Enrichment of trace elements in the clay size fraction of mining soils

Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps.     

Spatial and temporal variations of PM(2.5) concentration and composition throughout an urban area with high freeway density-the Greater Cincinnati study

The PM(2.5) concentration and its elemental composition were measured in the Cincinnati metropolitan area, which is characterized by intense highway traffic. The spatial and temporal variations were investigated for various chemical elements that contributed to the PM(2.5) fraction during a 1-year-long measurement campaign (December 2001-November 2002). The ambient aerosol monitoring was performed in 11 locations around the city during nine measurement cycles. During each cycle, four Harvard-type impactors were operating in parallel in specific locations to explore various factors affecting the PM(2.5) elemental concentrations. The sampling was performed during business days, thus assuring traffic uniformity. The 24-h PM(2.5) samples were collected on Teflon and quartz filters. Teflon filters were analyzed by X-ray fluorescence (XRF) analysis while quartz filters were analyzed by thermal-optical transmittance (TOT) analysis. In addition to PM(2.5) measurements, particle size-selective sampling was performed in two cycles using micro-orifice uniform deposit impactor; the collected fractionated deposits were analyzed by XRF. It was found that PM(2.5) concentration ranged from 6.70 to 48.3 mug m(-3) and had low spatial variation (median coefficient of variation, CV=11.3%). The elemental concentrations demonstrated high spatial variation, with the median CV ranged from 38.2% for Fe to 68.7% for Ni. For traffic-related trace metals, the highest concentration was detected in the city center site, which was close to a major highway. The particle size selective measurement revealed that mass concentration of the trace metals, such as Zn, Pb, Ni, as well as that of sulfur reach their peak values in the particle size range of 0.32-1.0 mum. Meteorological parameters and traffic intensity were not found to have a significant influence on the PM(2.5) elemental concentrations.     

Multivariate statistical evaluation of trace elements in groundwater in a coastal area in Shenzhen, China

Multivariate statistical techniques are efficient ways to display complex relationships among many objects. An attempt was made to study the data of trace elements in groundwater using multivariate statistical techniques such as principal component analysis (PCA), Q-mode factor analysis and cluster analysis. The original matrix consisted of 17 trace elements estimated from 55 groundwater samples colleted in 27 wells located in a coastal area in Shenzhen, China. PCA results show that trace elements of V, Cr, As, Mo, W, and U with greatest positive loadings typically occur as soluble oxyanions in oxidizing waters, while Mn and Co with greatest negative loadings are generally more soluble within oxygen depleted groundwater. Cluster analyses demonstrate that most groundwater samples collected from the same well in the study area during summer and winter still fall into the same group. This study also demonstrates the usefulness of multivariate statistical analysis in hydrochemical studies.     

Chemical characteristics and source apportionment of PM<Subscript>2.5</Subscript> using PCA/APCS,UNMIX, and PMF at an urban site of Delhi,India

The present study investigated the comprehensive chemical composition [organic carbon (OC), elemental carbon (EC), water-soluble inorganic ionic components (WSICs), and major & trace elements] of particulate matter (PM_2.5) and scrutinized their emission sources for urban region of Delhi. The 135 PM_2.5 samples were collected from January 2013 to December 2014 and analyzed for chemical constituents for source apportionment study. The average concentration of PM_2.5 was recorded as 121.9 ± 93.2 μg m^?3 (range 25.1–429.8 μg m^?3), whereas the total concentration of trace elements (Na, Ca, Mg, Al, S, Cl, K, Cr, Si, Ti, As, Br, Pb, Fe, Zn, and Mn) was accounted for ～17% of PM_2.5. Strong seasonal variation was observed in PM_2.5 mass concentration and its chemical composition with maxima during winter and minima during monsoon seasons. The chemical composition of the PM_2.5 was reconstructed using IMPROVE equation, which was observed to be in good agreement with the gravimetric mass. Source apportionment of PM_2.5 was carried out using the following three different receptor models: principal component analysis with absolute principal component scores (PCA/APCS), which identified five major sources; UNMIX which identified four major sources; and positive matrix factorization (PMF), which explored seven major sources. The applied models were able to identify the major sources contributing to the PM_2.5 and re-confirmed that secondary aerosols (SAs), soil/road dust (SD), vehicular emissions (VEs), biomass burning (BB), fossil fuel combustion (FFC), and industrial emission (IE) were dominant contributors to PM_2.5 in Delhi. The influences of local and regional sources were also explored using 5-day backward air mass trajectory analysis, cluster analysis, and potential source contribution function (PSCF). Cluster and PSCF results indicated that local as well as long-transported PM_2.5 from the north-west India and Pakistan were mostly pertinent.     

