Comparative study of the microstructural and magnetic properties of fly ashes obtained from different thermal power plants in West Bengal, India

This paper deals with the physical nature of the fly ashes obtained from two thermal power plants, situated in West Bengal, India. The fly ash samples are characterized by using comprehensive techniques with an emphasis on their ultrafine nature. The particle sizes of the samples are estimated using scanning electron microcopy (SEM) and found to lie within 0.18–5.90 μm. For morphology and compositional analysis, we also use SEM coupled with energy dispersive X-ray spectrometry. From X-ray study of the fly ashes the nature of conglomeration is seen to be crystalline, and the major components are mullite (Al₆Si₂O₁₃) and quartz (SiO₂). The magnetic measurement of the fly ash samples was carried out by SQUID magnetometer. ⁵⁷Fe Mössbauer spectra are obtained using a conventional constant-acceleration spectrometer with a ⁵⁷Co/Rh Mössbauer source. The hyperfine parameters obtained, in general, support the findings as made from XRD analysis and provide a quantitative measure of different iron ions present in the samples. The paper presents experimental data on the physical aspects of the fly ash samples of the thermal power plants which comprise coarse, fine, and ultrafine magnetic particulate materials and attempts to provide an exhaustive analysis.     

Fractions and leaching characteristics of mercury in coal

A huge amount of coal is always stored in open spaces in coal-fired power plants before combustion. Mercury released from coal by rain or flowing water is an environmental risk and can cause contamination of the soil around the storage area. To better understand mercury pollution and to control mercury emission before combustion, it is necessary to determine the mobility and leaching characteristics of mercury from coal. In this study, we collected ten coal samples from one coal-fired power plant and proposed a sequential extraction procedure to get five fractions of mercury for evaluation. Elemental Hg was found as the most dominant fraction, and sulfate Hg was shown to be the second largest fraction. The mercury in the organic and the soluble fractions were not the major fractions, but they should still be considered because of their high mobility.     

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.     

Investigation on chemical species of arsenic, selenium and antimony in fly ash from coal fuel thermal power stations

Investigations of the existing chemical forms and the concentrations of arsenic (As), selenium (Se) and antimony (Sb) in samples of fly ash obtained from six coal-fired power stations in various countries were carried out. The concentration of As was found to vary from 5.4 to 22.3 mg kg(-1), and the most common mode of occurrence of As in the fly ashes is in association with carbonates or Fe-Mn oxides. The concentrations of Se and Sb ranged from 2.3-5.2 and 1.0-3.9 mg kg(-1), respectively. The dominant chemical forms of Se and Sb in the fly ashes were as extractable species. Also, water-soluble As, Se and Sb in the fly ashes were extracted, and the chemical species of As, Se and Sb in the extract determined using HPLC-ICP-MS. This was done as the potential release of soluble As, Se and Sb through leaching of fly ash is of environmental concern. The most abundant form of As in the extract was the low toxicity As(V). The main species of Se was Se(IV), although it was found that the ratio of Se(VI) to Se(IV) in acidic fly ashes is higher than in alkaline fly ash samples. Antimony was mostly present as Sb(III).     

Assessment of organochlorine pesticide residues in Indian flue-cured tobacco with gas chromatography-single quadrupole mass spectrometer

Presence of pesticide residues in tobacco increases health risk of both active and passive smokers, apart from the imminent potential health problems associated with it. Thus, monitoring of pesticide residue is an important issue in terms of formulating stringent policies, enabling global trade and safeguarding the consumer’s safety. In this study, a gas chromatography-single quadrupole mass spectrometry (GC-MS) method based upon quantifier-qualifier ions (m/z) ratio was employed for detecting and assessing ten organochlorine pesticide residues (α-HCH, β-HCH, γ-HCH, δ-HCH, 2,4-DDT, 4,4-DDT, endrin, α-endosulfan, β-endosulfan and endosulfan sulphate) in 152 flue-cured (FC) tobacco leave samples from two major tobacco growing states, Karnataka and Andhra Pradesh, of India. In the majority of samples, pesticide residue levels were below the limit of quantification (LOQ). In few samples, pesticide residues were detected and they found to comply with the guidance residue levels (GRL) specifications of the Cooperation Center for Scientific Research Relative to Tobacco (CORESTA). Detection of the phase out pesticides like DDT/HCH might be due to transfer of persistent residues from the environmental components to the plant. This is the first report on these ten organochlorine pesticide residues in Indian FC tobacco.     

