Next Article in Journal
Susceptibility to Heat-Related Fluid and Electrolyte Imbalance Emergency Department Visits in Atlanta, Georgia, USA
Previous Article in Journal
Local Geographic Variation of Public Services Inequality: Does the Neighborhood Scale Matter?
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Characterization of Airborne Particles Collected from Car Engine Air Filters Using SEM and EDX Techniques

by
Birmania Heredia Rivera
and
Martín Gerardo Rodriguez
*
Physiology and Pharmacology Department, Center of Basic Sciences, Autonomous University of Aguascalientes, Aguascalientes 20931, Mexico
*
Author to whom correspondence should be addressed.
Int. J. Environ. Res. Public Health 2016, 13(10), 985; https://0-doi-org.brum.beds.ac.uk/10.3390/ijerph13100985
Submission received: 14 July 2016 / Revised: 13 September 2016 / Accepted: 21 September 2016 / Published: 1 October 2016

Abstract

:
Particulate matter accumulated on car engine air-filters (CAFs) was examined in order to investigate the potential use of these devices as efficient samplers for collecting street level air that people are exposed to. The morphology, microstructure, and chemical composition of a variety of particles were studied using scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX). The particulate matter accumulated by the CAFs was studied in two categories; the first was of removed particles by friction, and the second consisted of particles retained on the filters. Larger particles with a diameter of 74–10 µm were observed in the first category. In the second one, the detected particles had a diameter between 16 and 0.7 µm. These particles exhibited different morphologies and composition, indicating mostly a soil origin. The elemental composition revealed the presence of three groups: mineral (clay and asphalt), metallic (mainly Fe), and biological particles (vegetal and animal debris). The palynological analysis showed the presence of pollen grains associated with urban plants. These results suggest that CAFs capture a mixture of atmospheric particles, which can be analyzed in order to monitor urban air. Thus, the continuous availability of large numbers of filters and the retroactivity associated to the car routes suggest that these CAFs are very useful for studying the high traffic zones within a city.

1. Introduction

The composition of air, which is a mixture of solid particles, liquids, and gases, is important in determining life quality in big cities. Air pollution is a growing problem generated mainly by industrial and vehicular emissions. Particulate matter (PM) in urban areas is made up of dust deposited on the soil as well as by particles released by anthropogenic activities [1,2,3]. PM is usually characterized by its physical size or diameter and composition, ranging from nanometers (nm) to several tens of micrometers (µm). Particles with a diameter less than 10 μm are classified as PM10. Particles with diameters between PM10 and PM2.5 are defined as the coarse fraction [4,5]. PM2.5 includes all particles with diameters less than 2.5 μm, also known as fine particles. These fine particles are of special concern for two reasons. First, these particles are able to penetrate deep into the human respiratory system and can be absorbed into the blood, where they have been shown to cause biological effects. Second, these particles scatter light very efficiently and therefore play a major role in visibility impairment [6]. The smallest particles, ultrafines, have diameters <0.1 µm. Ultrafines, which are the most numerous but have the smallest mass and volume, are the subject of recent investigations into health effects [7]. Particle deposition in the various regions of human respiratory system depends strongly on particle size and shape by the complex action of aerosol deposition mechanisms [8], with the greatest fractional deposition occurring in the deep lung between 5 nm and 100 nm. The study of their composition is a powerful tool for evaluation of the effects of pollution on health and for identification of pollution sources [9].
Because of the diversity of sources, these particles vary greatly in their size, morphologies, and chemical composition, therefore, it is essential to understand the size distribution and chemical composition of the particles, particularly in the urban atmosphere. A detailed characterization of individual atmospheric particles also provides useful information about their sources, formation, reactivity, transport, and removal. Scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) analysis is commonly used for the study of single particles [10], as this method provides useful information on the morphology, elemental composition, and density of aerosols and also provides insight into the particle origin, which may be from anthropogenic or natural processes [11]. To date, PM2.5 is monitored by means of conventional sampling methods that include high-volume air sampling through a filter, and these methods have been used for decades to monitor atmospheric concentrations of PM. These systems use a pump to draw air through a glass fiber filter to collect particulate species, however, this type of sampling can be costly and is not always feasible. These stationary samplers are usually placed onsite where a power supply is necessary and cannot provide an overall air pollution level data for a large area, thus the determined air concentrations are somewhat site-specific.
Recently. Zhang et al. [12] and Katsoyiannis et al. [13] suggested that car air filters (CAFs) from taxis could act as “moving” high volume air samplers to provide city-integrated air concentrations with low variability for particle-bound contaminants. CAFs, which are necessary components of automobiles, are usually composed of polyurethane and other fiber-like materials, most frequently cotton, foam, or paper. The manufacturing process is accomplished using a pleated filter material and the addition of resins and glues. Paper air filters are widely used because these materials are disposable and inexpensive. The air filter set is usually placed inside a plastic or metal box connected to the throttle body with an intake tube. When the engine is working, air is taken into the cylinder and any dust in the air is retained on the CAF. Therefore, the CAFs have main functions of particle removal, engine protection, and maintaining performance at high levels. We have shown the usefulness of CAFs as samplers which can move a high volume of air, are inexpensive, and offer the possibility to determine the levels of air contaminants in downtown city streets. Their studies focused on the determination of pollutants in the CAFs; however, the filters retain dust, suggesting that these filters could be used to characterize the nature and composition of the PM trapped by urban automobiles filters. This idea represents a more realistic way of assessing the exposure of people to air pollution within the city. Therefore, the aims of this work were to estimate the size distribution and elemental composition of dust particles collected from the urban atmosphere by CAFs and to identify the main sources of street dust of Aguascalientes City in Mexico.