Characterization of Airborne Dust from Two Nonferrous Foundries by Physico-chemical Methods and Multivariate Statistical Analyses

Abstract

Airborne particulate matter was sampled at a copper smelter and at an aluminum casting plant. Size, shape, quantity, and microlocalization of chemical species in the particulates were measured using closed cassettes, cascade impactors, scanning electron microscopy, X-ray diffraction, infrared and atomic absorption spectrophotometries, secondary ion mass spectrometry, and photoelectron spectroscopy. Cluster and principal components analyses were used in interpreting results. Aerosol chemistry varies as a function of size, and composition becomes more complex as the aerosol size drops into the respirable fraction and lower. Surface chemical properties are evidenced where, generally, volatile species are enriched. A few site-specific elements and characteristics were identified. The formation of particulates may often be related to process and practices, yet the actual distribution of species in the air remains an intricate matter.     

Relationship among parameters of lake polluted sediments evaluated by multivariate statistical analysis

In the attempt to assess the relationship and interdependency among sediment toxic pollutants, in particular heavy metals, polycyclic aromatic hydrocarbons (PAH), and linear alkyl sulfonates (LAS) and some of the sediment typical components: inorganic carbon (IC), organic material (OM) and acid volatile sulphides (AVS), multivariate techniques of statistical analysis have been applied to a set of chemical data obtained by the analysis of the sediments of the Trasimeno Lake, a central Italy lake characterized by a large surface (128 km(2)) and a low mean depth (about 4.5 m). The results of principal component analysis (PCA) show interrelationships between: OM content and PAH, Pb, and Cu concentrations of the sediments, LAS and AVS, and AVS and IC. The effect of the different sampling periods on sediment composition and contamination level, and the clustering of the sampling sites as a consequence of pollutant load are also shown. The principal component bi-plot of the variables and samples indicates that PAH have the greatest influence on the separation of samples in the different sampling periods.     

Characterization of trace metal particles deposited on some deciduous tree leaves in an urban area

In 1996 and 1997 horse chestnut (Aesculus hippocastanum L.) and Turkish hazel (Corulys colurna L.) leaves were sampled at 2 m height in the Belgrade Botanic Garden, located in an urban area with heavy traffic. Using a scanning electron microscope with an energy dispersive X-ray spectroscopy (SEM-EDAX), the size, size distribution, morphology and chemical composition of individual particles were examined on the adaxial and abaxial surfaces of leaf discs of both species. The majority of particles observed on leaves belonged to a class of fine particles (D < 2 microm). Morphological and chemical composition indicated that the most abundant particles were soot and dust with minor constituents such as Pb, Zn, Ni, V, Cd, Ti, As and Cu. Using an electrochemical technique (DPASV), it was possible to measure trace metal concentrations (Pb, Cu, Zn) in a water-soluble fraction of deposits on each single leaf. Trace metal contents in the leaf deposits, increased during the vegetation period for both species and were considerably higher in A. hippocastanum due to different epidermal characteristics. The higher trace metal concentrations in deposits in 1997 reflected greater atmospheric pollution in the Belgrade urban area.     

Trends in hazardous trace metal concentrations in aerosols collected in Beijing, China from 2001 to 2006

Daily observations of hazardous trace metal concentrations in aerosols in Beijing, China were made in the period from 2001 to 2006. We considered coal combustion as a major source of some anthropogenic metals by achieving a correlation analysis and by investigating enrichment factors and relative composition of metals. A possible extra source of some specific metals, such as Cu and Sb, was brake abrasion particles, however, we did not think the transport-related particle was a major source for the hazardous anthropogenic metals even though they could originate from vehicle exhaust and brake/tire abrasion particles. A time-trend model was used to describe temporal variations of chemical constituent concentrations during the five-year period. Several crustal elements, such as Al, Ti, V, Cr, Mn, Fe, and Co, did not show clear increases, with annual rates of change of -15.2% to 3.6%. On the other hand, serious increasing trends were noted from several hazardous trace metals. Cu, Zn, As, Cd, and Pb, which are derived mainly from anthropogenic sources, such as coal combustion, showed higher annual rate of change (4.9-19.8%, p<0.001) according to the regression model. In particular, the Cd and Pb concentrations increased remarkably. We hypothesize that the trend towards increasing concentrations of metals in the air reflects a change that has occurred in the process of burning coal, whereby the use of higher temperatures for coal combustion has resulted in increased emissions of these metals. The increasing use of low-rank coal may also explain the observed trends. In addition, nonferrous metal smelters are considered as a potential, albeit minor, reason for the increasing atmospheric concentrations of anthropogenic hazardous metals in Beijing city.     

