Chemical characterization of airborne particulate matter in ambient air of Nagoya, Japan, as studied by the multielement determination with ICP-AES and ICP-MS.

The multielement determination of PM(10) (airborne particulate matter smaller than 10 microm) samples, which was collected by a high volume air sampler at the urban site of Nagoya City, was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The present analytical method was validated by analyzing urban particulate matter standard reference material of NIST SRM 1648. The analytical data for ca. 30 elements in PM(10) samples collected during a period from 8 September to 9 October, 2003, were obtained in the concentration range from sub-microg g(-1) to several-10 mg g(-1), but the data for 18 elements among ca. 30 elements were available for the characterization of PM(10) samples in ambient air, because of problems caused by the filter blanks. Then, the trends concerning the distributions of diverse elements in PM(10) samples were analyzed based on the enrichment factors and size distribution factors. The lithophile and siderophile elements were distributed more than 50% in coarse particle fraction (>2.1 microm), which was derived mainly from natural sources, such as soils and crustal minerals. On the other hand, chalcophile elements were distributed more than 50% in fine particle fraction (<2.1 microm), which was derived mostly from anthropogenic emission sources. The large enrichment of chalcophile elements in PM(10) samples as well as their mining influence factors (MIFs) suggested their wide use in industrial productions.     

Trace element levels of aerosols at an urban area of Korea by instrumental neutron activation analysis

Instrumental neutron activation analysis was used to measure the concentrations of about 27 elements associated with airborne PM 10 samples that were collected from a roadside sampling station at a moderately polluted urban area of Taejon city, Korea. The magnitude of their concentrations was clearly distinguished and spanned over four orders. If compared in terms of enrichment factors, it was found that certain elements (e.g., As, Br, Cl, Sb, Se, and Zn) are enriched in PM 10 samples of the study site. The factor analysis indicated three factors with statistical significance, which may exert dominant controls on regulating the metal concentration levels in the study area.     

Assessment of elemental contamination in road dust using EDXRF

Road dust samples were collected in different locations of heavy traffic, medium traffic, express way and industrial areas of Mumbai. The concentrations of various elements (Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Pb) in road dust samples were analyzed using EDXRF. The average elemental profile of road dust in Mumbai was comparable with studies carried out in other countries with slight variations. The estimated geo accumulation indices and enrichment factors indicated moderate elemental contamination and enrichment of anthropogenic elements in road dust samples. Factor analysis of elemental data resolved four sources namely crustal, tyre wear, vehicular/industrial emissions and break wear.     

Concentration levels and temporal variations of heavy elements in the urban particulate matter of Navi Mumbai, India

Coarse and fine fractions of particulate matter (PM) were collected and analysed for trace elements using Instrumental Neutron Activation Analysis and Energy Dispersive X-ray Fluorescence techniques. The result showed high concentrations of Fe, S, Zn and Pb in both the size fractions. The elemental data obtained is used to analyze the temporal and seasonal variations. The trend showed maximum concentrations of PM and metals during winter and minimum during the monsoon season. Enrichment Factor (EF) and source analysis was performed for the same data set to identify the strength of contribution of anthropogenic sources and the possible contributing sources in the study area. EF studies showed high enrichments of Zn, Pb and As in the fine fraction particles. Crustal, vehicular and industrial emissions are identified as the major contributing sources of PM in the study area.     

ICP-MS Measurement of Trace and Rare Earth Elements in Beach Placer-Deposit Soils of Odisha,East Coast of India,to Estimate Natural Enhancement of Elements in the Environment

Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration of trace and rare earth elements (REEs) in soils. Geochemical certified reference materials such as JLk-1, JB-1, and JB-3 were used for the validation of the analytical method. The measured values were in good agreement with the certified values for all the elements and were within 10% analytical error. Beach placer deposits of soils mainly from Odisha, on the east coast of India, have been selected to study selected trace and rare earth elements (REEs), to estimate enrichment factor (EF) and geoaccumulation index (I_geo) in the natural environment. Enrichment factor (EF) and geoaccumulation index (I_geo) results showed that Cr, Mn, Fe, Co, Zn, Y, Zr, Cd and U were significantly enriched, and Th was extremely enriched. The total content of REEs (ƩREEs) ranged from 101.3 to 12,911.3 µg g⁻¹, with an average 2431.1 µg g⁻¹ which was higher than the average crustal value of ΣREEs. A high concentration of Th and light REEs were strongly correlated, which confirmed soil enrichment with monazite minerals. High ratios of light REEs (LREEs)/heavy REEs (HREEs) with a strong negative Eu anomaly revealed a felsic origin. The comparison of the chondrite normalized REE patterns of soil with hinterland rocks such as granite, charnockite, khondalite and migmatite suggested that enhancement of trace and REEs are of natural origin.     

Concentrations and distributions of trace and minor elements in Chinese and Canadian coals and ashes

A total of 35 trace and minor elements including some of environmental significance were determined in each of a selection of 15 Chinese and 6 Canadian thermal coals and their ashes by using the SLOWPOKE-2 nuclear reactor facility of the University of Toronto. The concentrations and distributions of these constituents among the coals and their combustion products (viz. ash and volatile matter) are presented together with an interpretation of their significance in relation to the large scale combustion of these coals as thermal fuels in industrialized countries such as China and Canada. The detailed results showed wide variations in trace impurity concentrations (up to a factor of 100 and more) among the coals studied with few large differences between those of Chinese and Canadian origin except that the rare earths, Sc, Th, U, I, and Se were much higher in the former, other halogens, As and Na were lower. Values for elemental enrichment factors (EF) relative to normal crustal abundances indicated that only As(EF=13), Br(5.7), I(16), S(230), Sb(11) and Se(320) were appreciably enriched in coal. During static ashing at 750°C most of the halogens, S and Se were volatilized whereas most other inorganic constituents were highly retained and concentrated in the ash by factors of 6 to 11.     

Normalization strategies for river bed sediments: A graphical approach

The assessment of the degree of contamination of river bed sediments is a complex task, whose main difficulty arises from the application of correct normalization methods. A proper selection of background values and reference elements must be carried out to ensure a correct examination of the sediments. According to the results of our study, normalization by considering in-depth values lead to the most satisfactory results, when the background concentrations were inferred from the 25% lower hinge of box-plots graphs. This percentile was considered to be a conservative approach, which did not lead to overestimation of the actual contamination status of the sediments. Also, local background ranges were obtained by means of the calculation: median ± 2 median absolute deviation (MAD). Double-normalizations, as those made for the calculation of the Enrichment Factor, which use a reference element and a background value were considered more useful than single-normalizations against a reference element. Finally, the Enrichment Factors (EF) calculated on the basis of box-plot derived backgrounds were compared with those obtained by using average crustal and shale values, and local surface pristine values. The EFs obtained for the bulk fraction (< 2 mm) using crustal values were comparable to those obtained using local backgrounds, whereas shale values were more adequate for the fine fraction (< 63 µm). Pristine local values lead to an overestimation of the enrichment factors for most of the elements.     

Analysis of major and trace elements by INAA to predict the thousands year old sediment deposition environment in the Meghna river delta

Major, trace and rare earth elements have been measured in sediments of different layers to determine the controls of constituent minerals on the distribution of elements and sediment deposition environment in the Meghna river delta. The geochemical composition of sediments was enriched in SiO₂, Ca, Mg and Ba and depleted in Al, Fe, Ti, Mn, and Sr relative to PAAS (Post-Archaen Average Shale) value. The X-ray diffraction and elemental analyses demonstrate the dominant presence of quartz, micas, feldspar, chlorite, amphibole and clay minerals in sediments. The very low contents of trace elements suggest that the oxic condition was more prevalent during sediment deposition of Pleistocene-Holocene period and reflect the massive chemical weathering by biogeochemical reactions. The enrichment of light rare earth elements and La/Yb ratio reflect the intense silicate weathering of crustal materials and the high sediment depositional rate in the Meghna river delta.     