2. Materials and Methods

2.1. Study Area

The CAFs were collected from service agencies (Ford, Chevrolet, Toyota, and Nissan) located to the north of Aguascalientes City (21°53’ N, 102°18’ W). The CAFs were obtained from vehicles that circulate in the north of the city. This area is composed of main roads with six-lane highways, and four of these are considered to have high speeds and heavy traffic. These roads are paved with asphalt. Aguascalientes is the capital of the state of Aguascalientes, Mexico (Figure 1) and has an area of 385 km2, a population of 832,712 habitants, and more than 356,210 vehicles. Seasonal meteorological conditions at Aguascalientes include warm, dry weather, and the average annual rainfall ranges from 500 to 600 mm. This climate is characterized by evaporation that exceeds precipitation and is mainly associated with vegetative communities of desert-type scrub and vegetation, covering approximately 86.30% of the surface. The annual average temperature is 17.4 °C. The prevailing winds come from the southwest, but during the winter cold north winds and frosts often occur.

2.2. Sample Collection

Emissions from local vehicles have been reduced to meet Profepa and Aguascalientes emission standards. The rules establish a scheduled maintenance once or twice annually for vehicle inspection to maintain the vehicle in normal operating conditions, however, although these standards establish the measurement of solid particle emissions, although this is rarely done in practice. Manufacturers of new cars in Mexico offer engine warranties if the buyer obtains the preventive maintenance service. The service agencies recommend changing CAFs between 6000 and 10,000 km. The role of CAFs, which are located between the air intake and the engine, is to protect the engine from air particulate matter. We only collected CAFs from vehicles that sought service at authorized agencies with an average record of 12,347 ± 664 km, from different brand vehicles but, 2014–2015 models. The collection time was between 6 January and 30 March, 2015. The sample consisted of removal of 10 CAFs directly from the plastic box connected to the throttle body with an intake duct. The CAFs were then placed in sterilized plastic bags by the technician and stored in the laboratory at 4 °C until analysis.

2.3. Methodology to Remove Particles from the CAFs.

The collected CAFs were reviewed to rule out any perforations. Physical dimensions (length, width, height, and space between sheets) were used to estimate the surface air intake. The particles collected by the filters were divided into two categories; the first consisted of those particles that could be removed by friction. The other one are those adhered particles which were not removed by friction.
The first group was separated by shaking the filter on a vortex plate, any extra material or particles on the filter were detached gently with a fine brush. Individual samples were over-dried at 40 °C and 20% relative humidity for 24 h, then sieved through a 200-mesh sieve to remove other oversize materials. The dust recovered was weighed using an analytical balance (Figure 2). After sieving, five fractions were obtained with a following particle diameter: 74–60 µm, 59–56 µm, 55–44 µm, 43–20 µm, and 19–10 µm. Until analysis, sub-samples were weighted and stored in polyethylene flasks in a cool and dry place. The separated particles were observed using transmission and reflected light microscopy (model illuminated with optic fiber ring and equipped with a Panasonic GP-KR222 analog camera (Panasonic ,Tokyo, Japan) and frame grabber (Encore Electronics, Los Angeles, CA, USA). Image analysis was performed using a micrometer rule (200 line/mm) and the Image J software information about the program can be found on http://rsbweb.nih.gov/ij/. To study the particles deposited on the CAFs, the cellulose filter was removed from the metallic and polyurethane foam supports, and small pieces of filter were studied by scanning electron microscopy.

2.4. Scanning Electron Microscopy and EDX from Particles Adhered on the CAFs

For SEM sample preparation, filter pieces of about 0.5 cm2 were cut with scissors from the center of each sample CAF, and mounted on 12.5 mm SEM stubs for gold coating. A very thin film of gold (Au) was deposited on the surface of each sample using a Gold Sputter Coater (Desk II) vacuum coating unit (Denton Vacuum LLC, Moorestown, NJ, USA). The SEM-EDX analysis of morphology and chemical composition of individual particles was carried out using a computer-controlled field emission SEM instrument (JSM-6330F, JEOL, Peabody, MA, USA). The EDX was carried out for each elemental analysis using the line scan analysis technique, and the present elements were both qualitative and quantitatively measured (Oxford INCA X-Act, Oxford Instruments, Buckinghamshire, UK). Particle counting was performed using the Image J software. Only particles larger than 0.2 µm were counted. For quantitative element analyses, EDX spectrograms were recorded and the weight percentage of each element present in the spectrum was identified. As mentioned above, the CAFs samples were gold coated. Therefore, the gold data of EDX cannot be used to estimate the quantitative elemental analyses, the Au contribution was manually subtracted during the evaluation of the EDX spectra. Three new CAFs that were purchased from official service agencies were used as controls and were prepared and analyzed identically to the experimental samples.

2.5. Biological Particle Analysis

Palynological analysis of the organic material trapped on the CAFs was performed according to the method used for melissopalynology. Briefly, 0.1 g of dust was placed into 10 mL test tubes and washed by centrifugation and decantation using distilled water. Then, a 10% potassium hydroxide solution was added to the residue, which was then warmed at 70 °C for 10 mins with occasional stirring. The material was filtered on a 300 µm filter, centrifuged twice for 5 min at 3000 rpm, and then decanted twice. The residue was treated with 7 mL acetolysis mixture (9:1 v:v acetic anhydride and concentrated sulfuric acid). The sample was warmed to 80 °C for 5–10 minutes with occasional stirring. Next the acetolysis mixture was removed by centrifugation and decantation. The residue was washed with ethyl alcohol and transferred to an Eppendorf tube. Two drops of glycerin were added, and the open tube was placed into an incubator at 40 °C for 12 h. The slides were then prepared using the method of Jones [14]. They were observed with light microscopy. Some positive samples were prepared in a similar way for scanning electron microscopy as described in the paragraph above.