Structure of inorganic and carbonaceous particles emitted from heavy oil combustion

The combustion of heavy fuel oil for power generation is a great source of carbonaceous and inorganic particle emissions, even though the combustion technologies and their efficiency are improving. The information about the size distribution function of the particles originated by trace metals present into the fuels is not adequate. In this paper, we focused our attention on the larger distribution mode of both the carbonaceous and metallic particles. Isokinetic sampling was performed at the exhausts of two typical heavy oil flames and the samples were size-segregated by mean of an 8-stages Andersen impactor. Further investigation performed on the samples using electronic microscopy coupled with X-ray analysis (EDX) evidenced the presence of solid spherical particles, called plerosphere(1) as analogy with cenosphere, with typical dimensions ranging between 200 nm and 2-3 microm, whose atomic composition contains a large amount of the trace metals present in the parent oils (Fe, V, Ni, etc). EDX analyses revealed that the metal concentration increases as the plerosphere dimension decreases.     

Assessment of heterogeneity of metal composition of fine particulate matter collected from eight U.S. counties using principal component analysis

The main objectives of this study are to (1) characterize chemical constituents of particulate matter (PM) and (2) compare overall differences in PM collected from eight US. counties. This project was undertaken as a part of a larger research program conducted by the Johns Hopkins Particulate Matter Research Center (JHPMRC). The goal of the JHPMRC is to explore the relationship between health effects and exposure to ambient PM of differing composition. The JHPMRC collected weekly filter-based ambient fine particle samples from eight US. counties between January 2008 and January 2010. Each sampling effort consisted of a 5-6-week sampling period. Filters were analyzed for 25 metals using inductively coupled plasma mass spectrometry (ICP-MS). Overall compositional differences were ranked by principal component analysis (PCA). The results showed that weekly concentrations of each element varied 3-40 times between the eight counties. PCA showed that the first five principal components explained 85% of the total variance. The authors found significant overall compositional differences in PM as the average of standardized principal component scores differed between the counties. These findings demonstrate PCA is a useful tool to identify the differences in PM compositional mixtures by county. These differences will be helpful for epidemiological and toxicological studies to help explain why health risks associated with PM exposure are different in locations with similar mass concentrations of PM.     

Emissions of organic compounds and trace metals in fine particulate matter from motor vehicles: a tunnel study in Houston, Texas

Fine particulate matter (PM) samples collected in a highway tunnel in Houston, TX, were analyzed to quantify the concentrations of 14 n-alkanes, 12 polycyclic aromatic hydrocarbons, and nine petroleum biomarkers, as well as 21 metals, with the ultimate aim of identifying appropriate tracers for diesel engines. First, an exploratory multivariate dimensionality reduction technique called principal component analysis (PCA) was employed to identify all potential candidates for tracers. Next, emission indices were calculated to interpret PCA results physically. Emission indices of n-heneicosane, n-docosane, n-tricosane, n-tetracosane, n-pentacosane, fluoranthene, and pyrene were correlated highly and increased strongly with percentage carbon present in the tunnel emanating from diesel vehicles. This suggests that these organic compounds are useful molecular markers to separate emissions from diesel and gasoline engines. Additionally, the results are the first quantification of the metal composition of PM with aerodynamic diameters smaller than 2.5 microm (PM2.5) emissions from mobile sources in Houston. PCA of trace metal concentrations followed by emission index calculations revealed that barium in fine airborne particles can be linked quantitatively to diesel engine emissions, demonstrating its role as an elemental tracer for heavy-duty trucks.     

