Adsorption and detection of some phenolic compounds by rice husk ash of Kenyan origin

Rice husk ash (RHA) obtained from a rice mill in Kenya has been used as an inexpensive and effective adsorbent (and reagent) for the removal (and detection) of some phenolic compounds in water. The abundantly available rice mill waste was used in dual laboratory-scale batch experiments to evaluate its potential in: (i) the removal of phenol, 1,3-dihydroxybenzene (resorcinol) and 2-chlorophenol from water; and (ii) the detection of 1,2-dihydroxybenzene (pyrocatechol) and 1,2,3-trihydroxybenzene (pyrogallol) present in an aqueous medium. The studies were conducted using synthetic water with different initial concentrations of the phenolic compounds. The effects of different operating conditions (such as contact time, concentration of the phenolic compounds, adsorbent quantity, temperature, and pH) were assessed by evaluating the phenolic compound removal efficiency as well as the extent of their color formation reactions (where applicable). RHA exhibits reasonable adsorption capacity for the phenolic compounds and follows both Langmuir and Freundlich isotherm models. Adsorption capacities of 1.53 x 10(-4), 8.07 x 10(-5), and 1.63 x 10(-6) mol g(-1) were determined for phenol, resorcinol and 2-chlorophenol, respectively. Nearly 100% adsorption of the phenolic compounds was possible and this depended on the weight of RHA employed. For the detection experiments, pyrocatechol and pyrogallol present in water formed coloured complexes with RHA, with the rate of colour formation increasing with temperature, weight of RHA, concentration of the phenolic compounds and sonication. This study has proven that RHA is a useful agricultural waste product for the removal and detection of some phenolic compounds.     

Design of a Leaching Test Framework for Coal Fly Ash Accounting for Environmental Conditions

Fly ash from coal combustion contains trace elements which, on disposal or utilisation, may leach out, and therefore be a potential environmental hazard. Environmental conditions have a great impact on the mobility of fly ash constituents as well as the physical and chemical properties of the fly ash. Existing standard leaching methods have been shown to be inadequate by not representing possible disposal or utilisation scenarios. These tests are often criticised on the grounds that the results estimated are not reliable as they are not able to be extrapolated to the application scenario. In order to simulate leaching behaviour of fly ash in different environmental conditions and to reduce deviation between measurements in the fields and the laboratories, it is vital to study sensitivity of the fly ash constituents of interest to major factors controlling leachability. pH, liquid-to-solid ratio, leaching time, leachant type and redox potential are parameters affecting stability of elements in the fly ash. Sensitivity of trace elements to pH and liquid to solid ratio (as two major overriding factors) has been examined. Elements have been classified on the basis of their leaching behaviour under different conditions. Results from this study have been used to identify leaching mechanisms. Also the fly ash has been examined under different standard batch leaching tests in order to evaluate and to compare these tests. A Leaching Test Framework has been devised for assessing the stability of trace elements from fly ashes in different environments. This Framework assists in designing more realistic batch leaching tests appropriate to field conditions and can support the development of regulations and protocols for the management and disposal of coal combustion by-products or other solid wastes of environmental concern.     

Effects of leachant temperature and pH on leachability of metals from fly ash. A case study: Can thermal power plant, province of Canakkale, Turkey

Lignite powered electric generation plants result in increasing environmental problems associated with gaseous emissions and the disposal of ash residues. Especially, low quality coals with high ash content cause enormous quantities of both gaseous and solid fly ash emissions. The main problem is related to the disposal of fly ash, which, in many cases, contains heavy metals. It is known that toxic trace metals may leach when fly ash is in contact with water. In this study, fly ash samples obtained from the thermal power plant in the town of Can in Turkey were investigated for leachability of metals under different acidic and temperature conditions. The experimental results show that a decrease in pH of the leachant favors the extraction of metal ions from fly ash. A significant increase in the extraction of arsenic, cadmium, chromium, zinc, lead, mercury, and selenium ions from the ash is attributed to the instability of the mineral phases. These heavy metals concentrations increase with respect to increasing acidic conditions and temperature. Peak concentrations, in general, were found at around 30°C.     

