Distribution, availability, and sources of trace metals in different particle size fractions of urban soils in Hong Kong: Implications for assessing the risk to human health

The concentration and loading distribution of trace metals (Cu, Zn, Pb, Co, Ni, Cr, and Mn) and major elements (Al, Ca, Fe, and Mg) in different particle size fractions (2000-280, 280-100, 100-50, 50-10, 10-2, and <2 μm) of surface soils from highly urbanized areas in Hong Kong were studied. The enrichment of Pb, Cu, and Zn in the urban soils was strongly influenced by anthropogenic activities, and Pb accumulated in fine particles was mainly derived from past vehicular emissions as shown by Pb isotopic signatures. Trace metals primarily accumulated in clay, fine silt, and very fine sand fractions, and might pose potential health risks via the inhalation of resuspended soil particles in the air (PM₁₀ or PM_2.5), and ingestion of adhered soils through the hand-to-mouth pathway. The mobility, bioavailability, and human bioaccessibility of Pb and Zn in bulk soils correlated significantly with metal concentrations in fine silt and/or very fine sand fractions.     

Estimation of atmospheric trace metal emissions in Vilnius City, Lithuania, using vertical concentration gradient and road tunnel measurement data

A new approach for the estimation of trace metal emissions in Vilnius city was implemented, using vertical concentration profiles in the urban boundary layer and road tunnel measurement data. Heavy metal concentrations were examined in fine and coarse particle fractions using a virtual impactor (cut-off size diameter 2.5 μm). Negative vertical concentration gradients were obtained for all metals (Ba, Pb, V, Sb, Zn) and both fractions. It was estimated that the vertical concentration gradient was formed due to emissions from an area of about 12 km². Road tunnel measurements indicated that trace metal concentrations on fine particles were lower than those on coarse particles, which suggested that re-emitted road dust was highly enriched in trace metal due to historic emissions within the tunnel. Emission rates of different pollutants in the road tunnel were calculated using pollutant concentration differences at the tunnel entrance and exit and traffic flow data. Heavy metal emission rates from the area of Vilnius city were estimated using the vertical gradient of heavy metal concentrations and the coefficient of turbulent mixing, as derived from meteorological measurement data. The emission values calculated by the two different methods coincided reasonably well, which indicated that the main source of airborne trace metals in Vilnius city is traffic. The potential of the vertical concentration gradient method for the direct estimation of urban heavy metal emissions was demonstrated.     

Availability and bio-accessibility of metals in the clay fraction of urban soils of Sevilla

The availability of Cd, Cr, Cu, Ni, Mn, Pb and Zn present in the finest size particles of urban soils is studied by comparing the concentrations in the clay fraction with those extracted from the whole soil by either single-extraction or sequential extraction method. Many metals are preferentially present in the finest particles as compared to coarser fractions. This is true for most metals studied, except Mn and, perhaps, Cd. Those metals present in the clay fraction are often in easily bio-accessible forms, especially Cu, Pb and Zn. The results suggest that bio-accessible forms of these three metals are distributed among the three sequential fractions, and even the fraction considered as ‘residual’ is also bio-accessible to a significant extent. The statistical analysis shows some distinctions among metals that are compared to the ‘urban’, ‘natural’, or intermediate behaviour of the various metals as proposed earlier in the literature.     

Characterization of atmospheric particulates, particle-bound transition metals and polycyclic aromatic hydrocarbons of urban air in the centre of Athens (Greece)

The concentrations of trace metals and polycyclic aromatic hydrocarbons (PAHs) adsorbed to total suspended particulate (TSP) and finer fractions of airborne particulate matter (PM) were determined from a site in the centre of Athens (Greece), which is characterized by heavy local traffic and is densely populated, during the winter and summer periods in 2003-2004. Also, we collected and analyzed samples of diesel and gasoline exhaust particles from local vehicles (buses, taxis and private cars) and from chimney exhaust of residential central heating appliances. A seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. The most commonly detected trace metals in the TSP and PM fractions were Fe, Pb, Zn, Cu, Cr, V, Ni and Cd and their concentrations were similar to levels observed in heavily polluted urban areas from local traffic and other anthropogenic emissions. Analysis of 16 PAHs bound to PM showed that they are mostly traffic related. In general, the fine particulate PAHs concentrations were higher than coarse particles. The most common PAHs in PM(10.2) and PM(2.1) were pyrene, phenanthrene, acenapthylene and fluoranthene, which are associated with diesel and gasoline exhaust particles. The results of this study underlined the importance of local emission sources, especially vehicular traffic, central heating and other local anthropogenic emissions. Compared with other big cities, Athens has much higher levels of airborne particles, especially of the finer fractions PM(10) and PM(2.5), correlated with traffic-related air pollution.     

