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.

The wild plant Gnaphalium lavandulifolium as a sentinel for biomonitoring the effects of environmental heavy metals in the metropolitan area of México Valley.

Biomonitoring is a valuable tool for assessing the presence and effects of air pollutants such as heavy metals (HM); due to their toxicity and stability, these compounds can affect human health and the balance of ecosystems. To assess its potential as a sentinel organism of HM pollution, the wild plant Gnaphalium lavandulifolium was exposed to four sites in the metropolitan area of México Valley (MAMV): Altzomoni (ALT) Coyoacán (COY), Ecatepec (ECA), and Tlalnepantla (TLA) during 2, 4, and 8 weeks, between October and November 2019. Control plants remained under controlled conditions. The chemical analysis determined twelve HM (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn) in the leaves. Macroscopic damage to the leaves, later determined in semi-thin sections under light microscopy, lead to a finer analysis. Transmission electron microscope (TEM) showed major structural changes: chromatin condensation, protoplast shrinkage, cytoplasm vacuolization, cell wall thinning, decreased number and size of starch grains, and plastoglobules in chloroplasts. All these characteristics of stress-induced programed cell death (sPCD) were related to the significant increase of toxic HM in the leaves of the exposed plants compared to the control (p < 0.05). Immunohistochemistry revealed a significant amount of proteases with caspase 3-like activity in ECA and TLA samples during long exposure times. Ultrastructural changes and sPCD features detected confirmed the usefulness of G. lavandulifolium as a good biomonitor of HM contamination. They supported the possibility of considering subcellular changes as markers of abiotic stress conditions in plants.

Health risk assessment of gaseous elemental mercury (GEM) in Mexico City.

Emissions of gaseous elemental mercury (GEM or Hg0) from different sources in urban areas are important subjects for environmental investigations. In this study, atmospheric Hg measurements were conducted to investigate air pollution in the urban environment by carrying out several mobile surveys in Mexico City. This work presents atmospheric concentrations of GEM in terms of diurnal variation trends and comparisons with criteria for pollutant concentrations such as CO, SO2, NO2, PM2.5, and PM10. The concentration of GEM was measured during the pre-rainy period by using a high-resolution active air sampler, the Lumex RA 915 M mercury analyzer. In comparison with those for other cities worldwide, the GEM concentrations were similar or slightly elevated, and they ranged from 0.20 to 30.23 ng m-3. However, the GEM concentration was significantly lower than those in contaminated areas, such as fluorescent lamp factory locations and gold mining zones. The GEM concentrations recorded in Mexico City did not exceed the WHO atmospheric limit of 200 ng m-3. We performed statistical correlation analysis which suggests equivalent sources between Hg and other atmospheric pollutants, mainly NO2 and SO2, emitted from urban combustion and industrial plants. The atmospheric Hg emissions are basically controlled by sunlight radiation, as well as having a direct relationship with meteorological parameters. The area of the city studied herein is characterized by high traffic density, cement production, and municipal solid waste (MSW) treatment, which constantly release GEM into the atmosphere. In this study, we included the simulation with the HYSPLIT dispersion model from three potential areas of GEM release. Emissions from industrial corridors and volcanic plumes localized outside the urban area contribute to the pollution of Mexico City and mainly affect the northern area during specific periods and climate conditions. Using the USEPA model, we assessed the human health risk resulting from exposure to inhaled GEM among residents of Mexico City. The results of the health risk assessment indicated no significant noncarcinogenic risk (hazard quotient (HQ) < 1) or consequent adverse effects for children and adults living in the sampling area over the study period. GEM emissions inventory data is necessary to improve our knowledge about the Hg contribution and effect in urban megacity areas with the objective to develop public safe policy and implementing the Minamata Convention.

Gaseous Elemental Mercury (GEM) in the Mexico City Metropolitan Area.

This paper presents atmospheric gaseous elemental mercury (GEM) data recorded during two short-term monitoring surveys in the Mexico City Metropolitan Area (MCMA) at 12th May 2019 and at 22nd May 2020, during conditions of low and high human activity respectively. Results, although they are limited, can be considered as the representative range of exposure to GEM of the inhabitants of MCMA; differences in results reveal the impact of human activities on GEM background levels (2.53 and 3.76 ng m-3, respectively). GEM concentrations and their spatial distribution does not allow for the identification of important industrial sources and do not reach intervention pollution levels. The activity of the Popocatépetl volcano is not likely to have an effect on GEM in the MCMA. In spite the evident decrease in GEM concentrations compared with data previously reported, monitoring must be carried out routinely given Mexico's participation in the Minamata Convention on Mercury.