A review of the impact of fireworks on particulate matter in ambient air

To determine the impact of fireworks (FW) and firecrackers (FC) on particulate matter (PM) in ambient air, we reviewed evidence related to ambient PM during FW/FC periods; specifically, PM concentration, size, morphology, chemical components, including water-soluble ions and trace metals, and associated human health risks caused by exposure to FW/FC PM were reviewed. A large body of research suggests that outdoor ambient PM levels increase significantly during FW/FC displays. Furthermore, FW/FC PM remains suspended in the air, contributing to high PM concentrations for a long period. Increased PM from burning FW and FC mainly comprises fine and ultrafine spherical particles. Elevated levels of various trace metals, ions, elemental carbon (EC), organic carbon (OC), and organics in PM are present during FW/FC periods.Implications: Unique physical and chemical properties of ambient PM during short-term FW/FC burning can lead to a substantial increase in adverse health effects compared with during non-FW/FC periods. Further epidemiological and toxicological research into the potential health effects resulting from exposure to various pollutants from FW/FC is vital. Geographical distributions of PM concentrations during FW displays highlight the importance of implementing PM controls at the regional level and formulating stricter protective environmental legislation, particularly in Asian (e.g., India, China, or Taiwan) where festivals are not the only periods celebrated with FW/FC.     

Storage and distribution of trace metals and spheroidal carbonaceous particles (SCPs) from atmospheric deposition in the catchment peats of Lochnagar, Scotland.

Lochnagar is a remote mountain lake to the south-east of the Cairngorm region in Scotland. Its catchment receives anthropogenic trace metals solely from atmospheric deposition. Ten peat cores were taken from the catchment and analysis confirmed that they have been contaminated by trace metals. The peats have an high affinity for trace metals and this results in metal accumulation in the surface peat layers. The formation of trace metal sulphides may also reduce remobilisation. In this way, trace metals derived from atmospheric deposition have been scavenged and accumulated. In contaminated peat layers, 77.4% Hg, 89.6% Pb, 93.4% Cu, 72.4% Zn and 86.5% Cd of the total stored are from anthropogenic sources. The accumulated trace metals in the peats can potentially influence the lake system through erosion. Spheroidal carbonaceous particle (SCP) profiles were used to date the peat cores. By referring to the SCP profiles in the peats and comparing these with the trace metal profiles in the lake sediments, the mobility of trace metals in the catchment peats is confirmed.     

Competition between alga (Pseudokirchneriella subcapitata), humic substances and EDTA for Cd and Zn control in the algal assay procedure (AAP) medium

The chemical speciation of trace metals in natural waters has important implications for their biogeochemical behavior. Trace metals are present in natural waters as dissolved species and associated with colloids and particles. The complexation of one trace metal (Cd and Zn at 200 and 390 microg/l respectively) with a green alga Pseudokirchneriella subcapitata in colloid-free algal culture medium and in presence of colloidal humic substances (HS) is presented. The influence of the nature of colloids was also addressed using three "standard" HS: fulvic acid (FA) and, soil (SHA) and peat humic acids (PHA). The chemical speciation model, MINTEQA2, was used to simulate the influence of pH and standardized culture medium on metal association with humic substances. The model was successfully modified to consider the differences in the metal complexation with fulvic (FA) and humic acids (HA). The deviations of concentrations of metals associated with HS between experimental results and model predictions were within a factor of approximately 2. The results of speciation model highlight the influence of the experimental conditions (pH, EDTA) used for alga bioassay on the behavior of Cd and Zn. The computed speciation suggests working with a pH buffered/EDTA-free mixture to avoid undesirable competition effects. The behavior of Cd and Zn in solution is more strongly influenced by HS than by alga. Metal-HS associations depend on metal and humic substance nature and concentration. Cd is complexed to a higher extent than Zn, in particular at larger HS concentration, and the complexation strength is in the order FA相似文献   

Biomonitoring of concentrations of platinum group elements and their correlations to other metals

Biomonitoring of Pt, Pd, Pb, Mn, Cu, Fe and Zn was conducted using leaves (two and six months old) of laurel (Laurus nobilis L.) ornamental shrubs grown in 14 sampling sites located on the central green belts of six avenues and streets of Athens. In this biomonitoring, we determined, for the first time in Greece, the concentrations of the new urban 'pollutants' Pt and Pd, and we estimated the correlations among the concentrations of all the above-mentioned metals as well as among the metal concentrations and the traffic load. Cluster analysis and principal component analysis (PCA) of the data revealed three distinct groups of metals and two groups of sites (one with high and the other with relatively low levels of pollution). Using varimax-rotated PCA for the metals, four factors were extracted explaining 92.3% of the total shared variance, which are further discussed. The importance of seasonal timing of sampling is revealed by the data and discussed in connection with the meteorological conditions.     