3. Results

The analyses of the CAFs revealed that the average weight of the retained dust was 0.94 ± 0.72 g (n = 10). CAFs had a total filtration surface of 1.2 ± 0.5 m2, with a mean interspace between the sheets of 2.4 ± 1.23 mm, in agreement with data from the ISO 5011 test [15].
The dust retained by CAFs has a heterogeneous composition due to its varied origin, transport, and emissions. Poschl [16] indicated that the particle sizes, chemical composition, and mixing states of atmospheric aerosols significantly impact climate and human health. The dust particles varied greatly with respect to size, morphologies, and chemical composition. Particles trapped in the 200 µm mesh were represented mainly by large biological material that was visible to the naked eye. Small insects, such as beetles, wasps, earwigs, bees, and flies, as well as legs, antennae, eyes, and wings were found (Figure 2 and Figure 3), and plant debris, represented by fragments of wood, seeds, and leaves, was also observed, albeit less frequently. Inorganic particles and synthetic fibers were also found (Figure 4).
The observation of particles with reflected light microscopy allowed identification of the origin of removed particles, and many of these were biological in nature. Metallic particles observed under reflected light microscopy exhibited sizes ranging from 0.07 mm to 1.2 mm, with elongated shapes and shiny surfaces. Other material frequently present included natural and synthetic fibers characterized by transparency. The inorganic material was composed mainly of sands and small clays, which when viewed under a reflected light microscope were colorful (Figure 4a,b). These materials were a variety of shapes and sizes, conglomerates of sand with asphalt were observed in all CAFs and were identified as typical paving material (Figure 4e–g).
The size distribution analysis of particles removed from the CAFs is shown in Figure 5. These particles were mostly of a large size with equivalent diameters ranging from 74-10 µm. Particles within the range 74–60 µm were found in smaller amounts. They were lightweight, mainly waste of animal and vegetal origin like pieces of insects, leaves and wood (Figure 3). Nevertheless, particles with a size between 59–44 µm were the most abundant. Particles of 43–10 µm were found in smaller amounts.

3.1. Elemental Composition Was Analyzed by SEM with EDX.

The dust collected by the CAFs comes from Aguascalientes City, where the soil is classified as a semi-desert soil mainly composed of silicates and clay minerals, however, the dust collected by the CAFs displayed a more complex composition. The morphology and chemical composition of each particle was individually analyzed by SEM-EDX. The analysis of the dust particles separated from CAFs were composed of C, O, Si, Al, Ca, Mg, Na, K, Ti, and Fe. Si and Fe were the most abundant elements found in large particles; likewise, the particles display variable morphology. The shapes vary from rectangular to irregular, from spherical to triangular-like aggregates.
The analysis of control CAFs showed a clean surface free of particles (Figure 6a,b) with fiber diameters of 7.5 ± 2.5 µm, n = 50, and cavities much larger than fiber diameters (15.28 ± 2.5 µm, n = 50). The elemental composition of control CAFs was 52.5% C and 47.5% O (Figure 6), meanwhile in the CAFs collected; the particles retained were different sizes; with equivalent diameter range from 16 to 0.7 µm (Figure 6d,f).
Based on the elemental composition and morphology results, these particles were sorted into three categories: mineral particles (derived from soil sediments and weathered rock surfaces), metallic particles (derived from industrial activities), and biogenic particles (pollen derived from plants, considered as potentially allergenic).

3.2. Mineral Particles

Most of the mineral particles observed on the CAFs had a diameter between 10-1.8 µm (Figure 7). This figure depicts the typical microphotography of an aluminosilicate particle, with a diameter <10 µm. Figure 8a shows particles with a diameter less than 2.5 µm (1.1 ± 0.5µm). SEM-EDX microphotograph data revealed different kinds of aluminosilicates with irregular morphology, which were comprised of Al, Si, and O, along with other minerals such as Ca, Fe, Mg, K and Ti. They were identified as feldspars (Figure 7 and Figure 8). Figure 7 also shows a collected CAF cellulose matrix with broken filter fibers and wider spaces between them, as would be expected of the filters used. The presence of particles deposited in the deepest fibers was also observed. By detailed analysis of the particles retained on the CAFs, it was noticed that some of them suffered a nucleation and condensation, especially among the smaller (2.5 µm), shown as aggregates (Figure 8b).

3.3. Metallic Particles

The dust spectra analysis adhered to the CAFs revealed metallic particles (Figure 9 and Figure 10). Elemental mapping by EDX in one dimension recorded the elemental composition of two particles. The first with a diameter of 8 µm composed by Fe and Cr, whereas, the second has a small diameter of 3 µm with high content of Fe (Figure 9).
Platinum was another element found in the adhered particles, which was observed in some particles even through the whole line mapping (Figure 10). Figure 11 shows the SEM of large metallic particles found at dust removed from the CAFs. The corresponding EDX spectrum revealed that these particles contain >70% iron (Figure 11b). These particles were identified as iron oxides composed of surface layers and with an amorphous shape (Figure 11a). Some of the particles had fine edges, which are characteristic of anthropogenic activity, with specific forms like spheres or rhomboid shapes and rough surfaces (Figure 11c,d). In the same way, it also shows small particles attached to the large metal particles. The particle in Figure 11d is decorated on its surface with many fine iron-rich particles smaller than a few micrometers.