Current status and perspectives of accelerated carbonation processes on municipal waste combustion residues

The increasing volumes of municipal solid waste produced worldwide are encouraging the development of processes to reduce the environmental impact of this waste stream. Combustion technology can facilitate volume reduction of up to 90%, with the inorganic contaminants being captured in furnace bottom ash, and fly ash/APC residues. The disposal or reuse of these residues is however governed by the potential release of constituent contaminants into the environment. Accelerated carbonation has been shown to have a potential for improving the chemical stability and leaching behaviour of both bottom ash and fly ash/APC residues. However, the efficacy of carbonation depends on whether the method of gas application is direct or indirect. Also important are the mineralogy, chemistry and physical properties of the fresh ash, the carbonation reaction conditions such as temperature, contact time, CO₂ partial pressure and relative humidity. This paper reviews the main issues pertaining to the application of accelerated carbonation to municipal waste combustion residues to elucidate the potential benefits on the stabilization of such residues and for reducing CO₂ emissions. In particular, the modification of ash properties that occur upon carbonation and the CO₂ sequestration potential possible under different conditions are discussed. Although accelerated carbonation is a developing technology, it could be introduced in new incinerator facilities as a “finishing step” for both ash treatment and reduction of CO₂ emissions.     

A comprehensive physico-chemical, mineralogical and morphological characterization of Indian mineral wastes

This paper provides a comprehensive characterization of mineral waste such as fly ash, bottom ash, slag and construction demolition (C&D) collected from four different thermal power plants, three steel plants and three C&D waste generation sites in India. To determine utilisation potential and environmental concerns, as received fly ash, bottom ash, slag and C&D waste were analysed for physico-chemical, mineralogical and morphological properties. The physico-chemical properties analysed include pH, moisture content, acid insoluble residue, loss on ignition(LOI), carbon content, fineness, chloride content, sulphate content, reactive silica content, XRF and heavy metal analysis. Morphological and mineralogical characteristics were investigated using scanning electron microscopy–energy dispersive X-ray. Particle size distribution was obtained using particle size analyser. The material analysed has different compositions and were selected with a view to determine their suitability for different applications in cement and concrete industry and for further research studies.     

Characterisation of individual aerosol particles on moss surfaces: implications for source apportionment

The size, morphology and chemical composition of 8405 particles on moss surfaces (Hylocomium splendens) was investigated by scanning electron microscopy and energy-dispersive X-ray microanalysis. Two moss samples from three locations in Southern Norway (Alg?rd, Birkeland, Neslandsvatn) and two sampling years (1977 and 2005) each were selected leading to a total of 12 samples investigated. At all three locations, particle deposition decreased substantially with time. The major particle groups encountered include silicates, iron-rich silicates, metal oxides/hydroxides, iron oxides/hydroxides, carbonates, carbon-rich particles, silicate fly ashes, iron-rich silicate fly ashes, and iron oxide fly ashes. Between 1977 and 2005, the relative number abundance of the three fly ash groups decreased substantially from approximately 30-60% to 10-18% for the small particles (equivalent projected area diameter <1 microm), and from 10-35% to 2-9% for large particles with diameters ≥1 microm. This decrease of fly ash particles with time was overlooked in previous papers on atmospheric input of pollutants into ecosystems in Southern Norway. In general, the presence of fly ash particles is ignored in most source apportionment studies based on bulk chemical analysis. Consequently, the geogenic component (crustal component) derived from principal component analysis is overestimated systematically, as it has a similar chemical composition as the fly ash particles. The high abundance of fly ashes demonstrates the need to complement source apportionment based on bulk chemistry by scanning electron microscopy in order to avoid misclassification of this important anthropogenic aerosol component.     