Heavy metal contamination characteristic of soil in WEEE (waste electrical and electronic equipment) dismantling community: a case study of Bangkok,Thailand

Sue Yai Utit is an old community located in Bangkok, Thailand which dismantles waste electrical and electronic equipment (WEEE). The surface soil samples at the dismantling site were contaminated with copper (Cu), lead (Pb), zinc (Zn), and nickel (Ni) higher than Dutch Standards, especially around the WEEE dumps. Residual fractions of Cu, Pb, Zn, and Ni in coarse soil particles were greater than in finer soil. However, those metals bonded to Fe-Mn oxides were considerably greater in fine soil particles. The distribution of Zn in the mobile fraction and a higher concentration in finer soil particles indicated its readily leachable character. The concentration of Cu, Pb, and Ni in both fine and coarse soil particles was mostly not significantly different. The fractionation of heavy metals at this dismantling site was comparable to the background. The contamination characteristics differed from pollution by other sources, which generally demonstrated the magnification of the non-residual fraction. A distribution pathway was proposed whereby contamination began by the deposition of WEEE scrap directly onto the soil surface as a source of heavy metal. This then accumulated, corroded, and was released via natural processes, becoming redistributed among the soil material. Therefore, the concentrations of both the residual and non-residual fractions of heavy metals in WEEE-contaminated soil increased.     

Characteristics of colloids and their affinity for heavy metals in road runoff with different traffic in Beijing,China

The characteristics of colloids in urban road runoff with different traffic in Beijing, China, such as concentration, particle size, chemical property, and affinity for heavy metals were determined. The concentration of colloids was high, and an evident first flush effect was found in the runoff of road with heavy traffic. A large portion of colloids were distributed in the range of 1–10 μm. Traffic activity, rainfall intensity, and time of sample collection would not change the size distribution of colloids in the road runoff. The chemical property of colloids in the road runoff would be influenced by the soil erosion nearby green space, causing the content of organic colloids was high. The correlation coefficient between the concentration of colloids in colloidal fractions and the concentration of heavy metals (Cu, Zn, Cd, Pb, Fe, and Mn) in the road runoff with different traffic decreased with the same sequence from 0.02–0.2 μm, 0.2–0.45 μm, 0.45–1 μm, to 1–10 μm, suggesting that the heavy metals had stronger affinity for the colloids with small size. The concentration of Cu, Pb, and Zn exhibited significant correlations with the concentration of organic colloids in the road runoff. More aggregated spherical particles were found in the TEM image of the road runoff with heavy traffic. Zeta potentials and RMV data showed that the colloids with smaller size and the colloids in the road runoff with lighter traffic were much more stable.

     

Fate of metal-associated POM in a soil under arable land use contaminated by metallurgical fallout in northern France

Organic matter is a major metal-retaining constituent in soils. Among the diversity of organic components in soils, particulate organic matter (POM) accumulates large amounts of metals, but the fate of such metal-associated POM is unknown. We studied different POM size fractions and their corresponding mineral size-fractions isolated from the surface horizon of a soil affected by metallurgical fallout. Analyses of total and EDTA extractible metal contents performed on all size fractions demonstrated that with decreasing POM size, larger metal concentrations were observed but they were less extractable. Micromorphological study revealed the occurrence of opaque parts in decaying POM fragments and their individualization as fine, irregularly shaped opaque fragments in the soil matrix. This work suggested a mutual sequestration of metal pollutants and organic carbon as micro-meter sized, metal-enriched organic particles derived from POM, representing an original pathway for natural attenuation of risk related to metal contaminated soils.     