New approaches for assessment of occupational exposure to metals using on-site measurements

Traditional assessment of occupational exposure to metals typically involves static or personal aerosol sampling on a membrane filter followed by a laboratory determination of the metal content on the filter sample. These techniques give results with high accuracy and low detection limits. However, they all have a drawback in that, since the samples have to be analysed in a laboratory, the results will usually be obtained days or weeks after the sampling took place. Today there is available a new generation of portable electronic micro-balances and instruments for metal analysis based on X-ray fluorescence. These instruments will make on-site measurements of metal exposure possible, which opens the way for new approaches for assessment of occupational exposure to metals. In combination with high-flow pumps, short-term sampling is possible, which allows monitoring of the exposure variation during a work shift as well as the exposure during individual work tasks of short duration. Screening measurements and emission measurements are other examples of monitoring that are facilitated using on-site determinations. Measure control monitoring can effectively be performed using on-site measurements and is an effective tool in the assessment of workplace improvements. On-site determinations can also form an effective and pedagogic tool showing workers how to perform specific tasks and demonstrating the effectiveness of different measures intended to improve their work environment. Other examples are the assessment of skin exposure using aerosol deposition on pads and screening of contamination using bulk samples.     

Decadal time-scale monitoring of forest fires in Similipal Biosphere Reserve,India using remote sensing and GIS

Analyzing the spatial extent and distribution of forest fires is essential for sustainable forest resource management. There is no comprehensive data existing on forest fires on a regular basis in Biosphere Reserves of India. The present work have been carried out to locate and estimate the spatial extent of forest burnt areas using Resourcesat-1 data and fire frequency covering decadal fire events (2004–2013) in Similipal Biosphere Reserve. The anomalous quantity of forest burnt area was recorded during 2009 as 1,014.7 km². There was inconsistency in the fire susceptibility across the different vegetation types. The spatial analysis of burnt area shows that an area of 34.2 % of dry deciduous forests, followed by tree savannah, shrub savannah, and grasslands affected by fires in 2013. The analysis based on decadal time scale satellite data reveals that an area of 2,175.9 km² (59.6 % of total vegetation cover) has been affected by varied rate of frequency of forest fires. Fire density pattern indicates low count of burnt area patches in 2013 estimated at 1,017 and high count at 1,916 in 2004. An estimate of fire risk area over a decade identifies 12.2 km² is experiencing an annual fire damage. Summing the fire frequency data across the grids (each 1 km²) indicates 1,211 (26 %) grids are having very high disturbance regimes due to repeated fires in all the 10 years, followed by 711 grids in 9 years and 418 in 8 years and 382 in 7 years. The spatial database offers excellent opportunities to understand the ecological impact of fires on biodiversity and is helpful in formulating conservation action plans.     

Immobilization of B,F, Cr,and As in alkaline coal fly ash through an aging process with water

Fourteen different alkaline coal fly ashes (CFAs) were used for the experiment, in which each sample was mixed with water to be 28.6 % of water content (wt/wt) and aged for 1–4 weeks at 10–30 °C. This simple treatment is advantageous for decreases in water-soluble B, F, Cr, and As. Compared to non-aged CFAs, their water-soluble fractions remained 0.56–88 %, 21–85 %, 0.37–93 % and 2.6–88 %, respectively, after aging for a week at 20 °C, although the amounts of Cr and As released from some CFA samples increased. Considering the significant decrease in elution of sulfate, Ca and Al after aging, the immobilization, namely prevention of toxic element elution, could be related to formation of secondary minerals such as portlandite, gypsum and ettringite. Immobilization of B and Cr tends to proceed preferentially under colder conditions. Aging at higher temperatures enhances the leachability of Cr in some CFA samples. Contrary to the behavior of B and Cr, water-soluble F effectively decreases under warmer conditions.     