A new method for municipal solid waste incinerator (MSWI) fly ash inertization, based on colloidal silica

Municipal solid waste incineration (MSWI) is a straightforward way to manage waste, however the disposal of process byproducts, mainly bottom and fly ash, is still a problem, because of their hazardous contents. Fly ash is a byproduct of many other processes that involve combustion to produce energy. In this paper we present and discuss a new method for MSWI fly ash inertization, mainly based on the use of colloidal silica as a stabilization agent for metals. In the patented procedure, fly ash of different provenance can be used to produce an inert and non-hazardous material, that can be reused. In fact to make the recovery process more efficient, landfilling should be totally avoided. For this reason, to enhance the possibility of reuse, a washing process, for salts recovery, is proposed as a final step of the inertization procedure. The obtained inert material is called COSMOS (COlloidal Silica Medium to Obtain Safe inert), and it is composed of calcium carbonate, calcium sulfate, silicon oxide and a wide quantity of non-soluble amorphous compounds. COSMOS does not contain any corrosive salts. This makes it extremely interesting for cement industry applications with several other advantages, and environmental benefits. The new proposed inertization procedure appears very promising, because it allows MSWI fly ash to be considered a valuable resource. Thanks to the obtained results, a demonstration project, in the frame of LIFE+, has been funded by the European Commission (LIFE+ 2008 project ENV/IT/000434, ).     

Determination and evaluation of hexavalent chromium in power plant coal combustion by-products and cost-effective environmental remediation solutions using acid mine drainage

The chromium species leaching from a coal combustion fly ash landfill has been characterized as well as a novel approach to treat leachates rich in hexavalent chromium, Cr(VI), by using another natural waste by-product, acid mine drainage (AMD), has been investigated during this study. It is observed that as much as 8% (approximately 10 microg g(-1) in fly ash) of total chromium is converted to the Cr(VI) species during oxidative combustion of coal and remains in the resulting ash as a stable species, however, it is significantly mobile in water based leaching. Approximately 1.23 +/- 0.01 microg g(-1) of Cr(VI) was found in the landfill leachate from permanent deposits of aged fly ash. This study also confirmed the use of AMD, which often is in close proximity to coal combustion by-product landfills, is an extremely effective and economical remediation option for the elimination of hexavalent chromium in fly ash generated leachate. Speciated isotope dilution mass spectrometry (SIDMS), as described in EPA Method 6800, was used to analytically evaluate and validate the field application of the ferrous iron and chromate chemistry in the remediation of Cr(VI) runoff.     

Investigation into the relationship between major and minor element contents and particle size and leachability of boron in fly ash from coal fuel thermal power plants

A basic investigation of boron in discharged fly ash by coal fuel thermal power plants in several worldwide locations was carried out. Eight kinds of fly ash sample were prepared from eight coal fuel thermal power plants. Two of the fly ash samples were used to examine the relationship between the concentration of boron in fly ash and the particle size. When the particle size of fly ash is smaller, there is a possibility that it will be released into the air and spread over a wide area in the environment. However, it has become apparent that fly ash of smaller particle size has a higher concentration of boron and a higher enrichment factor. In other fly ash samples, the boron contents were examined and leaching tests were carried out. There is acidic fly ash as well as alkaline fly ash that contains larger amounts of acidic or basic salts. On alkaline fly ash, when the concentration of boron bound to Fe-Mn oxide is low; it has become apparent that leaching boron is increased in a solution with lower pH of approximately 4 which is nearly the pH of acid rain.     

Assessment of oxidative stress markers and concentrations of selected elements in the leaves of Cassia occidentalis growing wild on a coal fly ash basin

Assessment of oxidative stress levels and tissue concentrations of elements in plants growing wild on fly ash basins is critical for realistic hazard identification of fly ash disposal areas. Hitherto, levels of oxidative stress markers in plants growing wild on fly ash basins have not been adequately investigated. We report here concentrations of selected metal and metalloid elements and levels of oxidative stress markers in leaves of Cassia occidentalis growing wild on a fly ash basin (Badarpur Thermal Power Station site) and a reference site (Garhi Mandu Van site). Plants growing on the fly ash basin had significantly high foliar concentration of As, Ni, Pb and Se and low foliar concentration of Mn and Fe compared to the plants growing on the reference site. The plants inhabiting the fly ash basin showed signs of oxidative stress and had elevated levels of lipid peroxidation, electrolyte leakage from cells and low levels of chlorophyll a and total carotenoids compared to plants growing at the reference site. The levels of both protein thiols and nonprotein thiols were elevated in plants growing on the fly ash basin compared to plants growing on the reference site. However, no differences were observed in the levels of cysteine, reduced glutathione and oxidized glutathione in plants growing at both the sites. Our study suggests that: (1) fly ash triggers oxidative stress responses in plants growing wild on fly ash basin, and (2) elevated levels of protein thiols and nonprotein thiols may have a role in protecting the plants from environmental stress.     

