Tracking fine particles in urban and rural environments using honey bees as biosamplers in Mexico.

This work explores the efficiency of honey bees (Apis mellifera) as biosamplers of metal pollution. To understand this, we selected two cities with different urbanization (a medium-sized city and a megacity), and we collected urban dust and honey bees captured during flight. We sampled two villages and a university campus as control areas. The metal content in dust was analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Atomic Force Microscopy (AFM) and Scanning electron microscopy (SEM) were used to investigate the shape and size distribution of the particles, and to characterize the semiquantitative chemical composition of particles adhered to honey bee's wings. Principal Component Analysis (PCA) shows a distinctive urban dust geochemical signature for each city, with component 1 defining V-Cr-Ni-Tl-Pt-Pb-Sb as characteristic of Mexico City and Ce-As-Zr for dust from Hermosillo. Particle count using SEM indicates that 69% and 63.4% of the resuspended dust from Hermosillo and Mexico City, respectively, corresponds to PM2.5. Instead, the particle count measured on the honey bee wings from Hermosillo and Mexico City is mainly PM2.5, 91.4% and 88.9%, respectively. The wings from honey bees collected in the villages and the university campus show much lower particle amounts. AFM-histograms confirmed that the particles identified in Mexico City have even smaller sizes (between 60 and 480 nm) than those in Hermosillo (between 400 and 1400 nm). Particles enriched in As, Zr, and Ce mixed with geogenic elements such as Si, Ca, Mg, K, and Na dominate honey bee' wings collected in Hermosillo. In contrast, those particles collected from Mexico City contain V, Cr, Ni, Tl, Pt, Pb, and Sb. Such results agree with the urban dust data. This work shows that honey bees are suitable biosamplers for the characterization of fine dust fractions by microscopy techniques and reflect the urban pollution of the sites.

Metal(loid) bioaccessibility and risk assessment of ashfall deposit from Popocatépetl volcano, Mexico.

Ash emission from volcanic eruptions affects the environment, society, and human health. This study shows the total concentration and lung bioaccessible fraction of eight potential toxic metal(loid)s in five Popocatépetl ashfall samples. Mineralogical phases and particle size distribution of the ashfall were analyzed by X-ray diffraction (XRD) and Scanning Electron Microscope (SEM) techniques, respectively. The bioaccessibility test of Gamble solution (GS) and Artificial Lysosomal Fluid (ALF) were conducted to simulate extracellular (pH 7) and intracellular (pH 4.5) conditions, respectively. The studied metal(loid)s showed the following total concentration (mg kg-1): 1.98 (As), 0.17 (Cd), 134.09 (Cr), 8.66 (Cu), 697.33 (Mn), 55.35 (Ni), 8.77 (Pb), and 104.10 (Zn). Geochemical indices suggested that some metal(loid)s are slightly enriched compared to the local soil background concentrations. Several mineralogical phases were identified in the collected ashfall deposits, such as plagioclase, pyroxene, and Fe-Ti oxide, among others. According to the risk assessment results, the non-carcinogenic risk related to ashfall exposure returns an HQ > 1 for children. In contrast, the estimation of carcinogenic risk was found to be within the tolerable limit. Metal(loid)s showed low bioaccessibility (< 30%) in GS and ALF, with the highest values found in ALF solution for As (12.18%) and Cu (7.57%). Despite their metal-bioaccessibility, our findings also showed that dominant ash particle size ranged between fine (< 2.5 µm) and extremely fine (< 1 µm), considered highly inhalable fractions. The results obtained in this work indicate that volcanic ashes are bioinsoluble and biodurable, and exhibit low bioaccessibility when in contact with lung human fluids.

Characterization and Polydispersity of Volcanic Ash Nanoparticles in Synthetic Lung Fluid.

