Dissolution and solubility of trace metals from natural and anthropogenic aerosol particulate matter

An open flow reactor is used to simulate the dissolution process of mineral aerosol particles in atmospheric water droplets. Data on dissolution kinetic and solubility are provided for the major trace metals from two kinds of matrix: alumino-silicated and carbonaceous sample. The results emphasise that the metals contained in the carbonaceous aerosols are easier dissolved than in the alumino-silicated particles. The released concentrations are not related to the total metal composition or the origin of particles, but are directly associated with the type of liaisons whereby the metals are bound in the solid matrix. Thus, the metals coming from carbonaceous particles are adsorbed impurities or salts and hence are very soluble and with a dissolution hardly dependent on pH, whereas the metals dissolved from alumino-silicated particles are less soluble, notably the ones constitutive of the matrix network (Fe, Mn), and with a dissolution highly influenced by pH. Consequently, in the regions with an anthropogenic influence, the dissolved concentrations of metals found in the atmospheric waters are mainly governed by the elemental carbon content. Moreover, it appears that the dissolution kinetic of metals is not constant as a function of time. The dissolution rates are very rapid in the first 20 min of leaching and then they are stabilised to lower values in comparison to initial rates. By consequence, the total dissolved metal content is provided after the first 20 min of the droplet lifetime. For this reason, the effects of trace metals on the atmospheric aqueous chemistry and as atmospheric wet input to the marine biota are maximal for "aged" droplets.     

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.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.     

Atmospheric concentrations and dry deposition fluxes of particulate trace metals in Salvador,Bahia, Brazil

Respiratory system is the major route of entry for airborne particulates, being the effect on the human organism dependent on chemical composition of the particles, exposure time and individual susceptibility. Airborne particulate trace metals are considered to represent a health hazard since they may be absorbed into human lung tissues during breathing. Fossil fuel and wood combustion, as well as waste incineration and industrial processes, are the main anthropic sources of metals to the atmosphere. In urban areas, vehicular emissions—and dust resuspension associated to road traffic—become the most important manmade source.This work investigated the atmospheric concentrations of TSP, PM₁₀ and elements such as iron, manganese, copper and zinc, from three different sites around Salvador Region (Bahia, Brazil), namely: (i) Lapa Bus Station, strongly impacted by heavy-duty diesel vehicles; (ii) Aratu harbor, impacted by an intense movement of goods, including metal ores and concentrates and near industrial centers and; (iii) Bananeira Village located on Maré Island, a non-vehicle-influenced site, with activities such as handcraft work and fishery, although placed near the port. Results have pointed out that TSP concentrations ranged between 16.9 (Bananeira) and 354.0 μg m⁻³ (Aratu#1), while for PM₁₀ they ranged between 30.9 and 393.0 μg m⁻³, both in the Lapa Bus Station. Iron was the major element in both Lapa Station and Aratu (#1 and #2), with average concentrations in the PM₁₀ samples of 148.9, 79.6 and 205.0 ng m⁻³, respectively. Zinc, on the other hand, was predominant in samples from Bananeira, with an average concentration of 145.0 ng m⁻³ in TSP samples, since no PM₁₀ sample was taken from this site. The main sources of iron in the Lapa Station and Aratu harbor were, respectively, soil resuspension by buses and discharge of solid granaries, as fertilizers and metal ores. On the other hand, zinc and copper in the bus station were mainly from anthropic contributions, probably heavy-duty vehicle ageing and wearing actions releasing off Zn from tires and Cu from brake linings. In the Aratu harbor, the high copper concentrations found were probably due to the port's activities, as discharges of copper concentrate on its terminal, although other sources could be possible, as burning of diesel fuel on ships and heavy oil in heaters. Finally, the Bananeira site has been presented as a different profile, since this remote site has shown zinc as the most abundant element, demonstrating to have an unexpected anthropic contribution. On a mass-to-mass basis, both zinc and manganese were in high levels in the Bananeira site and their presence strongly suggest the impact of other sources, such as the Industrial Center of Aratu and/or a siderurgy plant, not far away from that location.     

A multi-approach monitoring of particulate matter, metals and PAHs in an urban street canyon

For the first time until now, the results from a prediction model (Atmospheric Dispersion Modelling System (ADMS)-Road) of pollutant dispersion in a street canyon were compared to the results obtained from biomonitors. In particular, the instrumental monitoring of particulate matter (PM10) and the biomonitoring of 14 polycyclic aromatic hydrocarbons (PAHs) and 11 metals by Quercus ilex leaves and Hypnum cupressiforme moss bags, acting as long- and short-term accumulators, respectively, were carried out. For both PAHs and metals, similar bioaccumulation trends were observed, with higher concentrations in biomonitors exposed at the leeward canyon side, affected by primary air vortex. The major pollutant accumulation at the leeward side was also predicted by the ADMS-Road model, on the basis of the prevailing wind direction that determines different exposure of the street canyon sides to pollutants emitted by vehicular traffic. A clear vertical (3, 6 and 9 m) distribution gradient of pollutants was not observed, so that both the model and biomonitoring results suggested that local air turbulences in the street canyon could contribute to uniform pollutant distribution at different heights.     

