Characterization of airborne trace metal and trace organic species from coal gasification

Fugitive emissions from a slagging fixed-bed coal-gasification pilot plant were analyzed by flameless atomic absorption spectrophotometry, gas chromatography, and mass spectrometry for trace metal and trace organic species. Analysis of the size distributions of airborne particulate matter inside the plant showed an abundance of large metal-containing particles; outdoor distributions in the vicinity of the plant resembled the indoor distributions, suggesting the importance of the gasifier in influencing ambient air quality. This conclusion was further supported by identification of similar organic compounds inside and outside the plant. Trace element enrichment factors based on the earth's crustal composition were greater than those based on the composition of the lignite used in the gasifier, showing the importance of characterizing the proper source material when inverstigating chemical fraction during aerosol formation. Enrichments in the present study were much greater than those found in previous sampling during aborted start-up and cleaning procedures, where normal operating temperatures had not yet been reached. Both studies showed evidence of enrichment factors which decreased with increasing particle size. Although much of the airborne mass was associated with large particles having low respirability, the high concentrations of some metals indoors suggests that further assessment of potential occupational exposures is warranted.     

Vertical distribution of heavy metals in grain size fractions in sedimentary rocks: Mosina–Krajkowo water well field, Poland

The paper presents the results of heavy metals determination in samples of sedimentary rocks from the Mosina-Krajkowo water well field (Poland). The concentration of heavy metals was analysed by type of rock (sand, gravel, warp, silt, till, and clay). Variation of heavy metal concentrations with depth was studied taking into account the age series of the rocks (fluvial sediments of the modern Warta River valley, sediments of the Baltic Glaciation, tills of the Middle-Polish Glaciation, sediments of the Masovian Interglacial (Holstein), tills of the Poznań series) and granulometric fractions. The grain sizes considered included: >2.0, 2.0-1.0, 1.0-0.5, 0.5-0.25, 0.25-0.1, 0.1-0.063, and <0.063 mm. The concentrations of the heavy metals studied were found to change with the type of rock, age series, and granulometric fraction. The levels of the metals were determined by the technique of atomic absorption spectrometry with flame atomisation (F-AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES).     

空气颗粒物中铅、镉超声浸取-原子吸收测定方法研究

用超声波震荡方法对大气滤膜样品进行前处理,提取待测元素。研究了浸取液种类、酸度、浸取时间和干扰因素等,确定了颗粒物样品溶液制备的最佳条件,与流动注射在线富集——原子吸收技术结合,建立了大气颗粒物样品测定Pb、Cd方法。结果表明,方法快速、准确,标准样品测定回收率在97％以上,6次测定方目对标准偏差小于2.6％。     

Toxic Metals in the Austrian Pine (Pinus Nigra) Bark in the Thrace Region, Turkey

Austrian pine (Pinus nigra) bark was collected in thirty-seven localities in the Thrace region, Turkey, for the determination of airborne toxic metal distribution. Five toxic metals, As, Cd, Cu, Pb, and Zn, were monitored using atomic absorption spectrometry. Distribution maps of toxic elements in the region were plotted according to Geographic Information System technology. In general, the concentrations of all investigated elements were not high in the region apart from the vicinity of big cities, Tekirdag, Istanbul and, close to Bulgarian border. However, the highest concentrations were not at pollution level. They have a similar distribution pattern throughout the region.     

ASD-ICP-AES联用快速测定土壤中部分重金属

采用样品全自动消解系统(Automated Sample Digestion)对土壤样品进行前处理,采用ICP-AES对土样中的重金属元素一次性测定.通过优化实验,获得土壤中各种重金属的最佳消解条件.结果表明,经优化的消解程序A1能够快速、稳定消解土壤样品,并获得理想测试结果.经检验,ASD-ICP-AES联用的土样测...     

Homogeneity and stability study of the candidate reference material Adamussium colbecki for trace elements

The preparation of a new candidate certified reference material (CRM) for trace elements based on the antarctic bivalve Adamussium colbecki(IRMM 813) was carried out by the Istituto Superiore di Sanità(ISS, Rome, Italy) in cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission (EC-JRC-IRMM), in the frame of the Italian National Programme of Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). Samples were collected at Terra Nova Bay (Ross Sea) during the 2000-2001 expedition in Antarctica. The preparation of a material suitable for certification was performed by the EC-JRC-IRMM. Measurements for homogeneity and short-term stability tests were carried out by ISS. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. For the above-mentioned tests, the determination of the elements of interest was performed on samples mineralised by microwave-assisted acid digestion. The analytical techniques employed to this end were inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry (ICP-DRC-Q-MS). The candidate material was shown to be fit for purpose with regard to homogeneity and short-term stability, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign.     

