Correlation of trace element content in air particulates with solar meteorological data in the atmosphere of Athens

In this paper, the relation between the trace element content in air particulates and solar meteorological data in the atmospheric environment of Athens, Greece, was studied. For this purpose, Sm, Br, As, Na, K, La, Ce, Cr, Ag, Sc, Fe, Zn, Co, Sb, Th were determined by INAA in respirable aerosols collected during winter 1993-1994. The results showed that the average cloudiness, sunshine, and the total solar radiation (sun and sky) on a horizontal surface, (3 variables) have no relation with trace element variation. However, diffuse solar radiation (sun and sky) on a horizontal surface seems to have statistically significant relationship with some of the trace element variation. It forms a single component with some trace elements after the application of the factor analysis. The increase of the same solar variable in the Athens City center, is one of the factors which cannot permit the emission of trace elements in the atmospheric environment from dust soil and car tires.     

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.     

高血压患者血清中八种金属元素的

通过对48名高血压患者和52名正常健康人进行血清中八种金属元素的检测,探讨了人体必需金属元素的含量变化是否与患高血压疾病有直接的关系。采用离心分离的方法处理样品,用火焰原子吸收分光光度法检测样品中钙、镁、钾、钠、锌、铜、铁和锰的水平含量。结果表明,患高血压组血清Na、Mg、Zn、Fe、Mn的水平含量均高于健康对照组,其中Na、Mn两组间比较差异显著（P＜0．05）,Zn、Fe两组间比较差异非常显著（P＜0．01）,Mg两组间比较差异无显著性（P＞0.05);患高血压组血清Na／K比值均高于健康对照组,Ca/Mg、Cu/Zn比值均低于健康对照组。检测的八种金属元素在人体内的含量多少与患高血压疾病有一定的关系。提示适当增补体内的Ca、K、Cu和Mg含量,减少Na的过多摄入,科学控制Zn、Fe、Mn的增加,注意体内Na/K、Ca/Mg和Cu/Zn比值的平衡关系,降低Na/K比,提高Cu/Zn比,补Ca的同时一定要注意适当补充Mg,保持体内各元素间的相互依赖关系,有利于高血压病的预防和治疗。     

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.     

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.     

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.     

Trace element determination in aerosols from the Antarctic Peninsula by neutron activation analysis

The knowledge of the composition of atmospheric aerosols in remote areas, like the Antarctic Peninsula is of great importance for the study of long-range transport of atmospheric contaminants and also from the climatological point of view. Instrumental neutron activation analysis was applied in the present work to determine the elements Al, V, Mn, Na, Cl, Ca, Au, Br, Sb, Sc, Fe, Zn, K, Th and La in aerosol samples collected in the Brazilian Antarctic Station Comandante Ferraz (62° S, 58° W) located on King George Island in the Antarctic Peninsula. The sources of the aerosols were investigated by means of Enrichment Factors and Principal Factor Analysis. Both methods yielded similar results. Sea and soil were identified as the major sources of aerosols, in the samples collected at the Brazilian Station.     

A contribution to the characterization of the aerosol sources in São Paulo

Fine and coarse particles in suspension in the atmosphere were collected on two Teflon filters with a dichotomous sampler. The concentration of Al, Br, Ca, Ce, Cl, Co, Cr, Fe, K, La, Mn, Na, P, Pb,, S, Sb, Sc, Se, Si, Sm, Th, V and Zn was determined by ED-XRF and INAA. The elemental concentration was analyzed by means of linear correlation coefficients, enrichment factors and principal factors analysis in order to identify the aerosol sources. The main sources of the aerosol particles were the marine ones, resuspended soil, fuel-oil combustion, phosphatic rocks, refuse incineration and residual high-temperature processes.     

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 element analysis of airborne particulate matters in relation to air pollution in Benin City, Nigeria

The methods of neutron activation analysis (NAA) and atomic absorption spectrometry (AAS) have been employed to determine the concentration levels of 18 trace elements in filter-collected airborne aerosols over an urban area in Nigeria. The highest concentrations measured in the samples were for Cl, Na, Al, Pb, Ca and Zn. The aerosol particles were found to contain higher concentrations of soil-derived trace elements, such as Al, Ti, K and Na than those derived from combustion and industrial activities such as As, Cd, Mn, Zn, Pb, Ni and Sb. The average precision of measurements varied between +/- 5.2% and 13% for most elements. Possible sources of the elements are also discussed.     