Distribution of polycyclic aromatic hydrocarbons in water, suspended particulate matter and sediment from Daliao River watershed, China

This study investigated the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in surface water, suspended particulate matter (SPM) and sediment of Daliao River watershed composed of the Hun River, Taizi River, and Daliao River. The sources of PAHs were evaluated employing ratios of specific PAHs compounds and principal component analysis (PCA). The total concentrations of PAHs ranged from 946.1 to 13448.5 ng l(-1) in surface water, from 317.5 to 238518.7 ng g(-1) dry weight in SPM, and from 61.9 to 840.5 ng g(-1) dry weight in sediments. The levels of PAHs are relatively higher in water and SPM, and lower in sediments, in comparison with those reported for other rivers and marine systems around the world. The composition of PAHs in these mediums was mainly 4-6 rings PAHs. The higher contents of low molecular weight PAHs in the water and SPM suggest a relatively recent local source of PAHs, entered into the river via wastewater discharge and atmospheric way. On the other hand, the heavy pollution of PAHs in sediment and water near heavy industrial area suggests that PAHs have been released from industrial wastewater.     

Determination of major natural and anthropogenic source profiles for particulate matter and trace elements in Izmir, Turkey

Samples of PM10 and PM2.5 were collected from several natural and anthropogenic sources using in-stack cyclone, grab sampling/resuspension chamber and ambient air samplers. The chemical characterization of the samples was achieved containing Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn using an inductively coupled plasma-optical emission spectrometer (ICP-OES). The elemental fractions (weight percent by mass), standard deviations and uncertainties were reported. The elemental compositions of PM emitted from mineral industries and cement kiln were dominated by terrestrial elements, particularly Ca, whereas the profile of top-soil mainly contained Al and Ca. The profiles of industrial sources were generally typical for related ones; however, significant differences were obtained for some of them. Similarly, the profiles of fuel burning emissions have significant differences compared to profiles obtained all around the world.     

Impact of atmospheric deposition of anthropogenic and natural trace metals on Northwestern Mediterranean surface waters: a box model assessment

Under stratified oligotrophic conditions (May-November), the surface mixed layer of the Northwestern Mediterranean constitutes a homogeneous water volume of 10-30 m depth. In other respects, the mean residence time of Ligurian surface waters (0-200 m) is 102 days. It is therefore possible to quantify the extent to which atmospheric deposition of trace metals affects surface waters. On the basis of literature data on anthropogenic and natural trace metals, we demonstrate that the ratios between total seawater labile atmospheric deposition during 102 days (Δc) and dissolved TM concentrations in Ligurian surface waters (c) illustrate the impact of atmospheric deposition on surface seawater (Δc/c). High ratios indicate surface TM enrichments, while low ratios indicate surface TM depletion, due to the quasi-complete sorption and removal of TMs by plankton during spring bloom. The simple box model proposed here may be used for other marine regions where hydrodynamical and physico-chemical constraints are well defined.     

Nickel speciation of residual oil fly ash and ambient particulate matter using X-ray absorption spectroscopy

The chemical speciation of Ni in fly ash produced from approximately 0.85 wt % S residual (no. 6 fuel) oils in laboratory (7 kW)- and utility (400 MW)-scale combustion systems was investigated using X-ray absorption fine structure (XAFS) spectroscopy, X-ray diffraction (XRD), and acetate extraction [1 M NaOAc-0.5 M HOAc (pH 5) at 25 degrees C]-anodic stripping voltammetry (ASV). XAFS was also used to determine the Ni speciation of ambient particulate matter (PM) sampled near the 400-MW system. Based on XAFS analyses of bulk fly ash and their corresponding acetate extraction residue, it is estimated that > 99% of the total Ni (0.38 wt %) in the experimentally produced fly ash occurs as NiSO4.xH2O, whereas > 95% of the total Ni (1.70 and 2.25 wt %) in two fly ash samples from the 400-MW system occurs as NiSO4.xH2O and Ni-bearing spinel, possibly NiFe2O4. Spinel was also detected using XRD. Acetate extracts most of the NiSO4.xH2O and concentrates insoluble NiFe2O4 in extraction residue. Similar to fly ash, ambient PM contains NiSO4.xH2O and NiFe2O4; however, the proportion of NiSO4.xH2O relative to NiFe2O4 is much greater in the PM. Results from this and previous investigations indicate that residual oil ash produced in the 7-kW combustion system lack insoluble Ni (e.g., NiFe2O4) but are enriched in soluble NiSO4.xH2O relative to fly ash from utility-scale systems. This difference in Ni speciation is most likely related to the lack of additive [e.g., Mg(OH)2] injection and residence time in the 7-kW combustion system.     