Quality assurance in measuring the elemental composition of the alga Fucus vesiculosus

Algae are increasingly used for the purpose of environmental biomonitoring, for instance in the long-term program of the Federal Environmental Specimen Bank of Germany. Therefore, for the studies presented here, freeze-dried samples of Fucus vesiculosus collected from the North Sea shores were analyzed for a broad range of elements by instrumental neutron activation analysis (INAA), while inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) were carried out on digests. The entire analytical procedures, including field sampling, cleaning of material, sample handling, determination of blanks and instrumental parameters, are described. Certified reference materials analyzed in parallel with real samples and intermethod comparisons were used for assuring the accuracy of the analytical data. Reproducibility of INAA measurements was between 4 and 6% depending on the element considered. Possible sources of uncertainty and variation of the contaminant origins are discussed. Boundary conditions for the performance of algae sampling within environmental monitoring programs and the application of this marine bioindicator for the purpose of controlling time-dependent and local differences in element patterns are presented.     

鞍山市环境空气颗粒物中重金属元素分布特征

研究了鞍山市环境空气中可吸入颗粒物(PM10和PM2.5)中重金属元素分布特征,结果表明鞍山市环境空气可吸入颗粒物中Zn、Pb、Al、Cu四种金属总和所占21种元素比例近85%。重金属元素在不同粒径颗粒物中的浓度水平有明显差别,更易富集在细颗粒物PM2.5上。     

Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina

A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources.     

Monitoring trace metals in urban aerosols from Buenos Aires city. Determination by plasma-based techniques

A study was undertaken, within the framework of a 3 years national project, to assess the content of 13 elements in airborne particulate matter collected in representative zones of the metropolitan area of Buenos Aires. The sampling strategy followed consisted in collecting simultaneously 67 samples of PM10 particulate matter in 9 sampling sites covering an area of about 30 km2 during one week. The collection was performed on ash-free fibre-glass filters using high volume samplers. A combination of aqua regia and perchloric acid was used for leaching metals from filters. Key elements, namely Al, Ca, Cu, Fe, Mn, Mo, Ni, Pb, S, Sb, Sn, Zn and Zr, were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) at micro g g(-1) and ng g(-1) levels. Analyte concentration varied from 130 ng g(-1)(Mo) to over 30%(Ca). Multivariate statistical analysis was performed on the data set including the measured elemental compositions for the monitored period. The atmospheric concentration found for Pb confirms the decreasing levels of this element since the introduction of unleaded gasoline in 1995: 88 ng m(-3)(2001) < 220 ng m(-3)(1997) < 3900 ng m(-3)(1994). The average S concentration above 3 microg m(-3) is somehow unexpectedly high for Buenos Aires since the relatively low S content of liquid fuels and the massive usage of natural gas imply low emissions of this element from combustion activities. To the best of our knowledge, S concentrations are reported for the first time for this city.     

Comparison of three sequential extraction protocols for the fractionation of potentially toxic metals in coastal sediments

In the determination of the best sequential extraction procedures (SEP) for the speciation of metals in sediment samples from the Lagos lagoon system, three sequential extraction procedures were compared for the fractionation of Cd, Cr, Cu, Pb, and Zn. The SEP compared included a modified Tessier??s procedure carried out in five steps, while the two other procedures were the three-step original Community Bureau of Reference (BCR) and the modified BCR techniques (four steps). Quantification of the metal concentration was achieved with a flame atomic absorption spectrophotometer. The results obtained by the three methods were compared, and the modified BCR and Tessier SEP were found to extract more Cu, Cr, Pb, and Zn in the reducible phase and therefore a decrease in the oxidizable phase than the original BCR SEP. The most mobile elements were found to be Cd, Pb, and Zn. These are of environmental concern, as these potentially toxic metals could be easily released into the aquatic environment with consequent ingestion by aquatic organisms, thereby entering the food chain. The mass balance (percent recovery) was found to be between 85% and 115% in most cases. Prior to the comparison, the analytical performance of the laboratory was tested using a secondary reference material, GLAURM, using the three-step modified BCR procedure. The results showed high reliability of the analytical performance of the laboratory for all the metals considered.     