Annual variations of the elemental concentrations of PM10 in ambient air of Nagoya City as determined by ICP-AES and ICP-MS.

PM10 samples were collected at an urban site of Nagoya City during September, 2003, to August, 2004, and annual variations of the concentrations of the elements in PM10 samples were examined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The annual concentration variations of ca. 30 elements in ambient air were in the range from sub-ng m(-3) to several microg m(-3). From an evaluation by the enrichment factors of the elements, elements such as Al, Ca, Fe, Mg, Ti, Mn, Ba, Sr, Ce, La, Nd, Co, Cs, and Pr, in PM10 samples were found to have originated mostly from natural sources, while the elements such as S, Zn, Pb, Cu, Ni, Sb, Sn, Cd, Bi, W, Tl, and In originated from anthropogenic emission sources. Furthermore, in seasonal variations of the elemental concentrations of PM10 samples in ambient air, the elements originated mostly from natural sources provided significantly high concentrations in spring during the "Kosa" period (the dust season from March to May). On the other hand, the elements mainly from anthropogenic emission sources provided relatively higher concentrations in autumn and winter, which may be explained by the fact that the urban atmospheric structure is stabilized by the temperature-inversion layer formed over the city in those seasons. In addition, all of the elements provided significantly low concentrations in the summer, due to the dilution effect of the oceanic winds as well as due to the convection of air mass up to the high levels.     

Characterization of urban air pollution by total reflection X-ray fluorescence

Besides photochemical smog, particulate air pollution is a constantly growing problem in urban areas. The particulate matter present in pollution events contains often toxic or health impacting elements and is responsible for low visibility, might be triggering respiratory diseases like asthma, and can play an important role in formation or duration of smog events. To characterize particulate pollution in two different cities, samples were taken during intensive field campaigns in Chicago, IL, in 2002 and Phoenix, AZ, in 2001. Both cities experience regularly photochemical smog events as well as particulate pollution, but show very different meteorological and topographical conditions. Therefore it is expected that the particulate composition varies significantly, providing information about different pollution forms. Sampling took place in both cases at elevated locations and had a temporal resolution of 1.5 h and 1 h, respectively. The samples were analyzed by total reflection X-ray fluorescence after digestion of the filter matrix. As expected the elemental composition of particulate matter varied between both cities substantially with Phoenix showing a higher abundance of crustal elements, and Chicago enrichment in anthropogenically produced ones. In both cities diurnal patterns were found, exerting maxima in the morning and minima in the early afternoon. The diurnal pattern was much more regularly and also more strongly pronounced in Phoenix. Phoenix's valley location permits for a more stable nocturnal boundary layer to build up during the night thus trapping particulates efficiently during this time, until mixing occurs in the early morning hours and the residual layer lifts. In Chicago, the diurnal variation was less extreme, but another pattern determines the situation with the lake breeze. The lake breeze corresponds to a shift in wind direction towards the east, i.e. from Lake Michigan during the late morning. It was found that certain elemental species were enriched during a lake breeze event whereas this was not the case during other days. In conclusion, the low sample mass needed for TXRF analysis and the corresponding short sampling times, permitted the observation and characterization of local meteorological patterns in Phoenix and in Chicago.     

A new approach for determination of crustal and trace elements in airborne particulate matter