3.4. Biological Particles

To obtain information about the morphology of pollen samples collected from the CAFs, dust samples were processed by acetolysis, and analyses of the images captured by optical microscopy and SEM were performed. A subfraction of 150 pollen grains were found in the analyzed dust of the 10 CAFs. Biological particles are typically identified by morphology and size range of 20 to 5 µm [17]. The pollen spectra was dominated by Shinus molle, Lollium perenne, Prosopis sp., Eucalyptus. Figure 12 shows a SEM image of pollen found in the CAFs. The pollen grain was found to be isopolar, radially symmetrical, non-angular, and 3-colporoidate, it was identified as a Psidium guajava pollen grain. The EDX results indicated that the main elemental composition of the pollen was C > O > Si > Zn > S > Fe > Al > Ca > K > Na > Ti (Figure 13).
It’s interesting to note that all them, had Si and S in its composition. We used the linescan mode to determine the elemental composition of pollen that had a surface free of particles; however, some pollen samples that had PM on the surface were also analyzed using the linescan mode (Figure 14). This maneuver allowed us to study the association between the compositions of pollen and the adhered particles. The EDX spectra show that silicon is truly a constituent of pollen, and the particle on its surface also has a silicon oxide composition (Figure 12 and Figure 14).

4. Discussion

CAFs have been used for monitoring polychlorinated dibenzodioxins (PCDD) [12], polycyclic aromatic hydrocarbons (PAHs) [18], and heavy metals [19]; however, studies related to air particles have not yet been reported. We have now expanded this hypothesis and evaluated CAFs as active samplers of air pollution. A detailed characterization of individual atmospheric particles provided useful information about their sources, transport, and possible health effects. The particles retained by CAFs was less than the maximum capacity reported for CAFs (587 g) [20]. Perhaps, the reason for this result is that part of the retained particles fall into the box, as the CAFs are designed as impact filters with cellulose folds, so that when the vehicle is in motion, the particles of air entering the duct reach the same speed of the vehicle, resulting in collisions of the particles with the filter and fragmented particles will fall into the box with small particles being deposited between the folds. The impact of particles on the filter could change the distribution of sizes to more fine and ultrafine particles, favoring the deposition on the filter. Such particles can contribute to the group of particles detected in exhaust emissions [21]. Nonetheless, we determined the total area of filtration and estimated that the retained material was 0.78 g/m2, while, filtration efficiency was not determined under strict conditions, because the filters were not weighed previously and were collected after a distance was traveled. The estimate of the material amount collected by the filter allows us to assume that the filters studied were working at 100% and could eventually collect particles of all sizes as reported by Song et al. [8,22]. This value is in agreement with similar studies performed to collect powder from roads and avenues. One such study of road dust loadings reported values from 0.3 to 24.44 g/m2, with an average of 3.82 g/m2 [3]. Therefore, our reported value fits well with the road dust loadings.
The nature of particles was inferred using light reflected microscopy, as these particles were easily identifiable by their reflective properties [23]. Animal and plant debris are frequently observed to be common elements of the aerosols collected from roads and highways [1,24,25]. The large metallic particles were found to have an initial source of waste removed by friction, vehicular, or anthropogenic activity. The multicolored inorganic particles were determined to be derived naturally from sands and small clays. A common observation was the presence of conglomerate asphalts [26]. This result was expected because Aguascalientes is a city with 100% paved streets. The constant friction of vehicles on the streets results in the release of small asphalt particles, which are then are impregnated with oil and PAHs [27].
The particles removed from the CAFs showed a distribution between 74 and 10 µm, and can thus be considered as large particles. The particles of 60–74 µm were mainly of plant and animal origin, and the particles between 74–10 µm were a mix of quartz, clay, metal and organic material composed mainly by pollen. Several studies have reported the large particles were the most abundant in dust from big cities in America and Asia [17]. Particles of 59–20 µm size were the most abundant, and they have been associated to a mineral origin and the transport of particles which are mixed with local powders from suburban areas to cities [3,17]. Similarly, CAF tests are often carried out with coarse Arizona dust, which has a size distribution predominantly in this range [28]. Particles smaller than 10 µm were less abundant in dust samples removed from CAFs, and rather were found in clusters with large particles and adhered to pollen grains.
Such particles were also observed adhered to the cellulose fibers CAFs (Figure 6, Figure 7, Figure 8, Figure 9 and Figure 10). These particles showed a diameter of between 16 and 0.7 µm, indicating that these filters are capable of retaining particles smaller than 2.5 µm. These results are comparable to published studies about vehicle cabin air inlet filters [29], somehow coinciding with the HEPA standards [15,26]. The design of automotive filters is based on their ability to filter particles, which is dependent on the mesh and the structure and composition of the fiber [30]. The analysis of CAFs showed spaces much larger than the fiber diameters, allowing substantial air flow, whereas fibers have a higher specific surface area. This arrangement promotes the deposition of particles with diameter less than 10 µm. These particles are deposited deep inside filters where they form agglomerates that decrease the filtration and the filter life [22]. The observation of agglomerates deep in the filter suggests that the separation method used was unable to remove all particles, and an alternative method must be used to estimate these particles.
The EDX spectrum peaks correspond to the energy levels for carbon and oxygen. The carbon percentage is higher than the oxygen percentage, as expected for cellulose (C6H10O5)n. Since hydrogen cannot be detected by SEM-EDX, this element does not appear in the SEM-EDX spectrum [31]. Thus, we found from the elemental analysis that control CAFs possess only carbon, oxygen, and hydrogen. These typical characteristics of cellulose materials have been described previously [32].
Mineral particles were the most abundant and likely derived from natural sources, although there was also potential contribution of anthropogenic activities, such as construction, transport, and paving [33,34]. The elemental composition was mainly of Si, Al and O, identified as aluminosilicates corresponding to the Earth's crust. The soil particle size analysis classifies to these particles as silt and clays and suggest that due to their aerodynamic size and vehicle traffic, these particles can travel long distances. The topology of paved roads favors its deposition in the streets and avenues of the city. The winds and continuous movement of vehicles, which leads to recirculation of particles in the air, generates an “urban dust cycle” [2].
Iron is the most abundant element in metallic particles [1,35]. These particles were found in many shapes (Figure 11). Due to the formation of aggregates of small iron particles, which could disintegrate and solubilize, soluble iron oxide has been found to play an important role in the production of highly deleterious hydroxyl radicals, which are known to be a pathogenicity factor of smaller particle PM10 [36]. The presence of chromium and platinum in the particles could be associated with chrome-plating process in automotive parts. In particular, platinum is an element used in catalytic converters, which catalyze the conversion of nitrogen oxides into nitrogen and oxygen. Platinum is released from exhaust fumes and has been previously studied [37]. Palacios et al. [38] concluded that platinum is a principal component in exhaust fumes, with a particle size of less than 10 µm, and is released into airborne and dust sediments.
The detection of N and H was not possible under these measurement conditions, despite their presence in the filtered matter. It is known that pollen is mainly composed of organic compounds, including proteins, lipids, carbohydrates, vitamins, and hormones, but that pollen also contains minerals. C, H, O, and N are the main elements that constitute those organic compounds. The C+O account for >75% of the organic compounds, while Na, K, Fe, Al, Zn, and Ca were present in minor amounts. Such a composition has been was used to sort plant matter from the other PM [25,39,40]. Duque et al. [41] found that the main elements in control pollen were C, O, N, P, Ca, S, K, Mg, Si, Cl, and Na. Similar trace elements were found in Platanus acerifolia leaves [42].
Numerous studies have been reported on the elemental composition of PM deposited on pollen and leaves [43,44] as well as on their relationship to allergies [45]. Interestingly, some grains of pollen possess significant concentrations of silicon and sulfur on the surface [46,47,48]. The silicon come from natural origin, however, the presence of S could be related with a process of adsorption of noxious gases.
The pollen spectra collected from the car air filters are typical species found in Aguascalientes State such as Shinus molle, Lollium perenne and Prosopis sp. Some of these plants are highly allergenic [49] and are widely distributed in the streets and gardens of Aguascalientes. The presence of Psidium guajava pollen in the samples analyzed from the CAFs, could be explained due some cars running in the Guajava Valley, a zone highly cultivated for exportation. A similar study performed by More et al. [50] showed that the use of CAFs as a pollen sampler was associated with the vehicle travel route.