Natural and pre-treatments induced variability in the chemical composition and morphology of lichens and mosses selected for active monitoring of airborne elements

To enhance the reliability of the moss and lichen transplant technique for active biomonitoring of trace metals in urban environments, we evaluated the natural variability in the chemical composition of the (epilithic and epiphytic) moss Hypnum cupressiforme and the epiphytic lichen Pseudevernia furfuracea from two reference areas in NE Italy. Green shoots of epilithic mosses and lobes of epiphytic lichens from larch branches showed rather homogenous composition and were selected for the exposure in nylon bags. As different physico-chemical pre-treatments are usually applied to selected cryptogamic material before its exposure, we also evaluated the effects of oven-drying at 120 degrees C for 24h, washing in 1N HNO3 solution, and in 0.5% NH4 oxalate solution at 85 degrees C for 15 h on the chemical composition and morphology of water-washed moss shoots and lichen lobes. Pre-treatments remarkably changed the chemical composition of selected materials but not their surface morphology.     

Analysis of trace elements and ions in ambient fine particulate matter at three elementary schools in Ohio

The results from a chemical characterization study of fine particulate matter (PM2.5) measured at three elementary schools in Central and Southeast Ohio is presented here. PM2.5 aerosol samples were collected from outdoor monitors and indoor samplers at each monitoring location during the period of February 1, 1999, through August 31, 2000. The locations included a rural elementary school in Athens, OH, and two urban schools within Columbus, OH. The trace metal and ionic concentrations in the collected samples were analyzed using an X-ray fluorescence spectrophotometer and ion chromatography unit, respectively. Sulfate ion was found to be the largest component present in the samples at all three of the sites. Other abundant components included nitrate, chloride, ammonium, and sodium ions, as well as calcium, silicon, and iron. The average PM2.5 concentrations showed similar temporal variations among the three sites within the study region. PM2.5 and its major component, sulfate ion, showed strong seasonal variations with maximum concentrations observed during the summer at all three of the sites. The indoor environment was found to be more contaminated during the spring months (March through May) at New Albany (a suburb of Columbus, OH) and East Athens (rural Ohio area). Potential source contribution function analysis showed that particulate matter levels at the monitoring sites were affected by transport from adjoining urban areas and industrial complexes located along the Ohio River Valley. A preliminary outdoor source apportionment using the principal component analysis (PCA) technique was performed. The results from the PCA suggest that the study region was primarily impacted by industrial, fossil fuel combustion, and geological sources. The 2002 emissions inventory data for PM2.5 compiled by Ohio Environmental Protection Agency also showed impacts of similar source types, and this was used to validate the PCA analysis.     

Enhancement of source traceability of atmospheric PM by elemental chemical fractionation

During a 1-year study (“Fine dust” Project) funded by the Lazio regional government (Italy), about 1000 daily PM₁₀ and PM_2.5 samples collected from six sites in the region were subjected to chemical fractionation based on differences in elemental solubility. In this way, it was possible to achieve meaningful characterization of the elemental composition of individual samples. For most of the investigated elements, we found significant differences between the extracted and the mineralized residual fraction. In general, fine particulate was best characterized by the composition of the extracted fraction, while coarse particles from traffic-related sources were best characterized using residues. For several metals (Cd, Pb, Sn, Sb and V) having a critical environmental impact, this result was particularly clear.The application of Principal Component Analysis (PCA) and receptor modelling (PCR) to the data set allowed us to evidence the enhancement of selectivity towards different emission sources that is obtained when chemical fractionated data are considered instead of total element content. Chemical fractionation seems to generate very selective markers for specific emission sources and in particular for re-suspended road dusts, one of the main factors responsible for the increase of elemental concentrations in urban areas.     

Exploratory study of some potential environmental impacts of CO2 sequestration in unmineable coal seams

An initial investigation into the potential environmental impacts of CO₂ sequestration in unmineable coal seams has been conducted, focusing on changes in the produced water during enhanced coalbed methane (ECBM) production, using a CO₂ injection process (CO₂-ECBM). A high volatile bituminous coal, Pittsburgh No. 8, was reacted with synthetic produced water and gaseous carbon dioxide at 40°C and 50 bar to evaluate the potential for mobilisation of toxic metals during CO₂-ECBM/sequestration. Microscopic and X-ray diffraction analysis of the post-reaction coal samples clearly show evidence of chemical reaction and chemical analysis of the synthetic produced water shows substantial changes in composition. These results suggest that changes to the produced water chemistry and the potential for mobilising toxic trace elements from coal beds are important factors to be considered when evaluating deep, unmineable coal seams for CO₂ sequestration.