An ICP-OES procedure was developed for fast and accurate determination of various crustal (Al, Ca, Fe, Mg, Si) and trace elements (Ba, Cu, Mn, Na, K, Sr, Ti, Zn) in airborne particulate matter. The method is based on a preliminary treatment of the aerosol samples with a mixture of nitric acid and hydrogen peroxide at elevated temperature leading to a mineralization of the organic sampling substrate, dissolution of soluble material and homogeneous suspension of the remaining non-soluble fraction. After dilution the derived slurry solutions were measured using ICP-OES. The reproducibility of analysis given as the relative standard deviation (% RSD) varied between 3.2 and 6.8% for bulk constituents such as Al, Ca, Fe, Mg and Si whereas values ranging from 3.5 to 9.1% were obtained for trace metals present with distinctly lower abundance in PM10 (e.g. Ba, Cu, Mn, Sr, Zn). The limits of detection (LOD) calculated as three times the standard deviation (3σ) of the signal derived from filter blank samples ranged from approximately 1?ng?m^?3 (Sr) to 71?ng?m^?3(Ca). The developed procedure was evaluated by comparing the obtained results with the findings derived for the same set of aerosol samples analyzed using a microwave procedure for sample dissolution with subsequent ICP-OES analysis. Finally the developed procedure was applied for the analysis of crustal and trace elements in PM10 samples collected at an urban site (Getreidemarkt, Vienna) and a rural site (Hartberg, Styria), in Austria. The concentrations of the investigated crustal elements varied between some hundred ng?m^?3 and few µg?m^?3 with highest concentrations for Fe and Si, distinctly reduced concentrations ranging from some ng?m^?3 (Sr) to more than hundred ng?m^?3 (K) were found for trace elements. Observed PM10 concentrations were found to be in accordance to literature findings from urban sites in central Europe.     

Determination of elemental and ionic compositions for diesel exhaust particles by particle induced X-ray emission and ion chromatography analysis.

The purpose of this study is to clarify the chemical characterization of PM2.5 and PM10 in diesel exhaust particles (DEP). Sampling of PM2.5 and PM10 in DEP was carried out in November 1999 using an automobile exhaust testing system at the National Traffic Safety and Environment Laboratory, with a diesel truck (engine type: direct injection, displacement: 7,961 cc, carrying weight: 2,020 kg, equivalent inertia weight: 5,600 kg) placed on a chassis dynamometer. Sampling conditions included idling, constant speed of 40 km/h, M-15 test pattern and 60%-revolution/40%-load of maximum power. Samples were collected on a polycarbonate membrane filter (Nuclepore, pore size: 0.8 microm) using a MiniVol Portable Air Sampler (Airmetrics Co., Inc.). The concentrations of several elemental and ionic species in the PM2.5 and PM10 samples were determined by particle induced X-ray emission (PIXE) and ion chromatography analysis. PIXE analysis of the PM2.5 and PM10 samples revealed 15 elements, of which Na, Mg, Si, S, Cl, Ca, Fe and Zn were found to be the major components. Ionic species were Cl-, NO2-, NO3-, SO4(2-), Na+, NH4+, K+ and Ca2+. Concentrations of elements and ionic species under the sampling condition of 60%-revolution/40%-load were highest in comparison with those of the other sampling conditions. The elemental and ionic species data were compared for PM2.5 and PM10; PM2.5 concentrations were 70% or more of PM10 concentrations for the majority of elements, and concentrations of ionic species in PM2.5 and PM10 were almost identical.     

Trace elements in the atmosphere determined by nuclear activation analysis and their interpretation

Concentrations of 30 elements in the atmospheric particulate material were determined by three defferent nuclear activation techniques, namely; photon, thermal neutron and 14 MeV neutron activation analysis. Trace element concentrations observed were interpreted in terms of Enrichment Factor, EF, of each element with respect to crustal abundance and coal in order to find any possible correlation between the existance of highly enriched elements in the atmosphere and pollution source materials. It was also found that enrichment factors of elements are inversly proportional with the size of particulate material. Supported in part by Funds For Overseas Research Grants and Education (FORGE) and Scientific and Technical Research Council (TBTAK) of Turkey.     

INAA study for characterization of PM10 and PM2.5 in Beijing and influence of dust storm

Summary PM₁₀ and PM_2.5 samples were collected simultaneously in Beijing, China, and analyzed by INAA and ICP-MS. Seasonal variations of the concentrations of ambient particles and their elemental compositions were found. The main sources of PM₁₀ and PM_2.5 in spring were the crust, coal burning and vehicle exhaust, in which the former was significant. During a strong dust storm, the concentrations of the crustal elements in PM₁₀ and PM_2.5 increased remarkably, but the concentrations of some anthropogenic elements decreased. The enrichment factors of these anthropogenic elements also decreased sharply during the dust storm, which indicated that they were mostly originated from local anthropogenic pollution and diluted by the huge amount of dust.     