高速公路路面沉积物的污染特性

对湖南省长潭西高速公路不同采样点的路面沉积物进行取样分析,并检测了样品的颗粒级配、COD、重金属(Cu、Zn、Pb和Cd)和有机质。结果表明,路面沉积物主要以粒径<0.15 mm的颗粒为主;较小颗粒物中的COD含量高于较大颗粒中的COD含量;粒径在0.15 mm以下的颗粒物所含重金属Cu、Zn、Pb和Cd的浓度普遍高于所选的土壤标准值,降雨一旦形成径流将会产生严重的污染危害;沉积物中的有机质含量对重金属的吸附有一定的影响,有机质含量越高,沉积物中重金属含量相对也高。     

Metals leachability from medical waste incinerator fly ash: A case study on particle size comparison

This paper presents the results from a study of metals leachability of medical waste incinerator fly ash in Japan on the basis of particle size. Sequential extraction and Toxicity Characteristic Leaching Procedure (TCLP) analysis were carried out in order to quantify the leaching amount of metals in each categorized particle size. Sequential extraction was also subjected to identify the preference of binding matrix of metals. The results of sequential extraction showed an increase both exchangeable and carbonate associated chromium concentrations in the bigger particle size fractions. Likewise, concentrations of carbonate matrix of arsenic and tin tended to increase in the bigger particle size fractions. In contrast, exchangeable associated cadmium as well as both exchangeable and carbonate matrices of barium were found higher in the smaller particle size fractions. However, no correlation was found in Kendal-tau correlation analysis between particle size of the ash and metals leachability of the TCLP.     

Chemical composition associated with different particle size fractions in municipal, industrial, and agricultural wastewaters

A more detailed characterization of particulate organic matter in wastewater streams is needed to improve solid-liquid separation and biological processes for wastewater treatment. The objective of this paper was to evaluate particle size distributions and the associated chemical composition for municipal, industrial, and agricultural waste streams. Most of the organic matter in these wastewaters was larger than a molecular weight of 10(3) amu and therefore would require extracellular hydrolysis before any bacterial metabolism. Particle size distributions were significantly different for the studied waste streams. In municipal wastewater, the organic matter was evenly distributed in all eight size fractions ranging from 10(3) amu up to 63 microm. The industrial and agricultural wastewaters, however, contained mainly soluble organic matter (<10(3) amu) and larger particles (>1.2 microm for the industrial and >10 microm for the agricultural waste) leaving a gap in the size range of large macromolecules and colloids. The relative protein and carbohydrate concentrations varied for the different size fractions compared to the measured chemical oxygen demand (COD) in the corresponding size fraction. Thus, the design of the solid-liquid separation at a treatment plant could be used to purposefully modify the overall chemical composition of the organic matter before further biological treatment. Particle size distributions will influence design and operation of biological nutrient removal processes such as denitrification or biological phosphorus removal that may be carbon limited if a large fraction of the organic matter is composed of large particles with slow hydrolysis rates. Measured particle size distributions for the different waste streams in this study (municipal, industrial, agricultural) were significantly different requiring specific approaches for treatment plant design.     

The Effect of Grain Size and Element Concentration in Identifying Contaminant Sources

The distribution of metal contaminants between different size fractions of marine sediments is well known. However, the use of size normalization techniques may alter the ability or usefulness in identifying potential sources in complex environments. In a reassessment of metal data from the shelf area of Sydney, Australia, the mud and sand fractions were investigated separately by PCA and PLS methodologies. The analyses were able to produce clear distinctions between industrial/urban sources when based on a suite of metals rather than individual (single-element) concentrations. Signature analysis by PLS with copper, lead, zinc, manganese, chromium, cobalt, nickel, and cadmium demonstrated the dispersion of the fine-grained contaminated material to the south in the East Australian Current. However, due to the commonality between many of the metals, a subset of four metals was used to define the signature. This significantly improved separation, showing clear plumes extending ～30 km from the source rivers.     