The inhalation of natural nanoparticles (NPs) emitted from volcanic activity may be a risk to human health. However, the literature rarely reports the fate and response of NPs once in contact with lung fluids. In this work, we studied the particle size distribution of ashfall from Popocatépetl volcano, Mexico. The collected ashes (n = 5) were analyzed with scanning electron microscopy (SEM) to obtain the elemental composition and morphology, and to determine the size of the ash particles using ParticleMetric software (PMS). The PMS reported most of the ash to have submicrometric size (<1 µm) and an average equivalent circle of 2.72 µm. Moreover, to our knowledge, this study investigated for the first time the behavior of ash NPs at different times (0 to 24 h) while in contact with in vitro lung fluid, Gamble Solution (GS) and Artificial Lysosomal Fluid (ALF) using dynamic light scattering (DLS). We found a large variability in the hydrodynamic diameter, with values less than 1 nm and greater than 5 µm. Furthermore, aggregation and disaggregation processes were recognized in GS and ALF, respectively. The results of this study increase the knowledge of the interaction between NPs and lung fluids, particularly within the alveolar macrophage region.

Oxidative potential of metal-polluted urban dust as a potential environmental stressor for chronic diseases.

Oxidative stress (OS) associated with metals in urban dust has become a public health concern. Chronic diseases linked to general inflammation are particularly affected by OS. This research analyzes the spatial distribution of metals associated with OS, the urban dust´s oxidative potential (OP), and the occurrence of diseases whose treatments are affected by OS. We collected 70 urban dust samples during pre- and post-monsoon seasons to achieve this. We analyzed particle size distribution and morphology by scanning electron microscopy, as well as metal(loid)s by portable X-ray fluorescence, and OP of dust in artificial lysosomal fluid by using an ascorbic acid depletion assay. Our results show that the mean concentration of Fe, Pb, As, Cr, Cu, and V in pre-monsoon was 83,984.6, 98.4, 23.5, 165.8, 301.3, and 141.9 mg kg-1, while during post-monsoon was 50,638.8, 73.9, 16.7, 124.3, 178.9, and 133.5 mg kg-1, respectively. Impoverished areas with the highest presence of cardiovascular, cancer, diabetes, and respiratory diseases coincide with contaminated areas where young adults live. We identified significant differences in the OP between seasons. OP increases during the pre-monsoon (from 7.8 to 237.5 nmol AA min-1) compared to the post-monsoon season (from 1.6 to 163.2 nmol AA min-1). OP values are much higher than measured standards corresponding to contaminated soil and urban particulate matter, which means that additional sources beside metals cause the elevated OP. The results show no risk from chronic exposure to metals; however, our results highlight the importance of studying dust as an environmental factor that may potentially increase oxidative stress.

Release of Nanoparticles in the Environment and Catalytic Converters Ageing.

A Three-Way Catalyst (TWC) contains a cordierite ceramic monolith coated with a layer of Al2O3, CexZr1-xO2 and platinoids mixture. Under standard operation, the platinoid concentration decreases, exposing the remaining washcoat structure. After that particle release stage, the sintering process follows where the crystalline CexZr1-xO2 solution is broken and begins to separate into ZrO2 and CeO2 phases. ZrO2 is released to the environment as micro and nanoparticles, while a small amount of CeO2 generates a new AlxCe1-xO2 composite. The main effect of Ce capture is the growth in the size of the polycrystal structure from 86.13 ± 16.58 nm to 225.35 ± 69.51 nm. Moreover, a transformation of cordierite to mullite was identified by XRD analysis. Raman spectra showed that the oxygen vacancies (Vö) concentration decreased as CexZr1-xO2 phases separation occurred. The SEM-EDS revealed the incorporation of new spurious elements and microfractures favouring the detachment of the TWC support structure. The release of ultrafine particles is a consequence of catalytic devices overusing. The emission of refractory micro to nanocrystals to the atmosphere may represent an emerging public health issue underlining the importance of implementing strict worldwide regulations on regular TWCs replacement.

Identification of refractory zirconia from catalytic converters in dust: An emerging pollutant in urban environments.