Particle Size Determination of Trace Elements in Urban Air

Abstract

Airborne urban particulate matter was collected and fractionated according to size by cascade impactors. The elements zinc, cadmium, copper and lead on each size fraction were analyzed by anodic stripping voltammetry. The elements aluminum, iron, manganese, calcium and magnesium were analyzed by atomic absorption spectrophotometry. The data showed three different classes of particle size distribution for these nine elements. Lead and cadmium belonged to the first class with more than 70 % of the total collected element associated with particles having aerodynamic diameters below 0.5 micron. The calculated average mass median equivalent diameter (MMD) of cadmium and lead was approx. 0.1 micron. In the second class about 60% of the elements Zn, Cu, Mg and Fe was associated with particles smaller than 0.5 micron. The average MMD's for these elements were between 0.3 and 0.4 micron. For the elements Al, Ca and Mn about 50% of the metal was associated with particles smaller than 0.5 micron and the MMD's were between 0.5 and 0.6 micron. Examination of elemental ratios (using Al as a reference element) showed that Pb and Cd were about 1000 times more concentrated in atmospheric particulate matter than in average crustal material and that in general the Pb/Al and Cd/Al ratios are inversely proportional to particle size. The Zn/Al and Cu/Al ratios of atmospheric partides were age or less independent of particle size and approx. 20 times higher than these same ratios in average crustal material. The ratios Fe/Al, Mn/AI, Ca/M and Mg/AI in all sizes of particulate matter were essentially identical to the same ratios in average crustal material.     

Particulate matter (PM10) from São Carlos-SP (Brazil): spectroanalytical techniques to evaluate and determine chemical elements

Chemical composition of PM10 was studied during the period of 2014–2015 in the city of São Carlos, Brazil (‘Dos Voluntários’ Square). PM10 samples were directly analysed by wavelength dispersive X-ray fluorescence – WD-XRF (Al, Ca, Ce, Cl, Fe, K, Mg, P, S, Si, Ti, V, and Zn), and by laser-induced breakdown spectroscopy – LIBS (Ba, Ca, Fe, K, Mg, Na, Si and Ti) both for qualitative purposes. For quantitative analysis of Al, Ba, Ca, Fe, K, Na, S, and Zn, the analytes were extracted from samples of PM10 collected, in filters of glass fibre, with an extractive acid solution (HNO₃ and HCl) and determined by inductively coupled plasma optical emission spectrometry – ICP OES. Spatial variations of elemental concentrations (ng m^–3) were significantly higher in winter Al (19.0), Ba (13.6), Ca (20.0), Na (27.0), S (37.1), and Zn (9.5), autumn showed the highest concentration of Na (26.4), spring showed the highest concentration of Fe (11.6), K (13.1) and also S (25.3) and summer did not show a high concentration in the comparison between the seasons at the site. Using principal component analysis (PCA), as a data interpretation tool, with the data obtained by the WD-XRF and LIBS it was not possible to obtain a good correlation, but with the data of ICP OES, it was possible to verify correlations between identified and determinate elements, with samples collected in the autumn, winter, spring and summer seasons in the city of São Carlos. These associated analytical techniques were excellent tools in environmental monitoring, through the analysis of PM10 samples, presenting reliable and efficiency strategy, and based on the PCA and the EF equation was possible to draw the profile of the possible origins of these elements in the city.     