Concentration, size distribution, and dry deposition rate of particle-associated metals in the Los Angeles region

Daily averaged atmospheric concentrations and dry deposition fluxes of particulate metals were measured seasonally at six urban sites and one non-urban coastal site in the Los Angeles region using a conventional total suspended particulate matter (TSP) filter, surrogate surface deposition plates, and a Noll Rotary Impactor (NRI), which provides information about particle size distribution in four size ranges above 6 μm. With the exception of the non-urban site, particulate metal concentrations and deposition fluxes were remarkably uniform spatially and temporally. At all sites there were significant metal concentrations on particles greater than 10 μm, a commonly used upper limit for many air quality monitoring studies, and these large particles were estimated to be responsible for most of the deposited mass of metals. Annual averaged values of deposition rates measured with a surrogate surface were in good agreement with values estimated using theoretical deposition velocities in conjunction with measured size-segregated particle concentrations. Image analysis of particles deposited on NRI stage A, which collects all particles greater than 6 μm, indicated nighttime metal concentrations and deposition at the non-urban coastal site was higher than in the day time due to offshore advection of urban air associated with the diurnal land breeze. Measured enrichments of crustal elements and metals were correlated, indicating efficient mixing of natural and anthropogenic material from different sources, hypothesized to be the result of cyclical resuspension and deposition of dust by moving vehicles and wind.     

Size distribution of airborne particulate matter and associated heavy metals in the roadside environment

The size distributions of airborne particulate matter (PM) and associated heavy metals Pb, Cd, Ni, Cr, V, Mn, Cu and Fe in different inhalable fractions (< 0.8 microm, 0.8-1.3 microm, 1.3-2.7 microm, 2.7-6.7 microm and > 6.7 microm) were determined at a traffic-orientated urban site in the city of Thessaloniki, northern Greece. The airborne PM displayed a bimodal distribution with most of the mass (52%) contained in the submicron size range (< 0.8 microm) and an additional minor mode (20%) in the coarse size fraction (> 6.7 microm). Characteristic size distributions of heavy metals allowed identification of three main behavioral types: (a) metals whose mass was resided mainly within the accumulation mode (Pb,Cd), (b) those which were distributed between fine, intermediate and coarse modes (Ni,Cu,Mn), and (c) those which were mainly found within particles larger than 2.7 microm in diameter (Fe). The mean mass median aerodynamic diameter (MMAD) of PM was found at 0.85+/-0.71 microm, while the mean MMADs of heavy metals followed the order Pb (0.96 +/- 0.71 microm) < Cd (1.14 +/- 0.82 microm) < V (1.38 +/- 0.63 microm) < Ni (1.45 +/- 0.88 microm) < Cu (2.04 +/- 0.77 microm) < Mn (2.61 +/- 1.23 microm) < Cr (2.91 +/- 1.40 microm) < Fe (3.82 +/- 0.88 microm). The measured distributions are believed to result from a combination of processes including local anthropogenic and natural sources, such as traffic, industrial emissions and resuspension of road dust.     

Inter-Urban Comparison of Ambient Volatile Organic Compound Concentrations in U.S. Cities

Airborne particulate matter from three ferrous foundries was sampled in granulometric fractions and analyzed by scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDXA), X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) to determine morphology and qualitative bulk and surface chemical compositions. Cluster and principal components analyses (PCA) were used as an aid for interpretation of results. A clear pattern of composition as a function of size emerges; in particular, trace metals accumulate in fine particles and volatile species on the surface of these. Chemical composition changes are also related to daily schedules where applicable: trace metals appear during pouring operations, silicon is generated during mold making and unmolding. Cluster and PCA greatly ease examination of data and offer pictorial representations of results; in particular, the chemical composition versus particle size relationship is very neatly illustrated by PCA graphs.     

Occurrence of coal and coal-derived particle-bound polycyclic aromatic hydrocarbons (PAHs) in a river floodplain soil

A PAH contaminated river floodplain soil was separated according to grain size and density. Coal and coal-derived particles from coal mining, coal industry and coal transportation activities were identified by organic petrographic analysis in our samples. Distinct concentrations of PAHs were found in different grain size and density fractions, however, similar distribution patterns of PAHs indicated similar sources. In addition, although light fractions had the mass fraction by weight of less than 5%, they contributed almost 75% of the total PAHs in the soil. PAH concentrations of all sub fractions showed positive correlation with their TOC contents. Altogether, coal and coal-derived particles that were abundant in light fractions could be the dominant geosorbents for PAHs in our samples.     

Metal distributions in soil receiving urban pavement runoff and snowmelt.