Using catalytic converters is one of the most effective methods to control vehicle emissions. A washcoat of cerium oxide-zirconia (CeO2-ZrO2) has been used to enhance the performance of the catalytic converter device. To date, the prevalence of this material in the environment has not been assessed. In this study, we present evidence of the existence of inhalable zirconia in urban dust. Samples of the washcoat, exhaust pipe, topsoil, and road dust were analyzed by X-ray fluorescence, X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, photoluminescence (PL) spectroscopy, and thermally stimulated luminescence (TSL). The results showed a CeO2-ZrO2 phase separation after sintering. This causes the emission of ZrO2, CeO2, and CeZrOx particles smaller than 1 µm, which can likely reach the alveolar macrophages in the lungs. The Ce-Zr content in road dust exceeds geogenic levels, and a significant correlation of 0.87 (p < 0.05) reflects a common anthropic source. Chronic exposure to such refractory particles may result in the development of non-occupational respiratory diseases. The inhalable crystalline compounds emitted by vehicles are a significant environmental health hazard, revealing the need for further investigation and assessment of zirconia levels generated by automobiles in urban areas worldwide.

Metal bioaccessibility, particle size distribution and polydispersity of playground dust in synthetic lysosomal fluids.

Inhalation of playground dust-derived fine particles in schoolyards poses a risk from exposure to metal(oids) and minerals. In this work, we obtained the total concentration and bioaccessibility of metal(oids) with Gamble Solution (GS) and Artificial Lysosomal Fluid (ALF) synthetic solutions, simulating the extracellular neutral pH environment of the lung and the intracellular conditions of the macrophage, respectively. Scanning Electron Microscope (SEM), and Dynamic Light Scattering analysis (DLS) techniques were used to characterize particles with a size smaller than 2.5 µm, which can be assimilated by macrophages in the deep part of the lung. Arsenic (As), lead (Pb), copper (Cu), manganese (Mn), zinc (Zn), and iron (Fe) showed concentrations of 39.9, 147.9, 286, 1369, 2313, 112,457 mg·kg-1, respectively. The results indicated that all studied elements were enriched when compared to (i) local geochemical background and (ii) findings reported in other cities around the world. Bioaccessibility of metal(oids) in GS was low-moderate for most studied elements. However, in ALF assays, bioaccessibility was high among the samples: for lead (Pb = 34-100%), arsenic (As = 14.7-100%), copper (Cu = 17.9-100%), and zinc (Zn = 35-52%) possibly related to hydrophobic minerals in dust. SEM and DLS image analysis showed that playground dust particles smaller than 2.5 µm are dominant, particularly particles with a size range of 500-600 nm. The polydispersity detected in these particle sizes showed that most of them might be crystalline compounds (elongated shapes) forming agglomerates instead of combustion particles (spheres). Moreover, the circularity detected varies from 0.57 to 0.79 (low roundness), which corroborates this finding. The presence of agglomerates of ultrafine/nanoparticles containing highly bioaccessible metals in playground sites may have severe implications in children's health. Therefore, further studies are required to characterize the size distribution, structure, shape and composition of such minerals which are essential factors related to the toxicology of inhaled dust particles.

Identification of inhalable rutile and polycyclic aromatic hydrocarbons (PAHs) nanoparticles in the atmospheric dust.

Addressing the presence of rutile nanoparticles (NPs) in the air is a work in progress, and the development of methodologies for the identification of NPs in atmospheric dust is essential for the assessment of its toxicological effects. To address this issue, we selected the fast growing desertic city of Hermosillo in northern Mexico. Road dust (n = 266) and soils (n = 10) were sampled and bulk Ti-contents were tested by portable X-ray fluorescence. NPs were extracted from atmospheric dust by PM1.0-PTFE filters and further characterized by Confocal Raman Microscopy, Energy-dispersive X-ray spectroscopy (EDS) coupled to Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM). Results showed (i) the average concentration of Ti in road dust (3447 mg kg-1) was similar to natural values and worldwide urban dusts; (ii) the bulk geochemistry was not satisfactory for Ti-NPs identification; (iii) 76% of the total extracted PM1.0 sample corresponded to NPs; (iv) mono-microaggregates of rutile NPs were identified; (v) ubiquitous polycyclic aromatic hydrocarbons (PAHs) were linked to NPs. The genotoxicity of rutile and PAHs, in connection with NPs content, make us aware of a crucial emerging environmental issue of significant health concern, justifying further research in this field.