5. Conclusions

From reflected light microscopy and SEM- EDX studies, it follows that CAFs retain particulate matter of different nature, which could be classified into three main types: biological particles (material organic, plants and animal debris), mineral particles (clays and asphalt) and metal particles (composed mainly of Fe). For the study these particles were separated into two categories: those which they were removed from CAFs mechanically and those that remained attached to CAFs. The predominant particles were large particles that had a diameter between 59-20 µm. However, SEM revealed adhered particles smaller than a few micrometers. The particles adhered to the CAF fibers were between 16 to 0.7 µm. whereas, control filters showed a free surface of particles with a cellulose composition. These diverse groups of airborne particles had either natural or anthropogenic origin. The particle analyses provided insight into the possible source of these particles, mainly soil dust. The silicates were major contributors to the mineral particles. The metallic particles were composed of Fe, Cr, and Pt, and they were related to industrial activity, automotive parts and exhaust emissions. The palynological analysis of biological particles revealed the presence of pollen grains associated with the vegetation found along the high-traffic roads. These results allow us to say that car air filters capture a mixture of atmospheric particles, that can be analyzed to help monitor urban air.

Acknowledgments

The authors gratefully acknowledge the support from automotive agencies of Aguascalientes, Mexico, by donation of the filters used in this research. This work was supported by an Autonomous University of Aguascalientes Grant PIT-16-2. The first author acknowledge the support from CONACYT through postdoctoral fellowship “Apoyos al Fortalecimiento de la Calidad del Posgrado Nacional”. We are indebted to Aracely Adbache Ortíz for her technical assistance with the SEM-EDX analyses (Laboratorio de Microscopia de Alta Resolucion. Departamento de Biologia. Universidad Autonoma de Aguascalientes).

