Correlations among inorganic and organic elements in particulate matter (PM10) in urban area of Venezia-Mestre

Concentrations of inhalable particulate matter (PM10), Pb, Zn, Pt, Ce, Cd, Se and of Benzo(a)pyrene (BaP) were determined in three locations near Venice from September 2000 to September 2001. Meteorological conditions were considered during the sampling period. All components showed higher concentrations during winter, except for Cd and Se in the two sites at Mestre. Spatial and temporal variations were observed. There were correlations between Pb and Zn and PM10, Cd and Se, Pb and BaP and, in the main street sampling site, also between BaP and Pt. Their possible sources of emission are discussed on the basis of correlations among elements.     

A particle-size specific elemental mass balance for the apportionment of ambient aerosol

Photon and thermal neutron activation analysis were used to determine the concentrations of up to thirty elements in aerosol samples collected by cascade impactor in Toronto, Canada during the period July to December of 1985. Examination of the particle-size distributions thus obtained led to the development of a new receptor model. A size-specific elemental mass balance (SSEMB) was used to apportion the mean ambient Pb aerosol concentration amongst four contributing sources as follows: secondary lead refinery emissions (46%), refuse incineration (28%), automotive exhaust (25%) and re-entrained soil and dust (<1%). The predicted concentrations of Al, As, Br, Na, Pb, Sb, and Zn agreed with observed concentrations to within a factor of two for most elements in most particle size fractions.     

Natural sources and heavy metals

PTS, PM10 and PM2.5 samples have been collected at a rural site of south-east Italy (40 degrees 20' 13" N; 18 degrees 6' 47" E) from June to October, 2004 to investigate natural and anthropogenic contributions on particulate matter and heavy metal mass concentrations. It is shown that sharp-peak particulate-matter concentrations have been recorded during most African dust outbreaks occurred over south-east Italy. In particular, PM10 concentrations exceeding the 24-hour limit value of 50 microg/m3 have been monitored during dust events. Al, Cd, Cr, Cu, Fe, Mn, V, Ni, Pb, and Zn metal concentrations have been evaluated by an inductively coupled plasma atomic emission spectrometer and Al mass concentrations >500 ng/m3 have been observed in PTS and PM10 samples during the advection of African dust particles. Accordingly to geochemical calculations Al, Fe, and Mn, have a significant crustal origin while, Cd, Cu, Pb, and Zn are of anthropogenic origin. Moreover, Fe resulted predominant in the coarse particle fraction, while Ni, Pb, V, and Zn were predominant in the fine particle fraction. It is also shown that Cd, Mn, Ni, Pb, and V concentrations never exceeded guide and/or limit values recommended by the World Health Organization and the European Council Directives.     

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.     

Preliminary study on air pollution source identification in Xinzhen,Beijing, using NAA and PIXE

A total of 178 aerosol samples in two size fractions, PM10-2.5 (coarse) and PM2.5 (fine), were collected on nucleopore films using a Gent stacked filter unit sampler at the Graduate School of China Nuclear Industrial Group during May 2007 to November of 2009. Black carbon was determined by a reflectometer. A total of 16 elements, Mg, Al, S, Si, P, Cl, Ca, K, Ti, Mn, Fe, Ni, Cu, Zn, As and Pb, were determined by Particle Induced X-ray Emission. Mg, Al, Ca, K and Mn were also determined by Neutron Activation Analysis. Concentrations of all these elements were used to identify possible pollution sources and directions of the airborne particulate matter by means of softwares PMF and CPF. Some extraordinary events, such as sandstorms, firework and transboundary fire smoke were pinpointed by a combination of time series of multielement, relevant meteorological data and softwares Wind rose, Hysplit, and Google earth.     

Instrumental neutron activation analysis of elemental compositions in particles collected during Asian Dust period

Summary Instrumental neutron activation analysis was conducted on PM 10 samples collected in Daejeon city, Korea during September 2001 to May 2002. Our measurement data were analyzed to explain the behavior of particle-bound elemental components in relationship with Asian Dust (AD) events. The results of our analysis indicated that the major crustal elements (e.g., Al, Ca, Fe, K, Mg, and Ti) showed strong enrichment (about 3 to 9 times higher concentration levels) during the AD period accompanied by the increase in the PM 10 levels (e.g., by about 3 times). However, the concentrations of anthropogenically derived elements (such as As, Br, Sb, Se and Zn) exhibited moderate change during the AD period. Hence, the computation of enrichment factor (EF) indicated that the magnitude of EF values during the AD period was even smaller in the case of toxic metals than its non-AD counterpart. The existence of relatively low EF values during the AD period can be attributed to the excessive input of crustal components. The overall results of our study suggest that both absolute and relative elemental composition of aerosol particles can be altered significantly by the AD events.     