ICP－AES光谱法同时测定团体废物浸出液中的多种金属元素

采用翻转振荡方式以水为浸提剂浸提钢渣、尾矿渣、铬渣、铅渣、粉煤灰和电镀污泥试样，过滤后的浸提液经ＤＤＴＣ／ＣＣｌ４体系萃取富集后，用ＩＣＰ－ＡＥＳ法同时测定了Ｃｕ、Ｐｂ、Ｚｎ、Ｃｄ、Ｎｉ、Ｆｅ、Ｍｎ、Ｃｏ和Ｖ等多种金属元素．方法具有较好的精密度和准确度，宜于推广应用。     

X-ray diffraction spectrometric analysis of nickel refinery aerosols,process materials and particulates isolated from worker lung tissues

Results are reported of X-ray diffraction analysis of extracts derived from lungs of two nickel refinery workers and of three stationary air samples collected inside a nickel refinery. Since environmental samples from the 1950s and 1960s do not exist, two archived production control samples from that period were also analyzed. Because nickel has been found in respiratory tissue of workers retired for more than twenty years, it was likely that the residual nickel compounds must be rather insoluble. Preliminary surveys showed that sulfur was not present in the lung tissue deposits and thus water-soluble and sulfidic nickel were therefore extracted from the ten process samples before the X-ray analysis. A common compound that was found in all 10 samples was trevorite. This is a spinel-type mineral, much like magnetite where the divalent iron is replaced by nickel. It may be formed when trivalent iron reacts with nickel at 1100 degrees C. It has magnetic properties and is very insoluble. Samples from the lungs were obtained by burning off the organic tissue at 630 degrees C. Due to a relatively high detection limit for the X-ray diffraction technique, we were initially not able to detect any mineral nickel compound. But when particles extracted with a magnet were analyzed, a very clear diffraction pattern of trevorite was identified. The main residue after the magnetic separation had a low concentration of nickel (4 microg g(-1)), which suggests that trevorite was the dominating, if not the only, nickel compound present. In addition, chemical analyses were performed on 13 tissue samples from one single lung; one from each main bronchus, two from each lobe, and an additional one from the lower right lobe. Statistical testing showed a highly significant correlation between the five elements determined: Ni, Co, Cu, Fe and Cr. This suggests that these metals are isomorphous and substitute for each other in the mineral structure. These results may indicate that the nickel left in the lungs some years after exposure is trevorite, and may be biologically inert. However, further speciation of nickel compounds in the lungs seems warranted, and trevorite should be tested for its potential toxic effects.     

Inputs of heavy metals due to agrochemical use in tobacco fields in Brazil’s Southern Region

Only a few studies have assessed the joint incorporation of heavy metals into agricultural systems based on the range of agrochemicals used on a specific agricultural crop. This study was conducted to assess the heavy metals input through application of the main agrochemicals used in Brazilian tobacco fields. A total of 56 samples of different batches of 5 fertilizers, 3 substrates, 8 insecticides, 3 fungicides, 2 herbicides, and 1 growth regulator commonly used in the cultivation of tobacco in Brazil’s Southern Region were collected from 3 warehouses located in the States of Rio Grande do Sul, Santa Catarina, and Paraná. The total As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, and Zn content of the samples was then determined and compared with the regulations of different countries and information found in the available literature. The fertilizers were identified as the primary source of heavy metals among the agrochemicals used. Application of pesticides directly to the shoots of tobacco plants contributed very little to the supply of heavy metals. The agrochemicals used in Brazilian tobacco fields provide lower inputs of the main heavy metals that are nonessential for plants than those registered in the international literature for the majority of crop fields in different regions of the world.     