Speciation of nickel in Canadian subbituminous and bituminous feed coals, and their ash by-products

The nickel species in the feed coals and ash by-products from seven Canadian power plants (including one with a fluidized bed combuster) burning local subbituminous and bituminous coals with sulfur contents ranging from 0.22 to 3.6% have been examined using nickel XANES spectroscopy. XANES spectroscopy of Ni in coal and coal derived ash is complicated by a poor signal : noise ratio due to fluorescence of the much more abundant iron in the coal. Nevertheless, it has proved possible to show that the Ni environment in coals varies from largely oxidic species to mixtures of Ni-containing oxide and sulfide species. The nickel in one oxidized coal appears to be present as nickel sulfate. Nickel in all bottom and fly ash samples examined appears also to be present largely in oxygen anion environments. With the exception of one fly ash sample, for which the Ni exhibited spectral features similar to those for Ni(2+) in spinel or oxide phases, the nickel in the bottom and fly ash samples appears to exist largely as Ni(2+) in environments similar to those reported for Ni in silicate glasses. The data obtained indicate that the presence of potentially carcinogenic nickel sulfides in ash by-products from combustion of these coals is unlikely.     

Uptake of arsenic by alkaline soils near alkaline coal fly ash disposal facilities

The attenuation of arsenic in groundwater near alkaline coal fly ash disposal facilities was evaluated by determining the uptake of arsenic from ash leachates by surrounding alkaline soils. Ten different alkaline soils near a retired coal fly ash impoundment were used in this study with pH ranging from 7.6 to 9.0, while representative coal fly ash samples from two different locations in the coal fly ash impoundment were used to produce two alkaline ash leachates with pH 7.4 and 8.2. The arsenic found in the ash leachates was present as arsenate [As(V)]. Adsorption isotherm experiments were carried out to determine the adsorption parameters required for predicting the uptake of arsenic from the ash leachates. For all soils and leachates, the adsorption of arsenic followed the Langmuir and Freundlich equations, indicative of the favorable adsorption of arsenic from leachates onto all soils. The uptake of arsenic was evaluated as a function of ash leachate characteristics and the soil components. The uptake of arsenic from alkaline ash leachates, which occurred mainly as calcium hydrogen arsenate, increased with increasing clay fraction of soil and with increasing soil organic matter of the alkaline soils. Appreciable uptake of arsenic from alkaline ash leachates with different pH and arsenic concentration was observed for the alkaline soils, thus attenuating the contamination of groundwater downstream of the retired coal fly ash impoundment.     

Impact of Fly Ash from Coal-Fired Power Stations in Delhi, with Particular Reference to Metal Contamination

Indraprastha Power Station (IPP Stn) and Rajghat Power House (RPH), owned by Delhi Electric Supply Undertaking, are both coal-fired power stations located on Ring Road in New Delhi. Ash content of the coal used ranges between 38–47%. The ash is collected in electrostatic precipitators which have an efficiency of 99.3% (IPP station), and 99.7% (RPH). There are instances of major dust pollution around the power stations from fly ash dispersal. The main method of disposal of fly ash from the power stations is by mixing with water, the resultant slurry is pumped through pipes to ash disposal ponds. The supernatant from these ponds is discharged into River Yamuna. Field studies have revealed large quantities of fly ash being deposited into the river. Local populations of Eichhornia crassipes have reduced dramatically between 1987–1995, with a marked reduction in the year 1994–1995. Field studies, conducted in January, 1995 have investigated the impact of fly ash dispersal in the Delhi region with particular reference to metal contamination. Elemental concentrations for a range of elements are determined by ICP-AES in fly ash and top soils along four transects from the power stations up to a distance of 8 km. The effects of fly ash leachates from the ash settling ponds on the river are determined by analyzing river overbank soils and vegetation for their elemental contents. It is concluded that fly ash dispersal from the stacks are a source of alkali, alkaline-earth and to some extent heavy metals in soils in the vicinity of the power stations, and enrichment of elements in river overbank soils are a result of discharge of fly ash leachates from ash disposal ponds. However, the impact from both these sources of metal contamination is not large enough to give cause for concern. Marked reduction in populations of Eichhornia crassipes downstream of the river where it receives leachates from the ash disposal ponds are attributed to turbidity of the ash pond leachates and metal toxicity. Elemental enrichment in the floodplain soils, as a result of fly ash particle deposition during monsoons, may enhance the horticultural value of these soils as is shown by a healthy cultivated crop of Brassica juncea.     