Author Contributions

Both authors participated equally in the design and development of this research as well as the writing and revision of the manuscript. All authors read and approved the final manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Al-Khashman, O.A. Determination of metal accumulation in deposited street dusts in Amman, Jordan. Environ. Geochem. Health 2007, 29, 1–10. [Google Scholar] [CrossRef] [PubMed]
  2. Srivastava, A.; Jain, V.K.; Srivastava, A. SEM-EDX analysis of various sizes aerosols in Delhi India. Environ. Monit. Assess. 2009, 150, 405–416. [Google Scholar] [CrossRef] [PubMed]
  3. Chen, J.; Wang, W.; Liu, H.; Ren, L. Determination of road dust loading and chemical characteristics using resuspension. Environ. Monit. Assess. 2012, 184, 1693–1709. [Google Scholar] [CrossRef] [PubMed]
  4. Ott, D.K.; Cyrs, W.; Peters, T.M. Passive measurement of coarse particle matter, PM10–2.5. J. Aerosol. Sci. 2008, 39, 156–167. [Google Scholar] [CrossRef]
  5. Byeon, S.-H.; Willis, R.; Peters, M. Chemical Characterization of outdoor and subway fine (PM2.5–1.0) and Coarse (PM10–2.5) particulate matter in Seul (Korea) by computer-controlled scanning electron microscopy (CCSEM). Int. J. Environ. Res. Public Health 2015, 12, 2090–2104. [Google Scholar] [CrossRef] [PubMed]
  6. Dong, Y.; Hays, M.D.; Smith, N.D.; Kinsey, J.S. Inverting cascade impactor data for size-resolved characterization of fine particulate source emissions. Aerosol. Sci. 2004, 35, 1497–1512. [Google Scholar] [CrossRef]
  7. Gomes, J.; Guerreiro, C.; Lavrador, D.; Carvalho, P.A.; Miranda, R.M. TEM analysis as a tool for toxicological assessment of occupational exposure to airborne nanoparticles from welding. Microsc. Microanal. 2013, 19 (Suppl. S4), 153–154. [Google Scholar] [CrossRef]
  8. Hinds, W.C. Aerosol Technology: Properties, Behavior, and Measurements of Airborne Particles, 2nd ed.; Wiley: New York, NY, USA, 1999. [Google Scholar]
  9. Quiros, D.C.; Zhang, S.; Sardar, S.; Kamboures, M.A.; Eiges, D.; Zhang, M.; Jung, H.S.; Mccarthy, M.J.; Oliver-Chang, M.-C.; Ayala, A.; et al. Measuring particulate emissions of light ducty passenger vehicles using integrated particle size distribution (IPSD). Environ. Sci. Tech. 2015, 49, 5618–5627. [Google Scholar] [CrossRef] [PubMed]
  10. Sobanska, S.; Fargayrac, G.; Laureyns, J.; Brémard, C. Chemistry at level of individual aerosol particle using multivariate curve resolution of confocal raman image. Spectrochim. Acta A 2006, 64, 1102–1109. [Google Scholar] [CrossRef] [PubMed]
  11. Kushwaha, R.; Srivastava, A.; Lai, H.; Ghosh, B.; Jain, V.K. Particles size distribution of aerosols and associated metals, and source estimation in Delhi, India. Sustain. Environ. Res. 2012, 22, 317–325. [Google Scholar]
  12. Zhang, B.; Zhang, L.; Wu, J.; Liu, G.; Zheng, M. An active sampler for monitoring polychlorinated Dibenzo-p-Dioxins and furans in ambient air. Bull. Environ. Contam. Toxicol. 2011, 87, 1–5. [Google Scholar] [CrossRef] [PubMed]
  13. Katsoyiannis, A. Car engines air filters. A useful ambient air sampler and/or possible hazardous waste? Aerosol. Air Qual. Res. 2014, 14, 1102–1105. [Google Scholar] [CrossRef]
  14. Jones, G.H. Pollen analyses for pollination research, acetolysis. J. Poll. Ecol. 2014, 13, 203–217. [Google Scholar]
  15. ISO 5011. Inlet Air Cleaning Equipment for Internal Combustion Engines and Compressors. Performance Testing. Available online: https://www.iso.org/obp/ui/#iso:std:64762:en (accessed on 15 June 2016).
  16. Poschl, U. Atmospheric aerosols: Composition, transformation, climate and health effects. Angew. Chem. Int. Ed. 2005, 44, 7520–7540. [Google Scholar] [CrossRef] [PubMed]
  17. Pachauri, T.; Singla, V.; Satsangi, A.; Lakhani, A.; Kumari, K.M. SEM-EDX characterization of individual coarse particles in Agra, India. Aerosol Air Qual. Res. 2013, 13, 523–536. [Google Scholar] [CrossRef]
  18. Katsoyiannis, A.; Birgul, A.; Ratola, N.; Cincelli, A.; Sweetman, A.J.; Jones, K.C. Can car air filters be useful as a sampling medium for air pollution monitoring purposes? Environ. Int. 2012, 48, 65–70. [Google Scholar] [CrossRef] [PubMed]
  19. Cai, Q.-Y.; Xiao, P.-Y.; Lu, H.; Katsoyiannis, A.; Tian, J.-J.; Zeng, Q.-Y.; Mo, C.-H. Evaluation of car air filters´ efficiency as active samplers for polycyclic aromatic hydrocarbons and heavy metals. Aerosol. Air Qual. Res. 2013, 14, 431–439. [Google Scholar] [CrossRef]
  20. Air Filter Test. Available online: http://www.billswebspace.com/AirFilterTest.htm (accessed on 1 July 2016).
  21. Chen, J.; Yu, X.; Sun, F.; Lunn, X.; Fu, Y.; Jia, G.; Zhang, Z.; Liu, X.; Mo, L.; Bi, H. The concentrations and reduction of airborne particulate matter (PM10, PM2.5, PM1,) at Shelterbelt site in Beijing. Atmosphere 2015, 6, 650–676. [Google Scholar] [CrossRef]
  22. Song, C.B.; Park, H.S.; Lee, K.W. Experimental study of filter clogging with monodisperse PSL particles. Powder Technol. 2006, 163, 152–159. [Google Scholar] [CrossRef]
