbazone-functionalized silica gel has been synthesized and confirmed by IR and Raman spectrometry. The new solid-phase extractor is found to be stable in 1-6 mol L(-1) HCl or H(2)SO(4), and also in common organic solvents. It can be used to separate and enrich Hg(II) selectively from eight metal ions with similar characteristics such as Cd(II), Ni(II), Co(II), Mn(II), Pb(II), Zn(II), Cu(II) and Fe(III). The pre-concentration factor is as high as 500. The results show that this new solid extractor has a good stability and can be reused for many times without decreasing its extraction percentage. The micro-column packed with diphenylcarbazone-functionalized silica gel was used for on-line solid-phase extraction and determination of mercury in real samples by flow-injection spectrophotometry. At the optimal conditions, the linear range and the detection limit for the determination of Hg(II) is found to be 1-1500 and 0.90 ng mL(-1), respectively. The relative standard deviation of 11 replicate measurements is less than 3%. The proposed method was demonstrated to be simple, fast, selective, low cost and less pollution.     

Evaluation of the emission characteristics of trace metals from coal and fuel oil fired power plants and their fate during combustion

Coal as well as fuel oil combustion generates emissions of potentially toxic trace pollutants including organic and inorganic chemical compounds besides major pollutants. A study on As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, Se, and Zn emissions from a 220 MW coal-fired power plant equipped with a electrostatic precipitators (ESPs) and 6 MW oil fired-power plant was carried out, using stack monitoring kit, Envirotech APM 620, which is similar to EPA Method 29. Simultaneous sampling of coal, fuel oil, oil waste, bottom ash, fly ash, flue gases, and particles associated with the gas phase has been performed. This sampling method was used for trace metal sampling. The content of all these metals in coal, oil, oil waste, bottom ash, fly ash have been determined by XRF, whereas their contents in the flue gases, and particles associated with the gas phase has been analyzed with ICP-AES. The mass balances obtained for trace elements were satisfactory in case of fuel oil based power plant, whereas in case of coal fired power plant, the mass balance for all the trace elements were below 50% except for the As, Se, and Hg. The enrichment factors for all trace metals was <1 in both cases. The above sampling method is moderately adequate method for trace element sampling in coal as well as oil fired power plants except for Hg. The results indicate that trace metals emissions were higher in coal-based power plant than the fuel oil-fired power plant.     

Adsorption of metal ions on lignin

This study investigated the adsorption of the heavy metal ions Pb(II), Cu(II), Cd(II), Zn(II), and Ni(II) on a lignin isolated from black liquor, a waste product of the paper industry. Lignin has affinity with metal ions in the following order: Pb(II)>Cu(II)>Cd(II)>Zn(II)>Ni(II). The adsorption kinetic data can be described well with a pseudosecond-order model and the equilibrium data can be fitted well to the Langmuir isotherm. Metal ion adsorption was strongly dependent on pH and ionic strength. Surface complexation modelling was performed to elucidate the adsorption mechanism involved. This shows that lignin surfaces contain two main types of acid sites attributed to carboxylic- and phenolic-type surface groups and the phenolic sites have a higher affinity for metal ions than the carboxylic sites.     

A Calixarene-Based Fluorogenic Reagent for Selective Mercury(II) Recognition

The first calixarene-based fluorogenic Hg(II)-selective extractant, 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(N-(5-dimethylaminonaphthalene-1-sulfonyl)carbamoylmethoxy)-26,28-dimethoxycalix[4]arene (2), is reported. In solvent extraction from aqueous acidic solutions (HNO(3)), 2 exhibits excellent selectivity for Hg(II) over a wide range of transition, alkali, and alkaline earth metal cations. Quenching of its fluorescence due to Hg(II) coordination is unaffected by the presence of 100-fold excesses of alkali metal cations, alkaline earth metal cations, Ag(I), Tl(I), Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Pd(II), Zn(II), or Fe(III).     

Role of Brassica juncea (L.) Czern. (var. Vaibhav) in the phytoextraction of Ni from soil amended with fly ash: selection of extractant for metal bioavailability