Robinsonecio gerberifolius as a sentinel organism for atmospheric pollution by heavy metals in several sites of Mexico city and its metropolitan area.

Evaluate the effect of heavy metals (HM) on sentinel organisms such as vascular plants represent a model to estimate toxic hazard due to environmental pollution. In the present study, the plant Robinsonecio gerberifolius was used to evaluate the toxic effects of the HM contained in the leaves of plants that were exposed to 4 different sites in Mexico city and its metropolitan area, during the rainy and dry seasons in the period 2017-2019. The comet assay to evaluate genotoxicity revealed an increase with respect to control (p < 0.05), in 2nd and 8th week of exposure, in all 4 study sites and in both seasons, more significant in the rainy period. An increase in the induction of oxidative stress was also observed in the exposed leaves from the 4 study sites when compared with the control; in some cases, the increases were significant (p < 0.05). In general, α- and ß-carotenoids were increased at 8th week of exposure, in all plants exposed in both seasons, while miR398 increased in plants exposed in 2 study sites (p < 0.05). Finally, toxic HM like aluminum, vanadium, and cadmium, increased significantly in the rainy season, while lead increased in the dry season. We conclude that R. gerberifolius can be considered a sentinel plant for evaluating the presence and general toxic effects caused by the presence of toxic HM that have been documented in the atmosphere of Mexico City and its metropolitan area.

Historical trends of metals concentration in PM10 collected in the Mexico City metropolitan area between 2004 and 2014.

In this work, we report metals concentrations in 80 PM10 samples collected at four sites in the Mexico City Metropolitan Area (MCMA): Tlalnepantla (NE), Xalostoc (NE), Merced (C), and Pedregal (S), during the dry/cold season (October to January) for the 2004-2014 period. Mean PM10 mass concentration (66.1 µg m-3) significantly exceeds the annual mean air quality guidelines recommended by the World Health Organization. The statistical analysis of concentration data and meteorological parameters allows us to recognize the importance of wind intensity speed (Wsp) and wind direction conditions in the enrichment of PM concentrations. The proximity and magnitude of the emitting source is also relevant for PM concentration. Such conditions favored that higher metal concentration was recognized at the north of the studied area. By means principal component analysis (PCA) was difficult to identify the groups of metals associated with specific sources (anthropogenic and geogenic) given the high complexity of the study area and the long period of time evaluated. Metal concentration trend shows an important positive trend for Pt, V and Cr, while PM10, Ni, Cu, Ag and Sb show a trend of moderate increase. In contrast, Pb and Co registered a strong percentage reduction, while Hg, Mn, As and Cd show a slight reduction, probably resulting from the implementation of regulatory measures and influenced by urban changes associated at the north of the studied area. The results of this research provide information that should be considered for evaluating the impact of anthropogenic sources and applying regulatory measures to control emissions.

Mercury, Platinum, Antimony and Other Trace Elements in the Atmospheric Environment of the Urban Area of Mexico City: Use of Ficus benjamina as Biomonitor.

The application of Sb, Pt and Hg in the development of new strategic technologies has increased significantly in recent years. This study evaluates the impact of vehicular traffic on the rise in emission of Sb, Pt and Hg in the atmospheric environmen of Mexico City and their correlation to Co, Cr, Cu, Ni, Pb, V and Zn. Ficus benjamina leaves were collected as biomonitor of atmospheric metals deposited in areas exposed to heavy vehicular traffic. High enrichment factor values (metal(loid) concentration/background values) were calculated: 146 (Sb), 52.8 (Pb), 29.7 (Pt) and 25.1 (Cr). Enrichment factors of Ni, Zn, Co, V, Cu and Hg decrease in that order and are < 10. Principal component analysis allows recognize that most of the analyzed metal(loids) are related to traffic sources; Ni and Cr are also attributable to an additional anthropogenic source. No relationship was found relating Pb to vehicular sources.

Metal(loid) exposure on children from a historical metallurgical site.