Cycling of rare earth elements in the atmosphere in central Tokyo

Concentrations of 14 rare earth elements (REEs) in six size classes of airborne particulate matter (APM) (<0.43, 0.43-0.65, 0.65-1.1, 1.1-2.1, 2.1-11, and >11 μm) and in two different phases (suspended particulate and dissolved) in rainwater were determined by inductively coupled plasma mass spectrometry (ICP-MS). Positive Eu and Tb anomalies were observed in size-classified APM. These anomalies may be due to large emissions of Eu and Tb to the atmosphere resulting from the recent change in Japan from the use of cathode-ray tubes to plasma displays in television sets (Eu and Tb) and from the widespread use of magneto-optical disks (Tb). The light REEs were enriched in fine APM particles (diameter < 1.1 μm). Because compositions of La/Ce/Sm in fine APM (diameter < 1.1 μm) were similar to those in automobile catalyst, the light REE enrichment was attributed to automobile emissions. In contrast, the REE distribution pattern in the suspended particulate phase in rainwater was similar to that in coarse APM (diameter > 2.1 μm), and a positive Tb anomaly was observed, suggesting that coarse particles easily become trapped in rain droplets. A negative Eu anomaly was observed in the dissolved phase in rainwater, but not in APM or in the suspended particulate phase in rainwater. Unlike other REEs, Eu can exist as both bivalent and trivalent ions in nature, and Eu-selective dissolution from or adsorption onto the trapped particles of Eu might account for the negative anomaly. These results show that atmospheric REE cycling is affected by the physico-chemical properties of APM.     

Study of heavy metal pollution in seawater of Kepez harbor of Canakkale (Turkey)

In this work, the heavy metals cadmium and lead in Kepez harbor were studied with regard to the determination of the environmental pollution levels. Seawater samples of the Dardanelles (Canakkale Strait) were collected from the nearest station to Kepez harbor in July 2007. Then, the concentrations of these metals were determined after simple pretreatment of samples by the proposed inductively coupled plasma?Catomic emission spectrometry (ICP-AES) method. The analysis of a given sample is completed in about 15 min by the ICP-AES method, and the concentrations of Cd and Pb were found to be 73.80 mg L^???1 (relative standard deviation [RSD], 1.07%) and 9.39 mg L^???1 (RSD, 0.70%), respectively. The accuracy of the applied ICP technique was checked by recovery studies, and good recoveries were obtained. The pollution levels of Cd and Pb recorded in this study were compared with those in other studies to analyze the water sample in Kepez harbor.     

Trace metals biogeochemistry of Kumaun Himalayan Lakes,Uttarakhand, India

The increasing urbanization, along with tourism, has posed a major threat to the Kumaun Himalayan Lakes, Uttarakhand, India. The total metal concentration in the water, interstitial water, and sediments along with the metal fractionation studies were carried out to understand the remobilization of the trace metals from the sediments of the lakes. The high concentration of the metals in the water column of the lakes generally decreases with depth and the metals release from the sediment is mainly due to the prevalence of anoxic condition at the sediment–water interface and sediment column. The sediment shows that metals Fe and Cr are derived from detrital source, whereas Co, Ni, and Zn are derived mainly from the organic matter dissolution. The sparse correlation of the trace metals with Ti shows most of the metals have chiefly re-precipitated from the water column. The metals speciation studies also supports that metals experience a high rate of anoxic dissolution and their precipitation onto the sediments are determined by the sediment composition and organic matter content. The high concentration of manganese in the interstitial water in the lakes indicates dissolution of organic matter. The released manganese is adsorbed/precipitated as carbonate phase (Nainital Lake) and oxide pahse (in other lakes). The study shows that the trace metals are regenerated from the sediments due to oxyhydroxide dissolution and organic matter decomposition.     

Comparison of pressurized fluid extraction, Soxhlet extraction and sonication for the determination of polycyclic aromatic hydrocarbons in urban air and diesel exhaust particulate matter

In order to characterize and compare the chemical composition of diesel particulate matter and ambient air samples collected on filters, different extraction procedures were tested and their extraction efficiencies and recoveries determined. This study is an evaluation of extraction methods using the standard 16 EPA PAHs with HPLC fluorescence analysis. Including LC analysis also GC and MS methods for the determination of PAHs can be used. Soxhlet extraction was compared with ultrasonic agitation and pressurized fluid extraction (PFE) using three solvents to extract PAHs from diesel exhaust and urban air particulates. The selected PAH compounds of soluble organic fractions were analyzed by HPLC with a multiple wavelength shift fluorescence detector. The EPA standard mixture of 16 PAH compounds was used as a standard to identify and quantify diesel exhaust-derived PAHs. The most effective extraction method of those tested was pressurized fluid extraction using dichloromethane as a solvent.     