A pot experiment was carried out to study the potential of the plant of Brassica juncea for the phytoextraction of metal from fly ash amended soil and to study correlation between different pool of metals (total, DTPA, CaCl(2) and NH(4)NO(3)) and metal accumulated in the plant in order to assess better extractant for plant available metals. The results of total metal analysis in the soil revealed the presence of Cr, which was found below detection limit (BDL) in the plants. The fly ash (FA) amendments and soil samples were extracted with different extractants and the level of metal vary from one extractant to another. The regression analysis between total and extractable metals showed better regression for all the tested metals except Mn (R(2)=0.001) in DTPA extraction. Correlation coefficient between metal accumulation by the plant tissues and different pool of metals showed better correlation with DTPA in case of Fe, Zn and Ni, whereas, Cu was significantly correlated with NH(4)NO(3) and other metals (Pb, Mn) with CaCl(2). The soil analysis results revealed that the mobility and plant availability of metals (Fe, Mn, Zn, Ni) within the profiles of amended soils was influenced by the change in pH, however, Pb and Cu was not affected. The metal accumulation in total plant tissues was found in the order of Fe>Ni>Zn>Mn>Cu>Pb and its translocation was found more in upper part. The plants grown on soil amended with 25%FA have shown significant increase in plant biomass, shoot and plant height, whereas, no significant effect was observed in root length. The cluster analysis showed 10%FA behave differently on the basis of physico-chemical properties and metal behavior. Thus, it may be concluded that B. juncea can be used for phytoextraction of metals, especially Ni in fly ash amendment soil.     

Simultaneous multi-element detection of metal ions bound to a Datura innoxia material

An on-line detection scheme has been developed for the determination of metal ion affinities for binding to a plant-based substrate. This involves monitoring the effluent of a column packed with cell-wall fragments from the plant Datura innoxia for 27 different elements simultaneously by coupling the column to an ICP emission spectrometer. Previously accepted procedures for removing native metal ions from biological materials by washing the material with a pH 2 solution were found to be insufficient for this material. Measurable amounts of Na, Mg, Al, Ca, Mn, Fe, Ni, Cr, Zn, Cd, Pb, Ba, Sr, and Si were all detected in an effluent from the introduction of 1.0M HCl following washing the material in a pH 2 solution. Metal ion breakthrough curves for Cd(2+), Zn(2+), Ni(2+), Cu(2+), and Pb(2+) were found to exhibit an affinity order of Pb(2+)>Cu(2+)>Zn(2+) congruent with Cd(2+)>Ni(2+) for an equimolar mixture of these metal ions. This configuration also enabled the displacement of metal ions to be detected as the breakthrough curve for a subsequent metal ion was monitored. Comparison of Ni and Zn binding indicates a simple ion exchange model is insufficient to explain sequential binding of these metal ions.     

An optical fiber chemical sensor for mercury ions based on a porphyrin dimer

The synthesis of a novel fluoroionophore, 5-p-[[4-(10',15',20'-triphenyl-5'-porphinato) phenyloxyl]-1-butyloxyl]phenyl-10,15,20-triphenylporphine (DTPP), and its application for preparation of a Hg(II)-sensitive optical fiber chemical sensor are described. The response of the sensor is based on the fluorescence quenching of DTPP by coordination with Hg(II). The porphyrin dimer-based sensor shows a linear response toward Hg(II) in the concentration range 5.2 x 10(-7)-3.1 x 10(-4) mol x L(-1), with a working pH range from 2.4 to 8.0. The sensor shows excellent selectivity for Hg(II) over transition metal cations including Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II), and Fe(III). As a sensing agent, the porphyrin dimer shows obviously better fluorescence response characteristics toward Hg(II) compared to porphyrin monomer or metalloporphyrin. The effect of the composition of the sensor membrane was studied, and the experimental conditions were optimized. The sensor has been used for determination of Hg(II) in water samples.     

An efficient one pot synthesis of water-dispersible calix[4]arene polyhydrazide protected gold nanoparticles--a "turn off" fluorescent sensor for Hg[II] ions

In the present study, we report the synthesis of aqueous stable gold nanoparticles by using calix[4]arene polyhydrazide (CPH) as both reducing and capping agents. The calix[4]arene polyhydrazide reduced gold nanoparticles (CPH-AuNps) were characterized by UV/Vis, particle size analyzer (PSA) and transmission electron mictroscopy (TEM). The records confirmed high stability of CPH-AuNps in aqueous solution over a long period of time and even at varied pH. Additionally, CPH-AuNps have been investigated for its application as "Turn Off" fluorescent sensor for Hg[II]. A concentration of Hg[II] in the limit of 10 nM to 10 microM can be detected based on fluorescence quenching of the CPH-AuNPs and it was also concluded from the spectroscopic data that CPH-AuNPs possess excellent selectivity to Hg[II] over several metal ions like Pb[II], Cu[II], Cd[II], Mn[II], Zn[II] and Ni[II].     

Development and validation of a one-step immunoassay for determination of cadmium in human serum.