Combining multivariate analysis and geochemical approaches for assessing heavy metal level in sediments from Sudanese harbors along the Red Sea coast

Multivariate statistical analysis and geochemical approaches were exploited for the assessment of the level of some heavy metals (Mn, Fe, Ni, Cu, Zn and Pb) in sediments from Sudanese harbors along the Red Sea coast. Principal component analysis, as a multivariate statistical analysis approach, was applied to identify contribution sources by heavy metals in sediments. While a single source (crustal) was recorded in the bulk sediments and coarse sediment grains (grain-size 1000-500 µm), two sources (crustal and anthropogenic) were recorded in fine sediment grains (grain-size < 500 µm). Furthermore, enrichment factor (EF), as a geochemical approach, appointed polluted sites by heavy metals in the study area. Based upon a previous study addressed the interpretation of EF values, minor to moderate anthropogenic enrichment were recorded in sediments from some sites in the study area. The main anthropogenic activities that believed to be the major sources of pollution by heavy metals in the study area are discharges from oil refinery, industry, shipping activity and domestic waste. Hierarchical cluster analysis (HCA), as another multivariate statistical analysis approach, was applied for the concentrations of heavy metals in bulk sediments to group sediments according to their mineralogical composition. The output of HCA is that sediments from the Port-Sudan harbor can be divided mainly into three areas — east, west and south. For the Sawakin harbor, no apparent trend for the spatial distribution of heavy metals in sediments was recorded.     

Study of seasonal variation and source characteristic of PM10 of Shanghai urban atmosphere using PIXE

This study is a one-year monitoring of the inhalable particulate matter (PM10) of Shanghai (from January 2006 to December 2006) to study PM10 pollution. Proton-induced X-ray emission (PIXE) was used to investigate the chemical elements in Shanghai PM10. The study finds seasonal variation in both mass concentration and of chemical elements in PM10. The results of the enrichment factor show that the chemical elements in the inhalable particles could be divided into two categories, soil elements from earth crust and anthropogenic pollution elements. The high enrichment factors suggest that anthropogenic activities were the dominant source for elements such as S, Cu, Cl, Zn, Pb and Br. Strong correlation of K, Ca, Fe and Ti, from factor analysis, indicates these elements coming from earth crust or soil, S, Zn and Pb from industrial pollution and/or traffic and Cl from coal combustion.     

Determination of elemental composition of atmospheric aerosol in the urban area of Islamabad, Pakistan

Summary This study provides useful information about the level and chemical composition of particulate matter and about the possible sources of the aerosol pollutant in Islamabad, the capital of Pakistan. Atmospheric aerosol samples were collected during winter (January and February) 1995, from two locations of Islamabad, namely of Sector F-7 and Sector I-9. Twenty-four elements were detected by using thermal neutron activation analysis (NAA) and atomic absorption spectrometry (AAS). The concentration of total suspended particulates (TSP) in the area around the industrial sector (I-9) was found to be more than twice higher (297 μg/m³) than in the Sector F-7 (133 μg/m³). The enrichment factor analysis revealed Zn, As, Br, Sb, I and Pb, originated mainly from anthropogenic sources. The elemental ratio analysis indicated that both Sectors I-9 and F-7 are under the influence of coal burning processes whereas transportation is responsible for the toxic pollutants Pb and Br. The present results were discussed and compared with those of the literature. The results may also serve as base line level as this work employed samples collected in 1995 and many of the air environmental change factors occurred after the sampling year.     

Heavy metal determination in atmospheric particulate matter by Instrumental Neutron Activation Analysis

Instrumental Neutron Activation Analysis (INAA) is employed for its important analytical properties. Fundamentally, INAA is a multi-elemental technique allowing the determination of about 40 elements with a good Limit of Detection. In this paper we applied this nuclear technique to study the element composition in PM10 determining about 30 elements.25 filters were collected in downtown Rome from October 1999 to April 2000 and irradiated at the nuclear reactor Triga Mark II (ENEA-Casaccia Laboratories). The γ-ray measurements have allowed the quali- and quantitative analysis. The element levels in PM10 with the relative correlations have been determined: basically, the concentrations are very low.Furthermore, the enrichment factors of all elements will be reported in order to understand the natural or anthropogenic origins of the particulate matter: some elements may be attributed to long-range transport phenomena from other natural and/or anthropogenic sources.