Cigarette smoking and nickel exposure

The tobacco plant contains nickel and several other toxic metals, most probably absorbed from the soil, fertilizing products or from pesticides. It has been stated that nickel in a burning cigarette might form the volatile, gaseous compound, nickel tetracarbonyl, and thereby be introduced into the respiratory tract. Accordingly, the main objective of the present study was to find out if nickel content in inhaled smoke from ordinary cigarettes and nickel-contaminated cigarettes handmade by nickel process workers might be a supplementary source of nickel exposure to cigarette smoking process workers leading to additional risk of occupational respiratory cancer in these workers. Blood and urine samples from 318 randomly selected employees from Falconbridge Nickel Refinery in Kristiansand, Norway, allocated to 197 smokers and 121 non-smokers, were analysed for nickel content. Nickel quantities in tobacco from various cigarette brands, from nickel-contaminated cigarettes made by process workers or from cigarettes added known amounts of various nickel salts were analysed before being smoked. The cigarettes were smoked in a smoking machine device applying an electrostatic filter. Blood and urine, tobacco, ash and precipitates in the filter from the main stream smoke of the cigarettes were analysed for nickel quantities by atomic absorption spectrometry methods as previously described by the authors. The nickel concentrations in blood plasma and urine were quite similar among smokers and non-smokers, 6.2 and 48.1 microg L(-1) in smokers, and 6.4 and 50.5 microg L(-1) in non-smokers respectively. We recovered 1.1% or even less of nickel in the mainstream smoke after smoking the entire cigarettes without leaving any butt. Most of the tobacco nickel was recovered in the ash. We conclude that the inhaled nickel in the working atmosphere is probably the main source of the nickel exposure to the respiratory tract in these workers. It remains to be determined why cigarette smoking still seems to be a decisive cofactor in the development of respiratory tract cancer in nickel workers.     

Correlation between soil characteristics and lead and cadmium content in the aboveground biomass of Virginia tobacco

The study was conducted on alluvial-meadow, maroon-forest soils and vertisols with Virginia tobacco. The total content of lead and cadmium is measured through decomposition by HF, HClO₄, and HNO₃ acids. A solution of 0.005 M diethylentriaminepentaacetic acid + 0.1 M triethanolamine, pH 7.3 was used for extraction of the elements’ mobile forms from soils. The preparation of plant samples was made by means of dry ashing and dissolution in 3 M HCl. An atomic absorption spectrometer “Spektra AA 220” of the Australian company Varian was used for determination of Pb and Cd content in the soil and plant samples. Certified reference materials (three soils and tobacco leaves) were also analyzed for the verification of the accuracy of Pb and Cd determination. A correlation/regression analysis was conducted between pH, humus content, total and mobile forms of lead and cadmium in the soil, and the concentration of these elements in the aboveground biomass of Virginia tobacco. It was established that there are no statistically significant dependencies determined between soil pH and lead concentration in the plant organs of Virginia tobacco. Regressional dependencies of great significance were determined between the humus content, total and mobile lead and cadmium in the soil, and the element concentration in the leaves of the three harvesting zones.     

Development of a new automated clean-up system for the simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas emissions by GPC-SPE

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples.     