The data obtained in this study represent a comprehensive assessment of human exposure to metal(loids) enriched in the environment, derived from metallurgical activities in Cedral, a town in North-Central Mexico. A multi-elemental analysis (As, Cd, Cr, Cu, Fe, Mn and Sb) shows high metal(loid) content in environmental media (tailings samples, dust samples and particulate matter < 2.5 µm collected in the urban area). Blood samples from school-age children were collected and analyzed to determine exposure levels. The assessment of the data obtained from this study shows that Sb and Cd are highly enriched elements in the environment of Cedral; their respective levels in the blood samples analyzed are 10.9 and 11.3 times higher than their pediatric reference levels. The statistical analysis indicates a strong relationship between metal(loid)s in blood samples and both dust and PM2.5 samples, which reveal that ingestion and inhalation could represent important exposure routes for metal(loid) intake. Continuous monitoring in the area is paramount to assess the health impact posed by the different routes of exposure. It is also important to implement health education programs to decrease the population's exposure to metal(loid)s and to design urgent remediation measures, to be implemented as soon as possible.

Moss (Hypnum amabile) as biomonitor of genotoxic damage and as bioaccumulator of atmospheric pollutants at five different sites of Mexico City and metropolitan area.

Mexico City has been classified as one megacity, its altitude, thermal inversions, and high seasonal radiation are factors that prevent dispersion of pollutants, which effects are detrimental to health. Therefore, it is important to have an organism that allows evaluate the damage caused by such exposure, as is the case of mosses that obtain nutrients from the atmosphere; this property makes them excellent biomonitors to evaluate genotoxic damage caused by exposure to pollutants, in addition to its large accumulation capacity. For these reasons and to relate the effects of atmospheric pollution with a biological response, we propose to use the moss Hypnum amabile as a bioaccumulator of atmospheric pollutants and biomonitor of the genotoxic effect that the air pollution can induce it through the comet assay. Mosses were placed in five localities of Mexico City and the metropolitan area on the first days of each month of the dry (cold and warm) and rainy seasons, with a 30-day exposure, after which they were changed for a new sample (for 8 months). Each month, the moss exposed was collected and nuclei were isolated to perform comet assay. To demonstrate heavy metal bioaccumulation capacity, samples were observed in a transmission electron microscope and qualitative microanalysis by scanning electron microscopy was carried out parallel. The chemical analysis detected 14 heavy metals by mass spectrometry method with inductively coupled plasma source. Additionally, 22 polycyclic aromatic hydrocarbons were also determined by gas chromatography-mass spectrometry. Analysis of variance and Kruskal-Wallis test were performed to compare DNA damage of each station against control, which was maintained in the laboratory in a chamber with filtered air. This is the first study on the genotoxicity of mosses exposed to the atmosphere of Mexico City and metropolitan area that in addition to proving their accumulation capacity shows their ability to respond to atmospheric pollutants.

Insectivorous bats as biomonitor of metal exposure in the megalopolis of Mexico and rural environments in Central Mexico.

The Megalopolis of Mexico is one of the largest cities in the world and presents substantial problems of metal pollution. Insectivorous bats that inhabit this city are potentially exposed to metals and could therefore serve as a good biomonitor. We collected 70 adult male individuals of Tadarida brasiliensis (Chiroptera: Molossidae) from two areas inside the Megalopolis (Cuautitlán and Xochimilco) and two rural environments in Central Mexico (Tequixquiac and Tlalcozotitlán). We analyzed livers to determine the total concentrations of ten metals by the ICP-MS technique, compared concentrations among study sites to provide evidence of metal exposure, and explored the associations between metals and their accumulation patterns in bats. The hepatic metal concentrations we recorded were generally consistent with those of similar studies in insectivorous bats. Higher concentrations of Cu and Zn in Cuautitlán and Xochimilco bats were associated with vehicular traffic. Higher concentrations of V, Cr, and Co in Tequixquiac bats and Cd in Tlalcozotitlán bats were linked with industrial, agricultural, or sewage sources. Variations in Fe and Mn concentrations were related to geogenic sources or local conditions. Similar Ni and Pb concentrations were linked with strong homeostatic controls or historical pollution. Accumulation patterns showed that all urban bats belonged to a single population with similar degrees of metal exposure, while rural bats belonged to two different populations exposed to different metals. Our results highlight the need to monitor the emissions generated by particular sources in each study site.