Assessment of trace elements characteristics and human health risk of exposure to ambient PM2.5 in Hangzhou,China

A method for simultaneously determining the trace elements in particulate matter (PM) (PM2.5) by inductively coupled plasma mass spectrometry was established. The PM2.5-loaded filter samples were digested under the optimised conditions including a mixture of HNO₃–HCl–HF with ultrasonication proceeding at 70°C for 2 h. Recoveries of 90.83–103.33% were achieved for 20 elements (Co, Sr, Ag, Cd, Sb, La, Ce, Sm, W etc.) in NIST standard reference material 1648a (urban PM). PM2.5 samples were collected at urban site in Hangzhou from August 2015 to November 2015. PM2.5 concentrations of 15% sampling days exceeded the daily limitation and the mean concentrations of PM2.5 from August to November reached the 66.4% of the limitation. PM2.5 concentrations in summer were higher than that in autumn. The concentration of Zn was highest, following with Al, Pb, Mn, Cu and As. Significant enrichment was observed in Mn, Zn, Pb, Ag, V, Ni, Cu, As, Se, Hg, Co, Cd and W, which was probably induced by vehicular exhaust, oil and residual fuel combustion and industrial emissions. The daily mass concentrations of PM2.5 and elements fluctuated significantly. Rainfall could significantly reduce the concentration of Ti, Mn, Cu, Zn, As, Se, Hg, Sr, Ag, Cd, Sb, La, Ce, Sm and Pb, and the risk levels of carcinogenic elements and non-carcinogenic elements in rain day were significantly lower (43.7–81.4%) than those in non-rain day. The risk levels of Co, Cd and As could lead to adverse health outcomes through the respiratory system, which should deserve more attention, while the risk levels of Ni and non-carcinogenic elements (Hg, Mn, Cu, Zn, Pb, V) were under average risk acceptance.     

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.     

Assessing spatial distribution,sources, and potential ecological risk of heavy metals in surface sediments of the Nansi Lake,Eastern China

The study is conducted to investigate the spatial distribution, sources and ecological risk of seven heavy metals in surface sediments of Nansi Lake, Eastern China. A total of 29 samples were collected in surface sediments of Nansi Lake, and were analyzed for three nutrients (TN, TOC and TP), two major metals (Al and Fe), as well as seven trace metals (As, Cd, Cr, Cu, Hg, Pb and Zn). The mean concentrations of As, Cd, Cr, Cu, Hg, Pb, Zn, Fe and Al were 14.41, 0.22, 71.10, 30.1, 0.048, 29.14, 90.2, 30,816 and 70,653 mg kg^?1, respectively, and the mean contents of these metals were higher than the background values with the exception of Cu and Fe. The spatial distribution indicated that the contents of all seven heavy metals were characterized by relatively higher contents in the upper lake than the lower lake. The hotspots with high values of As, Cd and Hg were associated with the river mouths, and the hotspots of Pb were mainly located around the dam in the central part, while no significant associations were displayed between spatial distribution of Cr, Cu, Zn and the river mouths. The mean enrichment factor (EF) values of As, Cd, Hg and Pb were 2.03, 2.93, 3.21 and 2.18, respectively, showing their moderate enrichment, while Cr, Cu and Zn with mean EF values of 1.19, 0.89 and 1.01 were deficiency to minimal enrichment. Multivariate and geostatistical analyses suggested that PC1 controlled by Cr, Cu and Zn was a lithogenic component, and come from parent rocks leaching. PC2 including Cd and partially Hg represented the factor from industrial wastewater discharge. PC3 showed elevated loadings of As and partially Cd, and could be attributed to the agricultural practices. While PC4 including Pb and partially Hg, was dominated by coal combustion. The results of potential ecological risk suggested that sediment environment of Nansi Lake suffered from high ecological risk.     

Short-term and spatial variation of selected metals in the atmosphere of Niterói City, Brazil

In this work, the atmospheric concentration of selected trace elements (Cd, Fe, Mn, Pb, V and Zn) was determined in total suspended material (TSP) from three sampling sites located at Niterói, an urban medium city of Rio de Janeiro, Brazil. TSP samples were collected with a high volume air sampler and glass fibber filters. The determinations of Cd, Pb and Zn were performed by ICP-AES while V was determined by ETA-AAS and Fe and Mn were measured by FAAS. Among all elements, Fe showed the highest concentrations (0.5-12.5 μg/m³) during the study but the concentrations of all elements varied along the week. The maximum levels of TSP, Fe, Mn, Cd and V were observed on Wednesday which was characterised by the highest winds frequency with higher speeds coming from the North quadrant, mainly from the Northeast direction. Enrichment factors showed that Cd, Pb and Zn are enriched in all sites suggesting that anthropogenic sources play important roles for those elements. Statistical analysis has been carried out to evaluate the effect of meteorological parameters and characterisation of sampling sites.     