Elemental composition of air masses under different altitudes in Azores,central north Atlantic

Between 8th July 2002 and 18th June 2004, aerosol samples were collected in Azores. Their inorganic composition was obtained by neutron activation analysis in order to study the differences of aerosols in two atmospheric altitudes of the central north Atlantic: (1) PICO-NARE observatory (Lower Free Troposphere-LFT) at Pico mountain summit (38,470oN, 28,404oW, 2,225 m a.s.l.) in Pico Island, Azores, where air masses from the surrounding continents (Africa, Europe, Central and North America) pass through, carrying aerosols with anthropogenic (Sb, Br, Mo, U, Se and Tb) and/or natural emissions (Fe, Co, La, Na, Sm, Cr, Zn, Hf, K and Th); (2) TERCEIRA-NARE station (Marine Boundary Layer) at Serreta (38,69oN, 27,36oW, 50 m a.s.l.), in Terceira Island, Azores, where natural aerosols (I, Cl, Na, Br and other soil related elements) are predominant. However, a combined interpretation of the data points out to a co-existence of the anthropogenic elements Sb and Mo, eventually with similar origins as the ones passing Pico Mountain summit. Very high concentrations and enrichment factors for Sb, Mo and Br in LFT, higher than the ones found in other areas, confirm atmospheric long-range transport mainly from the west boundary of north Atlantic; this may indicate eventual accumulation and persistence of those elements in the area due to the presence of Azores high pressures or the Hadley cells effect. A significant correlation between Fe and Yb and the enrichment of rare earth elements (La, Sm, Tb and Yb) and Th in LFT aerosols, both reflect a mineral dust intrusions from north Africa (Sahara and Sahel region).     

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.     

Analysis of heavy metals in road-deposited sediments

Road-deposited sediments were analysed for heavy metal concentrations at three different landuses (residential, industrial, commercial) in Queensland State, Australia. The sediments were collected using a domestic vacuum cleaner which was proven to be highly efficient in collecting sub-micron particles. Five particle sizes were analysed separately for eight heavy metal elements (Zn, Fe, Pb, Cd, Cu, Cr, Al and Mn). At all sites, the maximum concentration of the heavy metals occurred in the 0.45-75 μm particle size range, which conventional street cleaning services do not remove efficiently. Multicriteria decision making methods (MCDM), PROMETHEE and GAIA, were employed in the data analysis. PROMETHEE, a non-parametric ranking analysis procedure, was used to rank the metal contents of the sediments sampled at each site. The most polluted site and particle size range were the industrial site and the 0.45-75 μm range, respectively. Although the industrial site displayed the highest metal concentrations, the highest heavy metal loading coincided with the highest sediment load, which occurred at the commercial site. GAIA, a special form of principal component analysis, was applied to determine correlations between the heavy metals and particle size ranges and also to assess possible correlation with total organic carbon (TOC). The GAIA-planes revealed that irrespective of the site, most of the heavy metals are adsorbed to sediments below 150 μm. A weak correlation was found between Zn, Mn and TOC at the commercial site. This could lead to higher bioavailability of these metals through complexation reactions with the organic species in the sediments.     

Partitioning of metals between the aqueous phase and suspended insoluble material in fog droplets

This paper discusses the partitioning of metals (K, Na, Ca, Mg, Al, Cu, Fe, Pb and Zn) between the aqueous phase and the suspended insoluble material in fog samples collected in the Po Valley during two extensive fields campaigns. Metals represent on average 11% of the mass of suspended insoluble matter, while the main component is carbon (both organic carbon, OC = 35%, and black carbon, BC = 8%). The unaccounted suspended matter mass is very high, on average 46%, and is attributable to non metallic species, such as O and N and of Si. The principal metals in the insoluble suspended fraction are Fe and Al (2-5%), while the contributions of other metals (Na, Mg, Cu, Pb and Zn) are lower than 1%. Ca and K exhibited high blank values and could not be detected above blank detection limit threshold. The main components in the aqueous phase are NO3- (34%), WSOC (23%), SO4(2-) (18%) and NH4+ (19%), while trace metals and remaining cations and anions accounted for less than 1% of solute mass. The main dissolved trace metals in fog droplets are Zn, Al and Fe, while the main metallic cations are Na and Ca. Fe and Al are the only metals preferentially distributed in the suspended insoluble matter of fog droplets (partitioning ratio respectively 37% and 33%). All other metals are mostly dissolved in the aqueous phase (mean partitioning ratios of Mg, Pb, Zn, Cu and Na are 69%, 70%, 77%, 81% and 87%). These findings are in agreement with literature data on metal speciation in cloud and rain samples. The dependence of partitioning ratios on pH is investigated for the different metals, with only Al showing a clear partitioning ratio decrease with increasing pH. Conversely, the other metals show no dependence or a complex and highly variable behaviour. The partitioning ratio of iron (mean 37%) observed in the Po Valley fog samples is much higher than the water extractable iron in aerosol particles (typically 1-2 %): this fact can be explained by differences in the aerosol sources and composition among sites and by chemical processes in the aqueous phase, such as complexation and redox reactions involving organic ligands (oxalate, or other organic acids as humic-like organic matter) which may promote Fe solubility.     

Chemometric Assessment of the Interactions Between the Metal Contents,Antioxidant Activity,Total Phenolics,and Flavonoids in Mushrooms

The elemental composition and antioxidant activity have been obtained for regional mushrooms species, wild and cultivated, from Dambovita County, Romania. A multivariate approach and data mining techniques (principal component analysis and cluster analysis, respectively) were applied in order to evaluate the correlation matrix for these parameters for both caps and stipes of mushrooms. The associations between metallic elements (i.e., Fe, Cu, Cd, Pb, Co, Ni, Zn, Mn, Cr, Na, K, Ca and Mg) correlated with antioxidant activity, total phenolics, and total flavonoids were carried out by using a full factorial linear design. The multivariate functional analysis revealed on associated accumulation of several elements in mushrooms. In the cluster analysis, the dataset was treated to appreciate the correlation between metals group (e.g., heavy metals, such as Fe, Cu, Cd, Pb, Co, Ni, Zn, Mn, Cr, and important nutritional elements, such as Na, K, Ca, and Mg). Fungal species with similar characteristics in terms of metal accumulation formed two distinctive clusters. From a point of view of the consumer, the content of Cd and especially Pb in the fruiting bodies of the analyzed mushrooms species may be considered elevated, so that mapping the risk is compulsory. Applying the chemometric tools in the sense mentioned above, as well as in helping the scientific research by optimizing the number of data points, was shown to be extremely useful.     

Evaluation of trace element contents in Swertia paniculata Wall.

Important mineral elements (Fe, Zn, Mn, Cu, Co, Na, K, Ca and Li) were determined in the leaves and roots of Swertia paniculata collected from three different altitudes in three seasons using atomic absorption spectroscopy. The highest concentrations of Zn, Cu, Mn, Fe, Co, Na, K, Ca and Li were found to be 193.0?±?5.6, 26.0?±?7.6, 303.0?±?8.5, 1507.0?±?2.5, 88.0?±?1.2, 345.0?±?1.2, 11622.0?±?6.4, 3461.0?±?3.5 and 48.0?±?4.5?mg?kg(-1), respectively. The overall concentration of K was found to be the highest, whereas the level of Cu was the lowest. The concentrations of Cu and Li were quite low in all samples, whereas Zn, Mn, Co and Na were found in moderate concentration and K, Ca and Fe were found in very high concentrations in all the samples tested.     

尿毒症患者与血清八种元素含量关系的研究

检测了３７例尿毒症患者血清微量元素Ｆｅ、Ｃｕ、Ｚｎ和常量元素Ｋ、Ｎａ、Ｃａ、Ｍｇ、Ｐ的含量，并进行比较，探讨其相互关系，以期为尿毒症的发生发展及防治措施提供依据．结果发现尿毒症患者血清Ｋ、Ｐ、Ｍｇ极显著高于对照组（均Ｐ＜０．０１），而Ｎａ、Ｃａ、Ｚｎ、Ｃｕ、Ｆｅ及Ｎａ／Ｋ、Ｃａ／Ｍｇ则极显著低于对照组（均Ｐ＜０．０１），且Ｎａ／Ｋ、Ｃａ／Ｍｇ与肾实质受损程度呈负相关，提示Ｎａ／Ｋ、Ｃａ／Ｍｇ降低与尿毒症的发生发展过程有密切的关系．     

Comparison of the Results of Atomic Absorption and X-ray Fluorescence Analysis of Metals in Atmospheric Aerosols

Factors responsible for the systematic discrepancies between the results of atomic absorption (standard procedure) and X-ray fluorescence determination of metals in atmospheric aerosols preconcentrated on a filter were studied. Patterns describing the errors in the results of determining Fe, Cu, Pb, Zn, Mn, and Cr by the proposed procedures depending on the type of the metal compound and the concentration of SiO₂ in aerosol particles were found. It was shown that the underestimation of the results of atomic absorption analysis in comparison to those obtained by X-ray fluorescence is due to the incomplete decomposition of some analyte compounds and the adsorption of Fe, Cu, and Pb on the precipitated SiO₂.     

Air quality control monitoring at an urban and industrialized area

Air particulate matter analysis has been performed since 1999, within a contract for air quality monitoring of an urban waste incinerator. Air collection was made with Gent samplers, which collect size-fractionated aerosol samples in three sampling sites. Samples were analyzed by instrumental neutron activation analysis (INAA) and proton induced X-ray emission (PIXE). In this study some INAA results are discussed. PM₁₀ mass concentrations are compared with the limit values for human health protection regulated by the European Council Directive 1999/30/CE. Weekend day and weekday samples are compared concerning As, Co, Fe, K, La, Na, Sb, Sc, Se and Zn mean concentrations collected at Bobadela for 1999. Enrichment factors are also presented. Enrichments were found for As, Sb, Se and Zn for both fractions in the three sampling sites. In order to quantify the evolution for the 1999-2001 period, basic statistics was performed for the enriched elements. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of heavy metal concentrations in plants exposed to different degrees of pollution using ICP-AES

Plant samples (Plantago lanceolata - narrow leaf plantain and Cichorium endiviae - endive) were collected in the surroundings of heavy metal emission sources and in other less contaminated areas. After digestion in a closed microwave system using HNO(3), the concentrations of Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn were determined using ICP-AES. Detection limits for all the elements of interest are given. Differences in heavy metal uptake rate between both plant species were observed. The uptake is more intensive for endive than for narrow leaf plantain. High concentrations of some heavy metals were determined in the unwashed plant samples as a result of exposure to aerosols. Tukey's statistical test was used to confirm the discrepancy of Cr concentration in plant samples from various areas. Washing the leaves with water was found to remove a large amount of water-soluble aerosols.