Micromorphology and chemistry of airborne particles in Brussels during agriculture working periods in surrounding region

The main objective of our research was to compare the airborne particle micromorphology and chemistry in the Brussels environment during agriculture working periods in the surrounding farming region. We used specific methods and instrumentation that are adapted to the climate peculiarities of the Brussels region, the period of investigations (12 months) and the proposed objectives. For the agricultural works we defined the following six periods: before sowing, sowing, after sowing, before harvest, harvest and after harvest. The results indicate a possible temporal correlation between agricultural work periods and airborne particle concentration, micromorphology and chemistry in the Brabant-Brussels region. For wheat and corn plant-growth periods, the average particle size, defined as the area obtained by a planar projection of the particulate, showed important variations in time. For sugar beet and endive, the average area size variations are less important. The roughness and sphericity parameters for the growth periods of the four different plants also showed significant differences. Many of the larger particulates (> 10 microm) are aggregates of even finer particles coated with many still finer ones. The airborne particle chemistry averages (atomic percentage At%), showed that three constituents (Si, S and Fe) dominate all the samples (except for particles 3-10 microm in size, which contain a relatively large percentage of Al). Applying similar investigation methods to study the correlations between airborne particle dynamics in urban zones and the agriculture working periods in their surrounding regions could be of interest to better understand the complexity of the PM problematic.     

Organochlorine Pesticide Residues in Milk and Blood of Women from Anupgarh, Rajasthan, India

Anupgarh is the most fertile area of Rajasthan state where a variety of seasonal crops are grown. The availability of three manmade canals has enhanced the agricultural activities in this area. The farmers use huge amounts of pesticides to increase the crop productivity. Exposure of humans to these hazardous chemicals occurs directly in the fields and indirectly due to consumption of contaminated diet, or by inhalation or by dermal contact. The organochlorine pesticides are reported to be lipophilic and their presence in human milk and blood has been documented in different parts of the world. Blood and milk samples were collected from lactating women who were divided into four groups on the basis of different living standards viz residence area, dietary habits, working conditions and addiction to tobacco. The level of total organochlorine pesticides in blood ranged from 3.319mg/L—6.253mg/L while in milk samples it ranged from 3.209Mdash;4.608 mg/L. The results are in concurrence with the reports from other countries.     

紫外法测定水中总氮准确度影响因素的探讨

通过对紫外法测定水中总氮影响准确度因素的分析得出前处理、工作曲线的绘制、样品的重复性测定及标准物质的配制是影响准确度的主要因素,可通过采取提高操作人员的业务技术水平、多次绘制工作曲线、适当增加样品重复次数等方法来提高测量准确性。     

Speciation of Cr and its leachability in coal by-products from spanish coal combustion plants

This study evaluates the behaviour of total Cr and Cr (VI) during coal combustion in two Spanish power stations. The content and distribution of Cr in the feed coal and combustion wastes was determined and the Cr contents were normalized using enrichment factor indexes. The speciation of Cr in the fly ash fractions from the different hoppers of the electrostatic precipitators was established and the possibility that the Cr (VI) might lixiviate when ashes are disposed of at landfill sites was assessed. Differences in the distribution and behavior of Cr in the two power stations were observed. According to European directive 1999/31/CEE, soluble Cr(VI) in the fly ashes studied would be unlikely to pose an environmental or health risk when the ash is disposed of.     

Petroleum contaminated soil in Oman: Evaluation of bioremediation treatment and potential for reuse in hot asphalt mix concrete

This paper presents a study that aims at evaluating the leaching characteristics of petroleum contaminated soils as well as their application in hot mix asphalt concrete. Soil samples are environmentally characterized in terms of their total heavy metals and hydrocarbon compounds and leachability. The total petroleum hydrocarbon (TPH) present in the PCS before and after treatment was determined to be 6.8% and 5.3% by dry weight, indicating a reduction of 1% in the TPH of PCS due to the current treatment employed. Results of the total heavy metal analysis on soils indicate that the concentrations of heavy metals are lower when extraction of the soil samples is carried out using hexane in comparison to TCE. The results show that the clean soils present in the vicinity of contaminated sites contain heavy metals in the following decreasing order: nickel (Ni), followed by chromium (Cr), zinc (Zn), copper (Cu), lead (Pb), and vanadium (V). The current treatment practice employed for remediation of the contaminated soil reduces the concentrations of nickel and chromium, but increases the concentrations of all remaining heavy metals.