  23. Hagni, R.D. Reflected light microscopy of industrial minerals. In Proceedings of the 10th International Congress for Applied Minerology, Trondheim, Norway, 1–5 August 2011.
  24. Winiwarter, W.; Bauer, H.; Caseiro, A.; Puxbaum, H. Quantifying emissions of primary biological aerosol particle mass in Europe. Atmos. Environ. 2009, 43, 1403–1409. [Google Scholar] [CrossRef]
  25. Despres, V.R.; Huffman, J.A.; Burrows, S.M.; Hoose, C.; Safatov, A.S.; Buryak, G.; Fröhlich-Nowoisky, J.; Elbert, W.; Andreae, M.O.; Poschl, W.; et al. Primary biological aerosol particles in the adtmosphere. A Review. Tellus B. 2012, 64, 5598. [Google Scholar] [CrossRef]
  26. Moon, K.H.; Falchetto, A.C.; Jeong, J.H. Microstructural analysis of asphalt mixtures using digital image processing techniques. Can. J. Civ. Eng. 2013, 41, 74–86. [Google Scholar] [CrossRef]
  27. Moon, K.H.; Falchetto, A.C. Microstructural investigation of hot mix asphalte (HMA) mixtures using digital image processing (DIP). KSCE J. Civ. Eng. 2015, 19, 1727–1737. [Google Scholar] [CrossRef]
  28. Test Dust History. Powder Tecnology. Available online: http://www.powdertechnologyinc.com/test-dust-contaminants/test-dust-history/ (accessed on 1 May 2016).
  29. Muala, A.; Sehlstedt, M.; Bion, A.; Osterlund, C.; Bosson, J.A.; Behnding, A.F.; Pouzar, J.; Bucht, A.; Boman, C.; Mudway, I.S.; et al. Assesment of the capacity of vehicle cabin air inlet filters to reduce diesel exhaust-induced symptoms in human volunteers. Environ. Health. 2014, 13, 1–14. [Google Scholar] [CrossRef] [PubMed]
  30. Zhang, R.; Liu, C.; Hsu, P.-C.; Zhang, C.; Liu, N.; Zhang, J.; Lee, H.R.; Lu, Y.; Qiu, Y.; Chu, S.; et al. Nanofiber air filters with high-temperature stability for efficient PM2.5 removal from the pollution sources. Nano Lett. 2016, 16, 3642–3649. [Google Scholar] [CrossRef] [PubMed]
  31. Chen, H. Chemical composition and structural of natural lignocellulose, Chapter 2. In Biotechnology of lingocellulose. Theory and Practice; Springer: Dordrecht. The Netherlands, 2014; pp. 25–71. [Google Scholar]
  32. Yan, L.; Chen, J.; Bangal, P. Dissolving Cellulose in a Na/OH/thiourea Aqueous Solution: A Topochemical Investigation. Macromol. Biosci. 2007, 7, 1139–1148. [Google Scholar] [CrossRef] [PubMed]
  33. Boev, I.; Sijakova-Ivanova, T.; Mirakovski, D. Scanning electron microprobe characterization of air filters from the Kavadarci town and Tikves valley. Geol. Maced. 2013, 27, 13–24. [Google Scholar]
  34. Suzuki, K. Characterization of airborne particulates and associated trace metals deposited on tree bark by ICP-OES, ICP-MS. SEM-EDX and laser ablation ICP-MS. Atmos. Environ. 2006, 40, 2626–2634. [Google Scholar] [CrossRef]
  35. Sharma, S.G.; Srinivas, M.S.N. Study of chemical composition and morphology of ariborne particles in Chandigarh, India using EDXRF and SEM techniques. Environ. Monit. Assess. 2009, 150, 417–425. [Google Scholar] [CrossRef] [PubMed]
  36. Akram, W.; Madhuku, M.; Ahmad, I.; Xiaolin, L.; Zhang, G.; Yan, L. Morphology, microstructure and chemical composition of single inhalable particles in Shangai. China. Environ. Monit. Assess. 2014, 186, 8587–8598. [Google Scholar] [CrossRef] [PubMed]
  37. Goncalves, A.; Domínguez, J.R.; Alvarado, J. Determination of Pd, Pt and Rh in vehicles escape fumes by GF-AAS and ICP-OES. Talanta 2008, 75, 523–527. [Google Scholar] [CrossRef] [PubMed]
  38. Palacios, M.A.; Gómez, M.; Moldovan, M.; Gómez, B. Assessment of environmental contamination risk by Pt, Rh and Pd from automobile catalyst. Microchem. J. 2000, 67, 105–113. [Google Scholar] [CrossRef]
  39. Matthias-Maser, S.; Jaenicke, R. Examination of atmospheric bioaerosol particles with radii greater than 0.2 micrometers. J. Aerosol. Sci. 1994, 25, 1065–1613. [Google Scholar] [CrossRef]
  40. Coz, E.; Artiñano, B.; Clark, L.M.; Hernandez, M.; Robinson, A.L.; Casuccio, G.S.; Lersch, T.L.; Pandis, S.N. Characterization of fine primary biogenic organic aerosol in an urban area in the northeastern unites states. Atmos. Environ. 2012, 44, 3952–3962. [Google Scholar] [CrossRef]
  41. Duque, L.; Guimares, F.; Ribiero, H.; Sousa, R.; Abreu, I. Elemental characterization of the airborne pollen Surface using electron probe microanalysis (EPMA). Atmos. Environ. 2013, 75, 296–302. [Google Scholar] [CrossRef]
  42. Kutbay, I.; Akfirat, F.S. Mapping of biochemical constituents in Platanus acerifolia leaves by analytical techniques. Proc. Soc. Behav. Sci. 2015, 195, 1719–1727. [Google Scholar] [CrossRef]
  43. Okuyama, Y.; Matsumoto, K.; Okochi, H.; Igawa, M. Adsorption of air pollutants on the grain surface Japanese cedar pollen. Admos. Environ. 2007, 41, 253–260. [Google Scholar]
  44. Song, Y.; Maher, B.A.; Li, F.; Wang, X.; Sun, X.; Zhang, H. Particulate matter deposited on leaf of five evergreen species in Beijing, China: Source identification and size distribution. Atmos. Environ. 2015, 105, 53–60. [Google Scholar] [CrossRef]