Spatial and temporal distribution of metals in PM2.5 during 2013: assessment of wind patterns to the impacts of geogenic and anthropogenic sources.

The Mexico City Metropolitan Area (MCMA) was the object of a chemical elemental characterization (Ti, V, Cr, Mn, Co, Ni, Cu, Mo, Ag, Cd, Sb, Pb, La, Sm, Ce, and Eu) of PM2.5 collected during 2013 and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Sampling campaigns were carried out at five locations simultaneously-northwest, northeast, center, southwest, and southeast-during dry-warm season (April), rainy season (August), and dry-cold season (November). By means of enrichment factor (EF) and principal component analysis (PCA), it was possible to attribute the analyzed elements to geogenic and anthropogenic sources, as well as to identify a group of elements with mixed provenance sources. The highest concentrations for most metals were found in northwest and northeast, and during dry-warm (DW), confirming the trend observed in PM2.5 samples collected in 2011. Despite similarities between 2011 and 2013, an increase of 17% in PM2.5 mass concentration was observed, mainly attributable to geogenic sources, whereby the importance of wind intensity to the impact of emission sources is highlighted. The effect of wind intensity was revealed, by means of polar plots, as the controlling mechanism for this increase. This allowed us to conclude that high-speed episodes (5 m s-1) were responsible for raising geogenic metal concentrations rather than wind direction.

Atmospheric PM2.5 Mercury in the Metropolitan Area of Mexico City.

In this study, atmospheric mercury concentration in airborne particulate matter with an aerodynamic diameter ≤ 2.5 µm (PM2.5) was analyzed by ICP-MS. Samples were collected in the Mexico City Metropolitan Area (MCMA), during 2013, in five locations, Northwest, Northeast (NE), Central, Southwest and Southeast, along three seasons: dry warm, rainy, and dry cold (DC). It can be observed that NE shows the highest mercury concentration (p < 0.05), where pollution events were identified. The seasonal distribution shows that samples collected during DC present the highest concentration (p < 0.05). These results are in agreement with the distribution of important mercury industrial sources located in the northern urban area as well with the temperature and wind conditions during 2013. The comparison of data obtained in this work with those of similar previous studies clearly indicates a decrease, between 2006 and 2013, of mercury content in PM2.5 collected in MCMA.

Recognition of the importance of geogenic sources in the content of metals in PM2.5 collected in the Mexico City Metropolitan Area.

The study of airborne metals in urban areas is relevant due to their toxic effects on human health and organisms. In this study, we analyzed metals including rare earth elements (REE) in particles smaller than 2.5 µm (PM2.5), collected at five sites around the Mexico City Metropolitan Area (MCMA), during three periods in 2011: April (dry-warm season, DW), August (rainy season, R), and November (dry-cold season, DC). Principal component analysis allowed identifying factors related to geogenic sources and factors related to anthropogenic sources. The recognition of the high impact of geogenic sources in PM2.5 is in agreement with the REE distribution patterns, which show similar behavior as those shown by igneous rocks, confirming the influence of the regional geogenic material. Metals associated to geogenic sources showed higher concentration (p < 0.05) at NE of the MCMA and a significant correlation with prevalent winds. Geogenic metals show similar seasonal distribution, with the highest concentration during DW (p < 0.05), suggesting a possible metal resuspension effect which affects more significantly at lower relative humidity (RH). The metals associated with anthropogenic sources are in agreement with the urban complexity of the area, showing homogenous distribution throughout MCMA (p > 0.05) and no similar seasonal pattern among them. These unexpected results exposed outstanding information regarding the identification of different geogenic sources as the main contributors of metals in the atmospheric environment in the MCMA and highlighted the importance of meteorology in the spatial and seasonal metal patterns.

Increase in platinum group elements in Mexico City as revealed from growth rings of Taxodium mucronatum ten.