A sensitive and simple one-step immunoassay was developed and validated for quantitative determination of Cd(II) in human serum. In this method, a monoclonal antibody that recognizes Cd(II)-EDTA complexes was directly immobilized onto microwell plates. The serum sample containing metallothionein(MT)-bound and non-MT-bound Cd(II) was acidified to displace the Cd(II) from MT. The sample was then treated with metal-free EDTA to convert Cd(II) to Cd(II)-EDTA complexes. A mixture of Cd(II)-EDTA complexes derived from serum samples and Cd(II)-EDTA conjugated with peroxidase enzyme was incubated in the wells to compete for binding sites of the immobilized antibody. After addition of peroxidase substrate, the bound fraction of the enzyme conjugate was measured by a microplate reader, and the signal was inversely proportional to the concentration of the Cd(II) in the sample. The assay limit of detection was 0.24 microg/L, and the effective working range at coefficient of variation of < or = 10% was 0.24-100 microg/L. Analytical recovery of spiked Cd(II), in the concentration range between 0.8 and 50 microg/L, was 97.8 +/- 4.0%. The assay was selective for Cd(II); other metal ions (Mn, Co, Cu, Zn, Mg, Hg, Ca, Ni, Fe, and Pb), tested at concentrations considerably higher than those present in human serum, did not significantly interfere with the assay. The assay results correlated well with those obtained by graphite furnace atomic absorption spectrometry (r = 0.984).     

Preconcentration and determination of trace metal ions from aqueous samples by newly developed gallic acid modified Amberlite XAD-16 chelating resin

Gallic acid was immobilized on Amberlite XAD-16 by coupling it through -N=N group. The resulting chelating resin Amberlite XAD-16 gallic acid, characterized by thermogravimetric analysis (TGA), infrared (IR) spectra and BET analysis, was used to preconcentrate Cr(III), Mn(II),Fe(III),Co(II), Ni(II) and Cu(II)ions. The resin was employed for the preconcentration of the metal ions present in river water and industrial area aqueous samples. Several parameters like effect of pH, effect of time, effect of sample volume and flow rate of sample were investigated. The sorption capacities for the resin were 216 micromol g(-1), 180 micromol g(-1), 403 micromol g(-1), 281 micromol g(-1), 250 micromol g(-1) and 344 micromol g(-1) for Cr(III), Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) respectively. The preconcentration factors for Cr(III), Mn(II), Fe(III), Ni(II), Co(II) and Cu(II) were found out to be 300, 200, 400, 285.7, 300 and 400 respectively. The effect of various interfering ions was also studied. Results were validated by using standard addition method for river water sample.     

Behaviour of metals under the conditions of roasting MSW incinerator fly ash with chlorinating agents.

A total elemental analysis was performed on a municipal solid waste (MSW) fly ash sample, before and after it was treated at 1000 degrees C, to reveal the metal distribution between the volatile matter and the ash residue. Metals such as Pb, Zn, Cd, and to a lesser degree, Cr, Mn and Ni, were volatilized. Addition of chlorinating agents generally increased the volatility of certain elements. More acid resistant compounds were formed in the ash residue after the heat treatment using CaCl2 as a chlorinating agent. The efficiencies of volatilization of the metals, using Cl2 as a chlorinating agent, were generally higher compared with using CaCl2. However, CaCl2 was found to be a more selective chlorinating agent for volatilizing the heavy metals of concern, i.e., Pb, Cd, Zn and Cu. The efficiencies of volatilization of the recovered metals were approximately proportional to their standard free-energy changes (delta G(o) for the corresponding chlorination reactions.     

Effect of Cu(II), Cd(II) and Zn(II) on Pb(II) biosorption by algae Gelidium-derived materials

Biosorption of Pb(II), Cu(II), Cd(II) and Zn(II) from binary metal solutions onto the algae Gelidium sesquipedale, an algal industrial waste and a waste-based composite material was investigated at pH 5.3, in a batch system. Binary Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II) solutions have been tested. For the same equilibrium concentrations of both metal ions (1 mmol l(-1)), approximately 66, 85 and 86% of the total uptake capacity of the biosorbents is taken by lead ions in the systems Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II), respectively. Two-metal results were fitted to a discrete and a continuous model, showing the inhibition of the primary metal biosorption by the co-cation. The model parameters suggest that Cd(II) and Zn(II) have the same decreasing effect on the Pb(II) uptake capacity. The uptake of Pb(II) was highly sensitive to the presence of Cu(II). From the discrete model it was possible to obtain the Langmuir affinity constant for Pb(II) biosorption. The presence of the co-cations decreases the apparent affinity of Pb(II). The experimental results were successfully fitted by the continuous model, at different pH values, for each biosorbent. The following sequence for the equilibrium affinity constants was found: Pb>Cu>Cd approximately Zn.