Leaching Characteristics of Fly Ash from Thermal Power Plants of Soma and Tunçbilek, Turkey

Use of lignite in power generation has led to increasing environmental problems associated not only with gaseous emissions but also with the disposal of ash residues. In particular, use of low quality coal with high ash content results in huge quantities of fly ash to be disposed of. The main problem related to fly ash disposal is the heavy metal content of the residue. In this regard, experimental results of numerous studies indicate that toxic trace metals may leach when fly ash contacts water. In this study, fly ash samples obtained from thermal power plants, namely Soma and Tunçbilek, located at the west part of Turkey, were subjected to toxicity tests such as European Committee for standardization (CEN) and toxicity characteristic leaching (TCLP) procedures of the U.S. Environmental Protection Agency (U.S. EPA). The geochemical composition of the tested ash samples from the power plant show variations depending on the coal burned in the plants. Furthermore, the CEN and TCLP extraction results showed variations such that the ash samples were classified as `toxic waste' based on TCLP result whereas they were classified as `non-toxic' wastes based on CEN results, indicating test results are pH dependent.     

A review on applicability of naturally available adsorbents for the removal of hazardous dyes from aqueous waste

The effluent water of many industries, such as textiles, leather, paper, printing, cosmetics, etc., contains large amount of hazardous dyes. There is huge number of treatment processes as well as adsorbent which are available for the processing of this effluent water-containing dye content. The applicability of naturally available low cast and eco-friendly adsorbents, for the removal of hazardous dyes from aqueous waste by adsorption treatment, has been reviewed. In this review paper, we have provided a compiled list of low-cost, easily available, safe to handle, and easy-to-dispose-off adsorbents. These adsorbents have been classified into five different categories on the basis of their state of availability: (1) waste materials from agriculture and industry, (2) fruit waste, (3) plant waste, (4) natural inorganic materials, and (5) bioadsorbents. Some of the treated adsorbents have shown good adsorption capacities for methylene blue, congo red, crystal violet, rhodamine B, basic red, etc., but this adsorption process is highly pH dependent, and the pH of the medium plays an important role in the treatment process. Thus, in this review paper, we have made some efforts to discuss the role of pH in the treatment of wastewater.     

Serial batch leaching procedure for characterization of coal fly ash

Although many leaching methods have been used for various purposes by research groups, industries, and regulators, there is still a need for a simple but comprehensive approach to leaching coal utilization by-products and other granular materials in order to estimate potential release of heavy metals when these materials are exposed to natural fluids. A serial batch characterization method has been developed at the National Energy Technology Laboratory that can be completed in 2–3 days to serve as a screening tool. The procedure provides an estimate of cumulative metals release under varying pH conditions, and leaching the sample at increasing liquid/solid ratios can indicate the rate at which this process will occur. This method was applied to eight fly ashes, adapted to the acidic or alkaline nature of the ash. The leachates were analyzed for 30 elements. The test was run in quadruplicate, and the relative standard deviation (RSD) was used as a measure of method reproducibility. RSD values are between 0.02 and 0.70, with the majority of the RSD values less than 0.3. The serial batch leaching procedure was developed as a simple, relatively quick, yet comprehensive method of estimating the risk of heavy metal release from fly ash when it is exposed to natural fluids, such as acid rain or groundwater. Tests on a random selection of coal fly ashes have shown it to be a reasonably precise method for estimating the availability and long-term release of cations from fly ash.     