Labile species of Pb, Zn and Cd determined by anodic stripping staircase voltammetry and their toxicity to tetrahymena

The amounts of free ions and labile complexes of Pb, Zn and Cd have been determined in a complex organic growth medium by use of anodic stripping staircase voltammetry, ASSV. It was possible to determine the labile fractions of metals and to obtain good correlation with data on the toxicity of the metals to Tetrahymena when using a specific reduction potential (E(s)) for each element, - 600, - 800 and - 1200 mV vs. SCE for Pb, Zn and Cd, respectively. The labile fractions in the organic growth medium were less than 1% for Pb (Pb precipitated), 15% for Zn (as labile complexes) and 30-40% for Cd (as free ions) for total heavy metal concentrations of 0.5mM-2mM. The toxicity to Tetrahymena decreased in the order Cd Zn Pb. The effect of Pb was greater than predicted by ASSV, probably because Tetrahymena additionally ingests the lead-containing precipitate and therefore is exposed to concentrations of Pb exceeding those of the soluble species found in the medium. The results stress the importance of using different specific reduction potentials when different elements are compared, instead of one potential common to all elements. The use of a fixed potential may lead to erroneous conclusions regarding the concentrations of labile species in solution.     

Characterization of Metals in Surface Sediments from Xiaoyang River,Jiangsu, China

Some metal species and fractions have high affinity to anthropogenic activities, making it feasible to characterize the spatiotemporal characteristics of human-induced degradation of ecosystems. The accumulation of Fe, Mg, Mn, Zn, Cu, Cr, Ni, and Pb, their fractions, physiochemical parameters, and nutrients was evaluated in the surface sediments at 11 sites on the Xiaoyang River in urban and suburban locations in Jiangsu, China for the assessment of pollution. The sediment quality was evaluated based on sediment quality guidelines, enrichment factors, geoaccumulation index, potential ecological risk index, and risk assessment code. Principal component analysis and cluster analysis were used to identify the sources of the metals. The total concentrations of metals, enrichment factors, and geoaccumulation indices demonstrated that all sites were significantly polluted with Zn and significantly to moderately polluted by Cu, Pb, and Ni. Moreover, higher metal enrichment was present downstream through downtown Sheyang due to extensive human activities. However, the potential ecological risk indices and risk assessment codes revealed high bioavailability and toxicity of Pb in this region. These results indicated that the metal fraction showed higher susceptibility. The accuracy of the ecological risk assessment was evaluated in the river, indicating a heavy anthropogenic impact.     

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.     

Analysis of voltammetric data for the evaluation of seasonal changes of the Ni, Cd, Pb and Cu content in atmospheric particulate PM2.5

In this paper, the preliminary results of a study on concentration of heavy metals in PM2.5 (atmospheric particles with aerodynamic diameter less than 2.5 microm) fractions of atmospheric particulate matter, sampled in Milan, are presented. This work aims to develop an electroanalytical method to analyse Pb, Cu, Cd and Ni in PM2.5 and to investigate seasonal and weekly trends in the amount of PM2.5 and its composition for considered metals. The samples have been selected within the seasons ranging from September 2002 to November 2003 so that they represent the possible seasonal changes; the samples within this period have been chosen in order to have data relevant to both working days and holidays. The determination of Cd, Pb and Cu has been carried out by Differential Pulse Anodic Stripping Voltammetry, whereas the concentration of Ni has been determined by Differential Pulse Adsorptive Cathodic Stripping Voltammetry. The concentrations of the metals in the sampled atmosphere and in the PM2.5 have been evaluated; through ANOVA possible seasonal or weekly variations in the above cited concentrations have been investigated.     

雾过程对大气气溶胶PM10中多环芳烃粒径分布的影响

在雾天气高发期间采集大气气溶胶PM10分级样品,测定了这些样品中的16种优控PAHs.结果表明：雾区近地层大气中PM2.1和PM9.0的平均质量浓度明显增加,雾过程改变了PM2.1的昼、夜浓度变化特征;雾前、雾中与雾后大气PM10中16种优控PAHs主要分布在比表面积大的细粒子上,平均有83.04%分布在Dp <2.1μm的范围,雾中1.1~2.1μm粒子的∑16PAHs浓度明显增加,Dp <0.65μm粒子的∑16PAHs浓度略有降低,说明雾过程对细粒子中∑16PAHs的浓度分布产生明显影响;雾前、雾中与雾后白天时间段,PM10分级粒子的∑16PAHs积聚模态分布出现较大差异,雾中积聚模态峰位置较雾前与雾后向较大粒径偏移;一次连续雾过程中,白天的∑16PAHs积聚模态峰位置随着雾的持续向大粒径方向偏移并停留在1.1~2.1μm;夜间的∑16PAHs积聚模态峰位置没有变化,均在1.1~2.1μm,说明PM10∑16PAHs的粒径分布受雾过程持续时间影响较大.     