Analysis of cadmium, nickel, and lead in commercial moist and dry snuff used in Pakistan

The extent to which smokeless tobacco endangers human health is an ongoing subject of debate. In this study, concentrations of toxic metals, cadmium (Cd), lead (Pb), and nickel (Ni), were measured in different snuff products (dry brown and black and moist green and brown), available and consumed in Pakistan. Concentrations of Cd, Pb, and Ni were determined in 23 samples of various brands of snuff by electrothermal atomic absorption spectrometry, after microwave-assisted acid digestion. The reliability of methodology was assured by analyzing certified reference material. The resulted data of toxic metals in different snuff products are comparable to the existing information with limited exceptions. It was estimated that 10 g intake of different types of snuff could contribute 14–68, 17–47, and 20–73 % of the provisional maximum tolerable daily intake for Cd, Ni, and Pb, respectively.     

Possible markers of traffic-related emissions

Looking for robust indicators of motor vehicle emissions it has been found that brake wear and linings are significant contributors of Cu, Mo and Sb to air particulate matter. These trace elements, whose mutual ratios in airborne particulate matter resulted quite different from those in crustal material, appear to be available fingerprinting tools to identify the contribution of on-road vehicles to traffic-derived particulate matter. In this study, the results of analytical determinations of Cu, Mo and Sb on PM(10), PM(2.5), vegetation and brake dust samples, together with gas (CO, NOx) concentrations, are discussed. Highly significant correlations among Cu, Sb and Mo were observed in particulate matter from Palermo and between Cu-Sb and Cu-Mo at Catania. Further significant positive correlations have been found in pine needles from Palermo, Gela and in platanus leaves from Catania.     

Saharan dust particles in snow samples of Alps and Apennines during an exceptional event of transboundary air pollution

Southern European countries are often affected in summer by transboundary air pollution from Saharan dust. However, very few studies deal with Saharan dust pollution at high altitudes in winter. In Italy, the exceptional event occurred on February 19, 2014, colored in red the entire mountain range (Alps and Apennines) and allowed to characterize the particulate matter deposited on snow from a morphological and chemical point of view. Snow samples were collected after this event in four areas in the Alps and one in the Apennines. The particulate matter of the melted snow samples was analyzed by scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS) and by inductively coupled plasma mass spectrometry (ICP-MS). These analyses confirmed the presence of Saharan dust particle components in all areas with similar percentages, supported also by the positive correlations between Mg-Ca, Al-Ca, Al-Mg, and Al-K in all samples.     

Comparison of three sequential extraction procedures for partitioning of heavy metals in car park dusts

The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.     

Determination of selected heavy metals in air samples from the northern part of Jordan

In this work, the atmospheric concentrations of selected heavy metals including lead (Pb), iron (Fe), cadmium (Cd), copper (Cu), nickel (Ni), manganese (Mn), and zinc (Zn) were measured for two different sampling sites (urban and rural) in the northern part of Jordan (Irbid city). Samples were collected according to a certain schedule for 1 year. High volume air samplers and glass fiber filters were used to collect the samples. Collected samples were digested using a mixture of analytical grade nitric acid and analytical grade hydrochloric acid, and analyzed to evaluate the levels of heavy metals by atomic absorption spectrophotometry. Six heavy metals (Pb, Fe, Cu, Ni, Mn, and Zn) were measured in all samples; the concentrations of Cd and Co were not detected in Irbid atmosphere by atomic absorption spectroscopy. The results were used to determine the levels of heavy metal pollutants in air, possible sources, and to compare the levels of selected heavy metals in the two studied sites. Aerosols from the rural site have lower concentrations for all the metals compared to those from the urban site. The daily and monthly variations of the elements were investigated. All heavy metals in urban and rural sites reached maximum concentrations in June, July, and August. This is consistent with the increased activities leading to particulate matter emission during the summer period. The enrichment factors with respect to earth crust and correlation coefficients of heavy metals were investigated to predict the possible sources of heavy metals in air.