The role of soil mineralogy on oral bioaccessibility of lead: Implications for land use and risk assessment.

Understanding the oral bioaccessibility of lead (Pb) present in soils in urbanized areas is important for the human exposure risk assessment. In particular, the role of the soil-mineralogy in the oral bioaccessibility has not been extensively studied. To investigate bioaccessibility, five types of periurban soils were collected, samples were spiked with the same amount of lead-chromates from traffic paint, and subjected to the in vitro Physiological Based Extraction Test (PBET). Ten samples of urban topsoils were collected at elementary schools playgrounds, Pb-bioaccessibility was measured, and a prediction equation for bioaccessibility was constructed. Mineralogy, and metal content were identified with a combination of X-ray powder diffraction, scanning electron microscopy, and portable X-ray fluorescence techniques. Traffic paint sample is made of 15% quartz (SiO2), 13% crocoite (PbCrO4), 55% calcite (CaCO3), and 17% kaolinite (Al2Si2O5(OH)4) and it contains high metal content (Pb, Cr, Zn, and Ca). Studied soils are characterized by variable amounts of acid-neutralizing minerals (carbonates) and low metal content. Spiked soils contained almost equal concentration of Pb, Cr, and Zn, because the contribution of these metals is from the added paint. However, obtained Pb-bioaccessibility at gastric and intestinal conditions are variable (40 to 51% gastric, 24 to 70.5% intestinal). Carbonate content shows significant correlation (p < 0.05) with Cr, Ca, calcite, crocoite, and Pb-bioaccessible at gastric conditions. Correlation of Pb-bioaccessible at intestinal conditions is significant (p < 0.05) with kaolinite. Variability of Pb-bioaccesibility in urban environments is commonly associated to differences in Pb-sources, however, our results show that the bioaccessibility of the same pollutant behaves different for each soil type. This suggests that soil mineralogy may play a role in Pb-releasing at gastrointestinal conditions. Soil information about mineralogical characteristics from this study may help to reduce exposure to lead from urban sources if data are incorporated into urban planning.

Source apportionment and environmental fate of lead chromates in atmospheric dust in arid environments.

The environmental fate of lead derived from traffic paint has been poorly studied in developing countries, mainly in arid zones. For this purpose, a developing city located in the Sonoran desert (Hermosillo, Mexico), was chosen to conduct a study. In this paper the lead chromate (crocoite) sources in atmospheric dust were addressed using a combination of Raman microspectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and Pb isotope measurements. A high concentration of Pb and Cr as micro- and nanostructured pigments of crocoite is reported in yellow traffic paint (n=80), road dust (n=146), settled dust in roofs (n=21), and atmospheric dust (n=20) from a developing city located in the Sonoran Desert. 10 samples of peri-urban soils were collected for local geochemical background. The paint photodegradation and erosion of the asphaltic cover are enhanced by the climate, and the presence of the mineral crocoite (PbCrO4) in road dust with an aerodynamic diameter ranging from 100nm to 2µm suggests its integration into the atmosphere by wind resuspension processes. A positive PbCr correlation (R2=0.977) was found for all studied samples, suggesting a common source. The Pb-isotope data show signatures in atmospheric dust as a product of the mixing of two end members: i) local soils and ii) crocoite crystals as pigments in paint. The presence of lead chromates in atmospheric dust has not been previously documented in Latin America, and it represents an unknown health risk to the exposed population because the identified size of crystals can reach the deepest part of lungs.