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.     

Risk assessment of heavy metals in suspended particulate matter in a typical urban river

Environmental Science and Pollution Research - Suspended particulate matter (SPM) is a major source of contamination in urban rivers as it serves as a carrier for pollutants, such as heavy metals....     

Wash effect of atmospheric trace metals wet deposition and its source characteristic in subtropical watershed in China

In order to better understand air pollution in deve-loping regions, such as China, it is important to investigate the wet deposition behavior of atmospheric trace metals and its sources in the subtropical watershed. This paper studies the seasonal change of trace metal concentrations in precipitation and other potential sources in a typical subtropical watershed (Jiazhuhe watershed) located in the downstream of the Yangtze River of China. The results show that typical crustal elements (Al, Fe) and trace element (Zn) have high seasonal variation patterns and these elements have higher contents in precipitation as compared to other metals in Jiazhuhe watershed. In addition, there is no observed Pb in base flow in this study, and the concentration magnitudes of Al, Ba, Fe, Mn, Sr, and Zn in base flow are significantly higher than that of other metals. During different rainfall events, the dynamic export processes are also different for trace metals. The various trace metals dynamic export processes lead to an inconsistent mass first flush and a significant accumulative variance throughout the rainfall events. It is found that in this region, most of the trace metals in precipitation are from anthropogenic emission and marine aerosols brought by typhoon and monsoon.

     

Comparison of speciation sampler and PC-BOSS fine particulate matter organic material results obtained in Lindon, Utah, during winter 2001-2002

The Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) has been previously verified as being capable of measuring total fine particulate matter (PM2.5), including semi-volatile species. The present study was conducted to determine if the simple modification of a commercial speciation sampler with a charcoal denuder followed by a filter pack containing a quartz filter and a charcoal-impregnated glass (CIG) fiber filter would allow for the measurement of total PM2.5, including semi-volatile organic material. Data were collected using an R&P (Rupprecht and Pastasnik Co., Inc.) Partisol Model 2300 speciation sampler; an R&P Partisol speciation sampler modified with a BOSS denuder, followed by a filter pack with a quartz and a CIG filter; a Met One spiral aerosol speciation sampler (SASS); and the PC-BOSS from November 2001 to March 2002 at a U.S. Environmental Protection Agency (EPA) Science to Achieve Results (STAR) sampling site in Lindon, UT. Total PM2.5 mass, ammonium nitrate (both nonvolatile and semi-volatile), ammonium sulfate, organic carbon (both non-volatile and semi-volatile), and elemental carbon were determined on a 24-hr basis. Results obtained with the individual samplers were compared to determine the capability of the modified R&P speciation sampler for measuring total PM2.5, including semi-volatile components. Data obtained with the modified speciation sampler agreed with the PC-BOSS results. Data obtained with the two unmodified speciation samplers were low by an average of 26% because of the loss of semi-volatile organic material from the quartz filter during sample collection.     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

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.     

An investigation on the physical,chemical and ecotoxicological characteristics of particulate matter emitted from light-duty vehicles

Particulate matter (PM) emitted from three light-duty vehicles was studied in terms of its physicochemical and ecotoxicological character using Microtox^® bioassay tests. A diesel vehicle equipped with an oxidation catalyst emitted PM which consisted of carbon species at over 97%. PM from a diesel vehicle with a particle filter (DPF) consisted of almost equal amounts of carbon species and ions, while a gasoline vehicle emitted PM consisting of ～90% carbon and ～10% ions. Both the DPF and the gasoline vehicles produced a distinct nucleation mode at 120 km/h. The PM emitted from the DPF and the gasoline vehicles was less ecotoxic than that of conventional diesel, but not in direct proportion to the emission levels of the different vehicles. These results indicate that PM emission reductions are not equally translated into ecotoxicity reductions, implying some deficiencies on the actual environmental impact of emission control technologies and regulations.     

Biomonitoring of urinary metals in athletes according to particulate matter air pollution before and after exercise

Environmental Science and Pollution Research - Exposure to air pollution during physical exercise is a health issue because fine particulate matter (dimension &lt; 10 μm; PM10) includes...     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.