Tree rings may be used as indicators of contamination events providing information on the chronology and the elemental composition of the contamination. In this framework, we report PGEs enrichment in growth rings of Taxodium mucronatum ten for trees growing in the central area of Mexico City as compared to trees growing in a non-urban environment. Concentrations of PGE were determined by ICP-MS analysis on microwave-digested tree rings. The element found in higher concentrations was Pd (1.13-87.98 µg kg(-1)), followed by Rh (0.28-36.81 µg kg(-1)) and Pt (0.106-7.21 µg kg(-1)). The concentration trends of PGEs in the tree-ring sequences from the urban area presented significant correlation values when comparing between trees (r between 0.618 and 0.98, P < 0.025) and between elements within individual trees (r between 0.76 and 0.994, P < 0.01). Furthermore, a clear increase was observed for rings after 1997, with enrichment of up to 60 times the mean concentration found for the sequence from the non-urban area and up to 40 times the mean concentration for the pre-1991 period in the urban trees. These results also demonstrate the feasibility of applying T. mucronatum ten to be used as a bioindicator of the increase in PGE in urban environments.

Platinum in PM2.5 of the metropolitan area of Mexico City.

The increase in platinum (Pt) in the airborne particulate matter with size ≤2.5 µm (PM2.5) in urban environments may be interpreted as result of the abrasion and deterioration of automobile catalyst. Nowadays, about four million vehicles in Mexico City use catalytic converters, which means that their impact should be considered. In order to evaluate the contribution of Pt to environmental pollution of the metropolitan area of Mexico City (MAMC), airborne PM2.5 was collected at five different sites in the urban area (NW, NE, C, SW, SE) in 2011 during April (dry-warm season), August (rainy season) and December (dry-cold season). Analytical determinations were carried out using a ICP-MS with a collision cell and kinetic energy discrimination. The analytical and instrument performance was evaluated with standard road dust reference material (BCR-723). Median Pt concentration in the analyzed particulate was is 38.4 pg m(-3) (minimal value 1 pg m(-3) maximal value 79 pg m(-3)). Obtained Pt concentrations are higher than those reported for other urban areas. Spatial variation shows that SW had Pt concentration significantly higher than NW and C only. Seasonal variation shows that Pt median was higher in rainy season than in both dry seasons. A comparison of these results with previously reported data of PM10 from 1991 and 2003 in the same studied area shows a worrying increase in the concentration of Pt in the air environment of MAMC.

Assessment of atmospheric metal pollution in the urban area of Mexico City, using Ficus benjamina as biomonitor.

Concentrations of vanadium, chromium, cobalt, nickel, copper, zinc, antimony, and lead were measured in Ficus benjamina leaves from the Mexico City urban area in order to assess their enrichment against background values. The instrumental analysis was performed using inductively coupled plasma mass spectrometry and the analytical method was tested using two certified reference materials from the National Institute of Standards and Technology (1547 Peach Leaves and 1573a Tomato Leaves). Enrichment factors were calculated, i.e., total to background concentration ratio, for each metal. Low enrichments of vanadium, cobalt, nickel, and copper (≈2), and mild enrichments of chromium and zinc (4.4, 4.5 respectively) were found in the entire area; oppositely, high enrichments were assessed for antimony (28.6) and lead (17.2). However, results indicate that metal concentrations strongly depend on the specific urban sub-area. Increments of metals were attributed to natural, vehicular, and industrial sources.

Spatial distribution of heavy metals in top soils around the industrial facilities of Cromatos de México, Tultitlan Mexico.

The environmental damage caused by industrial activities in Cromatos de México, (Tultitlán, México) has been evaluated in terms of heavy metal concentrations in topsoils of the surrounding area. The concentrations of lead, copper and zinc demonstrate a significant enrichment with respect to unpolluted levels. Their maximum enrichment factors are 37.7, 21.1 and 9.6 mg kg⁻¹, respectively; such increase is related to traffic emissions. Nickel concentrations show no significant difference in the analyzed samples. Total chromium concentrations show a significant decrease with distance from the industrial facilities, ranging from 15 to 1,837 mg kg⁻¹. The enrichment factors of chromium (total), with respect to the background values reach up to 40.8 mg kg⁻¹. In spite of this pronounced increase, only three analyzed samples show chromium (VI) concentrations over 0.5 mg kg⁻¹ (instrumental detection limit) and do not exceed the values recommended by the Mexican official norm. The current results show that the chromium present in the studied area does not represent serious health risks and environmental damage in the zone, nevertheless, it is necessary to consider that the oxidation of chromium (III) is determinate by changes in redox and/or pH conditions which would imply significant impacts upon its toxic risk. This study suggests that the waste material generated during the industrial activities of Cromatos de Mexico represents a relevant metal pollution source for the area even 30 years after the closure of the industrial facilities.