川中丘陵区铁路旁土壤重金属含量及化学形态研究

对川中丘陵区成昆铁路的三圣段、吴场段和成渝铁路的五凤段3个典型路段铁路沿线土壤重金属Cd、Zn、Cu、Pb含量及其化学形态进行了研究,并运用次生相富集系数法对重金属的潜在生态风险进行评估。结果表明:铁路沿线土壤重金属Cd、Zn、Cu、Pb含量与对照点相比都有不同程度的升高。Cd不仅具有高的含量,且化学形态主要为酸可交换态和可还原态,残渣态含量很低,其有效态比例>75%,具有很强的生物活性和可迁移性。Cu、Pb、Zn的化学形态则主要为残渣态,酸可交换态比例很小,但是Pb和Zn的可还原态和可氧化态比例较高,所以有效态比例也较高,分别为51.1%~54.9%和36.2%~50%。土壤重金属Cu在各典型路段的次生相富集系数为1.4~4.2;Zn在三圣段、吴场段2个典型路段的次生相富集系数超过3.0,均具有较大的潜在生态风险。     

Heavy metals in PM10 sampled in the urban area of Campi Salentina (Apulia, southern Italy)

The following paper shows results of PM10 level and Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn concentrations present in this fraction for filters collected in the urban area of Campi Salentina (Apulia, Southern Italy) in 2004 in order to inquire into air quality. PM10 and lead concentrations did not exceed the standard values sanctioned by Italian Legislature with average values equal to 36.54 +/- 14.57 microg x m(-3) and 9.19 +/- 5.24 ng x m(-3) respectively. Significant correlations have been found between the pairs Fe-Mn, Ni-V, Cr-Ni and Cd-Cr. This suggests that these metals have a similar pollution source probably due to metallurgical activity. Multivariate statistical analysis showed that it is possible to distinguish the PM10 samples collected in sampling periods with different meteorological conditions. Indeed, metals concentration increases for samples characterized by scarce rains or by winds prevailing from North or North-West and is reduced due to different meteorological conditions, although there are some exceptions.     

Determination of chemical elements in airborne particulate matter collected at Lembang, Indonesia by particle induced X-ray emission

Monitoring the air quality in ambient air is an important step for assessing the air pollution level in one region and its impact to the human health. In this study, the determination of chemical elements concentrations in airborne particulate matter collected in suburban area of Lembang, Indonesia was carried out. Samples were collected using a Gent stacked filter unit sampler in two size fractions of <2.5 μm (fine) and 2.5–10 μm (coarse). Sampling was conducted twice a week for 24 h from January 2008 to June 2009 and 123 pairs of samples were collected. Black carbon was determined by reflectance and chemical elements analysis were performed using particle induced X-ray emission (PIXE). PIXE as one of ion beam analysis techniques is suitable for analyzing particulate matter for its multielemental analysis with good limits of detection. Results showed that none of daily concentrations of PM_2.5 and PM₁₀ exceeded the 24 h Indonesian NAAQS for PM_2.5 and PM₁₀. Chemical elements such as Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Hg and Pb were determined and the correlation between these elements was reported in order to understand the anthropogenic sources of particulate matter.     

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.     

Artifacts in the Determination of Trace Metal Binding Forms in Anoxic Sediments by Sequential Extraction

Abstract

The binding forms of Co, Cd, Cu, Pb, and Zn in an anoxic, sulfide-bearing sediment were investigated by performing both thermodynamic equilibrium calculations and sequential extractions. Care was taken to maintain oxygen-free conditions during the whole experiment. The calculations suggested that trace metals were bound to sulfidic minerals. Sequential extraction results, however, showed increased importance of exchangeable and reducible fractions in the order Cu < Cd < Pb < Zn < Co. Thermodynamic equilibrium calculations of the chemical reactions during extraction showed that Cd, Co, Pb, and Zn sulfides are to a significant extent soluble in the acetate-exchangeable (step 1 + 2) and oxalate-reducible (step 3) fractions. Neglecting the dissolution of sulfide minerals would lead to a misinterpretation of the experimental results.