宁东能源化工基地固体废物中汞含量分布及对环境影响

通过分析宁东能源化工基地各大燃煤电厂以及煤化工厂固体废物样品,研究了固体废物中的汞分布规律及环境影响。结果表明:汞易在脱硫石膏、粉煤灰和气化粗渣中富集,汞浓度分别为0.16、0.24、0.15 mg/kg,而炉渣和气化细渣中的汞含量则相对较低,分别为0.05、0.03 mg/kg。通过化学组成及汞含量数据分析发现,出现这种情况的原因与汞本身易挥发的性质和固体废物的物化性质有关。此外,通过固体废物浸出毒性实验发现,脱硫石膏、粉煤灰、气化粗渣的浸出汞浓度小于浓度限值(0.1 mg/L),而气化细渣因锅炉回用,不参与填埋,汞又不易在炉渣中富集,故总体上宁东能源化工基地的固体废物无汞环境污染倾向。     

Optimization of pulp mill effluent treatment with catalytic adsorbent using orthogonal second-order (Box-Behnken) experimental design

Novel catalytic adsorbent (ruthenium on carbon) was employed for the treatment of pulp mill effluent in the presence of hydrogen peroxide. Mathematical model and optimization of the process regarding the most favorable COD (%), TOC (%) and color (%) removal rates was developed and performed with experimental design taking into account catalytic adsorption process kinetics. As the initial experimental design, 3(3-1) half-fractional factorial design (H-FFD) was accomplished at two levels to study the significance of the main effects, such as catalytic adsorbent (g l(-1)) and hydrogen peroxide (ppm) concentrations using the response surface methodology (RSM). Finally, a four factor-three coded level central composite design (CCD) with 28 runs was performed in order to fit a second-order polynomial model. Validation of the model was accomplished by different criteria including coefficient of determination and the corresponding analysis of variance. The achieved removal rates for TOC (up to 75%), COD (up to 73%) and color (up to 68%) were observed for the defined optimal conditions: 1g l(-1) of ruthenium on carbon, 7 ppm of hydrogen peroxide, pH = 4 and ambient temperature. The proposed method benefited significantly improved TOC, COD and color removal efficiency, regenerability and reusability of the catalytic adsorbent and unaltered initial pH of an effluent in comparison to traditional adsorption or oxidation processes.     

Evaluation of genotoxicity of coal fly ash in Allium cepa root cells by combining comet assay with the Allium test

Fly ash is a by-product of coal-fired electricity generation plants. Its utilization and disposal is of utmost importance. Using onion (Allium cepa) root tip system, the present study was carried out to evaluate the potential toxic and genotoxic effects of fly ash, collected from a thermal power plant in West Bengal, India. Prior to testing, the collected fly ash sample was mixed with sand in different proportions. Allium bulbs were allowed to germinate directly in fly ash and after five days the germinating roots were processed for the Allium test. Additionally, the Allium test was adapted for detecting DNA damage through comet assay. The results from the Allium test indicate that fly ash at 100% concentration inhibits root growth and mitotic indices; induces binucleated cells as a function of the proportion, but is not toxic at very low concentration. In the comet assay, a statistical increase for DNA strand breaks was found only at higher concentrations. The sample was analyzed by flame atomic absorption spectrometer for Zn, Pb, Cu, Ni, Cd and As, whose presence could partly be responsible for the toxicity of fly ash. The study concludes that the classical Allium test can give a more comprehensive data when done in combination with the comet assay, which is faster, simpler and independent of mitosis. Also when fly ash is used for other purposes in combination with soils, it should be judiciously used at very low concentrations in order to protect the ecosystem health from any potential adverse effects.     

某粉煤灰堆放场对周围岩溶地下水的影响分析

结合粉煤灰堆放场的水文地质状况,通过稳定同位素示踪、浸溶和淋溶试验,探讨了灰场对周围岩溶地下水的影响。结果表明,堆场灰水已经达到下游部分水井,堆场在大气降水和冲灰水的浸泡、淋溶作用下,其中的Cr6+、F-和钙镁盐类大量析出并随灰水一起下渗,石灰岩碎石虽对氟化物有一定的吸附作用,但能力有限。根据试验数据分析认为,该粉煤灰堆放场是焦作市北中部岩溶地下水Cr6+、F-和总硬度升高的主要原因。