Wet and dry deposition of anthropogenic metals and particulates generated from urban and traffic activities can result in contamination of urban-land-use soils. These particulate residuals encompass a wide size gradation, from 1 to greater than 10 000 microm. This study hypothesized that such contamination of surficial soils can be analyzed and explained as a function of the soil/residual granulometry. This study analyzed the gradation-based physical characteristics for 10 urban transportation land-use sites with soil/residual complexes (SRCs) located throughout metropolitan Cincinnati, Ohio, and an urban residential reference site. Particle density (rho(s)) of SRCs ranged from 2.8 to 2.1 g/cm3, with the lower particle density associated with particles less than 100 microm. For each site, specific surface area generally increased with decreasing particle size, while the predominance of total surface area was associated with the coarser size fractions, except for the clayey glacial till reference site not influenced by traffic. Cumulative analysis for lead, copper, cadmium, and zinc associated with SRCs indicated that more than 50% of the metal mass was associated with particles greater than 250 microm, with more than 80% associated with particles greater than 106 microm. Study results are similar to rainfall-runoff and snowmelt distributions. Results provide guidance when considering potential fate and control of metals transported by urban drainage and are distributed across the SRC size gradation.     

Metals in particle-size fractions of the soils of five European cities

Soils from Aveiro, Glasgow, Ljubljana, Sevilla and Torino have been investigated in view of their potential for translocation of potentially toxic elements (PTE) to the atmosphere. Soils were partitioned into five size fractions and Cr, Cu, Ni, Pb and Zn were measured in the fractions and the whole soil. All PTE concentrated in the <10 microm fraction. Cr and Ni concentrated also in the coarse fraction, indicating a lithogenic contribution. An accumulation factor (AF) was calculated for the <2 and <10 microm fraction. The AF values indicate that the accumulation in the finer fractions is higher where the overall contamination is lower. AF for Cr and Ni are particularly low in Glasgow and Torino. An inverse relationship was found between the AF of some metals and the percentage of <10 microm particles that could be of use in risk assessment or remediation practices.     

Chemical characterization and source identification/apportionment of fine and coarse air particles in Thessaloniki,Greece

The distribution of air particulate mass and selected particle components (trace elements and polycyclic aromatic hydrocarbons (PAHs)) in the fine and the coarse size fractions was investigated at a traffic-impacted urban site in Thessaloniki, Greece. 76±6% on average of the total ambient aerosol mass was distributed in the fine size fraction. Fine-sized trace elemental fractions ranged between 51% for Fe and 95% for Zn, while those of PAHs were between 95% and 99%. A significant seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. Similar seasonal trend was exhibited by PAHs, whereas larger fine fractions in summer were shown by trace elements. The compositional signatures of fine and coarse particle fractions were compared to that of local paved-road dust. A strong correlation was found between coarse particles and road dust suggesting strong contribution of resuspended road dust to the coarse particles. A multivariate receptor model (multiple regression on absolute principal component scores) was applied on separate fine and coarse aerosol data for source identification and apportionment. Results demonstrated that the largest contribution to fine-sized aerosol is traffic (38%) followed by road dust (28%), while road dust clearly dominated the coarse size fraction (57%).     

Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff

Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.     

Size distribution of metals in urban aerosols in Seville (Spain)

The size distribution of metals in aerosols has been studied in 12 areas of the city of Seville. Urban particles were collected with a high-volume sampling system equipped with a cascade impactor, which effectively separates the particulate matter into six-size ranges. Forty-one samples were collected in spring 1996. Each filter was extracted with a mixture of nitric and percloric acids. The acid solutions of the samples were analysed in six-particle fractions by inductively coupled plasma atomic emission spectrometry (ICP-AES). The impactor stage fractionation of particles shows a typical bimodal distributions, one corresponding to the fine mode below 1 μm (55%), and the other to the coarse mode around 10 μm (32%). With regard to the size distribution of metals, we concluded that potentially toxic metals, such as nickel, lead and cadmium are mainly accumulated in the smaller particles, with percentages of 72.6, 69.4 and 63.8%, respectively. Lead have a concentration of 63.7 ng m⁻³, more than copper and manganese (26.7 and 16.5 ng m⁻³) and above all more than nickel, cobalt and cadmium (1.97, 0.54 and 0.32 ng m⁻³).