  45. Senechal, H.; Visez, N.; Charpin, D.; Shahali, Y.; Peltre, G.; Biolley, J.P.; Lhuissier, F.; Couderc, R.; Yamada, O.; Maltrat-Domenge, A.; et al. A review of the effects on major atmospheric pollutants on pollen grains, pollen content, and Allergenicity. Sci. World J. 2015, 2015, 940243. [Google Scholar] [CrossRef] [PubMed]
  46. Ribeiro, H.; Guimares, F.; Duque, L.; Noronha, F. Characterization of particulate matter on airborne pollen grains. Environ. Poll. 2015, 206, 7–16. [Google Scholar] [CrossRef] [PubMed]
  47. Crang, R.E.; May, G. Evidence for silicon as a prevalent component wall structure. Can. J. Bot. 1974, 52, 2171–2174. [Google Scholar] [CrossRef]
  48. Mamane, Y.; Noll, K.E. Characterization of large particles at a rural site in the eastern United States: Mass distribution and individual particle analysis. Atmos. Environ. 1985, 19, 611–622. [Google Scholar] [CrossRef]
  49. Diethart, B.; Sam, S.; Weber, M. Walls of allergenic pollen: Special reference to the endexine. Grana 2007, 46, 164–175. [Google Scholar] [CrossRef]
  50. More, S.; Thapa, K.K.; Bera, S. Potential of dust and soor from air-filters of motors vehicle engines as a forensic tool: First experimental palynological approach in India. J. forensic Res. 2013, 4, 1–7. [Google Scholar]
Figure 1. Map of Aguascalientes State.
Figure 1. Map of Aguascalientes State.
Ijerph 13 00985 g001
Figure 2. (a) Car air filter collected, (b,c) blends show the dust trapped, (d–f) macroparticles and dust retained.
Figure 2. (a) Car air filter collected, (b,c) blends show the dust trapped, (d–f) macroparticles and dust retained.
Ijerph 13 00985 g002
Figure 3. Mosaic of animal debris collected by the CAFs.
Figure 3. Mosaic of animal debris collected by the CAFs.
Ijerph 13 00985 g003
Figure 4. (a–c) Representative metallic and (c–g) inorganic particles observed by reflected light microscopy; (d) Synthetic fibers were also observed. Arrows on f and g indicate small particles.
Figure 4. (a–c) Representative metallic and (c–g) inorganic particles observed by reflected light microscopy; (d) Synthetic fibers were also observed. Arrows on f and g indicate small particles.
Ijerph 13 00985 g004
Figure 5. Distribution of particles removed from CAFs collected.
Figure 5. Distribution of particles removed from CAFs collected.
Ijerph 13 00985 g005
Figure 6. (a–c) Scanning electron micrographs and EDX spectrum of control filters and (d–f) collected CAFs.
Figure 6. (a–c) Scanning electron micrographs and EDX spectrum of control filters and (d–f) collected CAFs.
Ijerph 13 00985 g006
Figure 7. Identification of mineral K-feldspar particles by SEM-EDX (arrow particle <10 µm).
Figure 7. Identification of mineral K-feldspar particles by SEM-EDX (arrow particle <10 µm).
Ijerph 13 00985 g007
Figure 8. (a) Particles less than 2.5 µm and (b) nucleation and condensation of <2.5 µm particles that were deposited on CAF.
Figure 8. (a) Particles less than 2.5 µm and (b) nucleation and condensation of <2.5 µm particles that were deposited on CAF.
Ijerph 13 00985 g008
Figure 9. Metallic particles composed of (1) iron and (2) chromium.
Figure 9. Metallic particles composed of (1) iron and (2) chromium.
Ijerph 13 00985 g009
Figure 10. Metallic particle that contains platinum was found on CAF (black arrows).
Figure 10. Metallic particle that contains platinum was found on CAF (black arrows).
Ijerph 13 00985 g010
Figure 11. Iron particles with different morphologies. (a) Layer; (b) EDX spectrum; (c) rhomboid and (d) agglomerate.
Figure 11. Iron particles with different morphologies. (a) Layer; (b) EDX spectrum; (c) rhomboid and (d) agglomerate.
Ijerph 13 00985 g011
Figure 12. Pollen grain collected in Aguascalientes by CAFs.
Figure 12. Pollen grain collected in Aguascalientes by CAFs.
Ijerph 13 00985 g012
Figure 13. Frequency of elements in the composition of pollens collected by CAFs.
Figure 13. Frequency of elements in the composition of pollens collected by CAFs.
Ijerph 13 00985 g013
Figure 14. Pollen grain with adherent silicon particles collected by CAFs.
Figure 14. Pollen grain with adherent silicon particles collected by CAFs.
Ijerph 13 00985 g014

Share and Cite

MDPI and ACS Style

Heredia Rivera, B.; Gerardo Rodriguez, M. Characterization of Airborne Particles Collected from Car Engine Air Filters Using SEM and EDX Techniques. Int. J. Environ. Res. Public Health 2016, 13, 985. https://0-doi-org.brum.beds.ac.uk/10.3390/ijerph13100985

AMA Style

Heredia Rivera B, Gerardo Rodriguez M. Characterization of Airborne Particles Collected from Car Engine Air Filters Using SEM and EDX Techniques. International Journal of Environmental Research and Public Health. 2016; 13(10):985. https://0-doi-org.brum.beds.ac.uk/10.3390/ijerph13100985

Chicago/Turabian Style

Heredia Rivera, Birmania, and Martín Gerardo Rodriguez. 2016. "Characterization of Airborne Particles Collected from Car Engine Air Filters Using SEM and EDX Techniques" International Journal of Environmental Research and Public Health 13, no. 10: 985. https://0-doi-org.brum.beds.ac.uk/10.3390/ijerph13100985

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop