Seasonal variation and size distribution of aromatic acids in urban aerosols in Beijing, China.

Aromatic acids are an integral component of organic acids in the atmosphere, contributing to the formation of climate-altering brown carbon (BrC). To better understand the sources and formation processes of aromatic acids, we collected size-segregated particulate matter samples in urban Beijing from April 2017 to January 2018, which were analyzed using solvent-extraction followed by gas chromatography/mass spectrometry. Phthalic acid (o-PhA) had the greatest average annual concentration, followed by terephthalic acid (p-PhA), 4-hydroxybenzoic acid (4-OHBA), dehydroabietic acid (DA), syringic acid (SA), 3-hydroxybenzoic acid (3-OHBA), isophthalic acid (m-PhA), and vanillic acid (VA). We identified distinct seasonal variations in aromatic acids, with o-PhA peaking in summer due to photochemical activity, while p-PhA and 4-OHBA elevated in autumn and summer, respectively, influenced by open waste and biomass burning. Wintertime variations in all aromatic acids were driven by complex meteorology and increased anthropogenic emissions, including rural biomass burning for cooking and heating. Particle size distribution of aromatic acids was affected by seasonal agricultural activities and dust storms, multiple emission sources, and formation mechanisms. The o-PhA has predominantly bimodal distribution, with diverse sources and complex formation mechanisms including gas- and aqueous-phase chemistry. The applicability of o-PhA as a tracer for specific secondary organic aerosols has been questioned due to its potential primary sources. The 3-OHBA, 4-OHBA, VA, SA, and DA exhibited bimodal or trimodal patterns during haze and non-haze periods across different particle size ranges. The seasonal variation in VA/SA and VA/4-OHBA ratios demonstrated the complexity of biomass burning types, influenced by season, particle size, meteorological conditions, and combustion sources.

Respirable Metals, Bacteria, and Fungi during a Saharan-Sahelian Dust Event in Houston, Texas.

Although airborne bacteria and fungi can impact human, animal, plant, and ecosystem health, very few studies have investigated the possible impact of their long-range transport in the context of more commonly measured aerosol species, especially those present in an urban environment. We report first-of-kind simultaneous measurements of the elemental and microbial composition of North American respirable airborne particulate matter concurrent with a Saharan-Sahelian dust episode. Comprehensive taxonomic and phylogenetic profiles of microbial communities obtained by 16S/18S/ITS rDNA sequencing identified hundreds of bacteria and fungi, including several cataloged in the World Health Organization's lists of global priority human pathogens along with numerous other animal and plant pathogens and (poly)extremophiles. While elemental analysis sensitively tracked long-range transported Saharan dust and its mixing with locally emitted aerosols, microbial diversity, phylogeny, composition, and abundance did not well correlate with the apportioned African dust mass. Bacterial/fungal diversity, phylogenetic signal, and community turnover were strongly correlated to apportioned sources (especially vehicular emissions and construction activities) and elemental composition (especially calcium). Bacterial communities were substantially more dissimilar from each other across sampling days than were fungal communities. Generalized dissimilarity modeling revealed that daily compositional turnover in both communities was linked to calcium concentrations and aerosols from local vehicles and Saharan dust. Because African dust is known to impact large areas in northern South America, the Caribbean Basin, and the southern United States, the microbiological impacts of such long-range transport should be assessed in these regions.

Vertical stratification of aerosols over South Asian cities.

This study examines vertically resolved aerosol optical properties retrieved from Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) onboard CALIPSO satellite over several cities across South Asia from March 2010 to February 2021. Atmospheric layer-specific stratification of aerosols and dominant aerosol sub-types was recognized over each city with their seasonal trends. A contrasting pattern in aerosol vertical distribution over cities across Indo-Gangetic Plain (IGP) was noted compared to non-IGP cities, with considerable dependency on geographic location of the city itself. In all the cases, total extinction decreased with increasing altitude however, with varying degree of slope. A clear intrusion of transported aerosols at higher altitude (>3 km) was also evident. Extinction coefficient of type-separated aerosols indicate robust contribution of smoke aerosols, urban aerosols/polluted dust, and mineral dust below 3 km height. At higher altitude (>3 km), dust and urban aerosols dominate over majority of the stations. Overall, 51% of total columnar aerosols remained within 0-1 km height over South Asian cities, slightly high over the IGP (57%) against non-IGP cities (39%). Such distribution also has a seasonal pattern with higher fraction of aerosols remaining below 1 km during post-monsoon (October-November, 62%) and winter (December-February, 72%) compared to summer months (March-May, 39%). When partitioned against planetary boundary layer (PBL), 41% (59%) of aerosols remained within the PBL (free troposphere) that too exhibiting strong diurnal variations irrespective of seasons. Dominating aerosol types and their contribution to total aerosol loading was explored by comparing type-based aerosol extinction against total aerosol extinction. Dust, smoke and urban aerosols emerged as three predominating aerosol types, while presence of marine aerosol was noted over the coastal cities. Major fraction of smoke and urban aerosols remained within 2 km height from surface. In contrast, efficient transport of dust aerosol above 2 km height was evident particularly over IGP during summer.

Coupling Sr-Nd-Hf Isotope Ratios and Elemental Analysis to Accurately Quantify North African Dust Contributions to PM2.5 in a Complex Urban Atmosphere by Reducing Mineral Dust Collinearity.

Tracking Saharan-Sahelian dust across the globe is essential to elucidate its effects on Earth's climate, radiation budget, hydrologic cycle, nutrient cycling, and also human health when it seasonally enters populated/industrialized regions of Africa, Europe, and North America. However, the elemental composition of mineral dust arising locally from construction activities and aeolian soil resuspension overlaps with African dust. Therefore, we derived a novel "isotope-resolved chemical mass balance" (IRCMB) method by employing radiogenic strontium, neodymium, and hafnium isotopes to accurately differentiate and quantitatively apportion collinear proximal and synoptic-scale crustal and anthropogenic mineral dust sources. IRCMB was applied to two air masses that transported African dust to Barbados and Texas to track particulate matter (PM) spikes at both locations. During Saharan-Sahelian intrusions, the radiogenic content of urban PM2.5 increased with respect to 87Sr/86Sr and 176Hf/177Hf but decreased in terms of 143Nd/144Nd, demonstrating the ability of these isotopes to sensitively track African dust intrusions even in complex metropolitan atmospheres. The principal aerosol strontium, neodymium, and hafnium end members were concrete dust and soil, soil and motor vehicles, and motor vehicles and North African dust, respectively. IRCMB separated and quantified local soil and distal crustal dust even when PM2.5 concentrations were low, opening a promising source apportionment avenue for urbanized/industrialized atmospheres.

Three-dimensional nature of summertime aerosols over South Asia.

Three-dimensional (temporal-spatial-vertical) climatology of South Asian summertime (MAMJ, 2010-2019) aerosols and aerosol sub-types was explored using multiple high-resolution satellite-based observations and reanalysis dataset. Vertical stratification of aerosol layer and aerosol sub-types was identified using observation from space-borne lidar. Aerosol optical depth (AOD) was particularly high across the Indo-Gangetic Plain (IGP; AOD ± SD: 0.56 ± 0.12) and over eastern coast of India (AOD: 0.6-0.8), with prevalence of heterogeneous aerosol sub-types having strong spatial gradient. Clearly, aerosols over north-western arid part were highly absorbing (Ultra-violet Aerosol Index, UVAI > 0.80) and coarse (Ångström exponent, AE < 0.8), with an indication of desert/-mineral dust aerosols. In contrast, fine and moderate to non-absorbing aerosols (UVAI: 0.20-0.50) dominate from central to lower IGP, including in Bangladesh, with signature of anthropogenic emissions. Prevailing aerosols over twelve South Asian cities were classified into six aerosol sub-types constraining their particle size and UV-absorbing potential. Overall, mineral dust, smoke and urban aerosols were the three major aerosol sub-types that prevail across South Asia during summer. In particular, 58-70 % of retrieval days over Karachi and Multan were dust dominated; 57-64 % days were dust or urban aerosols dominated over Lahore, Delhi, Kanpur and Varanasi, and 56-77 % days were smoke or urban aerosols dominated over Dhaka, Kathmandu, Chennai, Mumbai, Colombo and Nagpur. Prevailing aerosols were vertically stratified as 50-70 % of total AOD was retrieved <2 km from the surface except in few cities where 70-80 % of AOD was retrieved <3 km height. Mineral dust and/or urban aerosols emerged as the most abundant aerosol types near the surface (<1 km) in all the cities except in Chennai, with their abundance remained as a function of emission sources and geographical location.

Persistent Uptake of H2O2 onto Ambient PM2.5 via Dark-Fenton Chemistry.

Particulate matter (PM) and gaseous hydrogen peroxide (H2O2) interact ubiquitously to influence atmospheric oxidizing capacity. However, quantitative information on H2O2 loss and its fate on urban aerosols remain unclear. This study investigated the kinetics of heterogeneous reactions of H2O2 on PM2.5 and explored how these processes are affected by various experimental conditions (i.e., relative humidity, temperature, and H2O2 concentration). We observed a persistent uptake of H2O2 by PM2.5 (with the uptake coefficients (γ) of 10-4-10-3) exacerbated by aerosol liquid water and temperature, confirming the critical role of water-assisted chemical decomposition during the uptake process. A positive correlation between the γ values and the ratio of dissolved iron concentration to H2O2 concentration suggests that Fenton catalytic decomposition may be an important pathway for H2O2 conversion on PM2.5 under dark conditions. Furthermore, on the basis of kinetic data gained, the parameterization of H2O2 uptake on PM2.5 was developed and was applied into a box model. The good agreement between simulated and measured H2O2 uncovered the significant role that heterogeneous uptake plays in the sink of H2O2 in the atmosphere. These findings suggest that the composition-dependent particle reactivity toward H2O2 should be considered in atmospheric models for elucidating the environmental and health effects of H2O2 uptake by ambient aerosols.

Estimation of the Seasonal Inhaled Deposited Dose of Particulate Matter in the Respiratory System of Urban Individuals Living in an Eastern Mediterranean City.

In this study, we present an estimation for the inhaled deposited dose rate in adult males and females during common exposure scenarios to urban background aerosols in an Eastern Mediterranean city (Amman, Jordan) based on a one-year database of measured particle number size distribution. The dose rates show seasonal variations reflecting the physical characteristics (i.e., modal structure) of the particle number size distribution. An additional factor was the varying deposition fraction (DF) for different regions and different human activities (exercising versus resting). The total dose rate was 3 × 109-65 × 109 particles/h (PM2.5 and PM10 doses 1-22 µg/h and 9-210 µg/h; respectively) depending on the gender, activity, and season. Based on the particle number metrics, the inhaled deposited dose in the head, Tracheobronchial, and alveolar were 7-16%, 16-28%, and 56-76%; respectively. Based on the PM2.5 metric, the corresponding dose rate was 9-41%,13-19%; and 46-72% respectively. As for the PM10 metric, they were 25-75%, 7-35%, and 15-55%; respectively.

Technical note: Understanding the effect of COVID-19 on particle pollution using a low-cost sensor network.

The 2020 coronavirus pandemic and the following quarantine measures have led to significant changes in daily life worldwide. Preliminary research indicates that air quality has improved in many urban areas as a result of these measures. This study takes a neighborhood-scale approach to quantifying this change in pollution. Using data from a network of citizen-hosted, low-cost particulate matter (PM) sensors, called Air Quality & yoU (AQ&U), we obtained high-spatial resolution measurements compared to the relatively sparse state monitoring stations. We compared monthly average estimated PM2.5 concentrations from February 11 to May 11, 2019 at 71 unique locations in Salt Lake County, UT, USA with the same (71) sensors' measurements during the same timeframe in 2020. A paired t-test showed significant reductions (71.1% and 21.3%) in estimated monthly PM2.5 concentrations from 2019 to 2020 for the periods from March 11-April 10 and April 11-May 10, respectively. The March time period corresponded to the most stringent COVID-19 related restrictions in this region. Significant decreases in PM2.5 were also reported by state monitoring sites during March (p < 0.001 compared to the previous 5-year average). While we observed decreases in PM2.5 concentrations across the valley in 2020, it is important to note that the PM2.5 concentrations did not improve equally in all locations. We observed the greatest reductions at lower elevation, more urbanized areas, likely because of the already low levels of PM2.5 at the higher elevation, more residential areas, which were generally below 2 µg/m3 in both 2019 and 2020. Although many of measurements during March and April were near or below the estimated detection limit of the low-cost PM sensors and the federal equivalent measurements, every low-cost sensor (51) showed a reduction in PM2.5 concentration in March of 2020 compared to 2019. These results suggest that the air quality improvement seen after March 11, 2020 is due to quarantine measures reducing traffic and decreasing pollutant emissions in the region.

Size-resolved particle emission factors of vehicular traffic derived from urban eddy covariance measurements.

Road traffic is one of the major sources of atmospheric particles in urban areas. Modelling the contribution of this source to urban pollution requires reliable estimates of emission factors possibly resolved in size. In this work, size-resolved particle emission factors (EFs) of the mixed vehicle fleet were measured in the urban area of Lecce (south-eastern Italy). The approach used is based on vertical fluxes measured with eddy-covariance, counting of vehicles, and estimation of footprints. Results show that the average EF in number (range 0.009-3 µm) was 2.2*1014 #/Veh km, being dominated by ultrafine particles (Dp < 0.25 µm) due to exhaust emissions. EF number size distribution decreases with particle size. A reduction of more than four orders of magnitude was observed at Dp ≅ 0.9 µm. EF mass size distribution reaches a maximum around Dp ≅ 0.3 µm then decreases until Dp ≅ 0.9 µm. For larger particles EF in mass increases for the influence of non-exhaust emissions. Average emission factor of PM1 was 56 mg/Veh Km and that of PM2.5 was 63 mg/Veh Km. A comparison of measurements taken in 2010 and 2015 in the same area shows a decreasing trend of the average total EF in number of about 56%, likely as a consequence of the increased use of new generation vehicles following more restrictive limits for particle emissions.

Urban vegetation and particle air pollution: Experimental campaigns in a traffic hotspot.

This work presents the main results of two experimental campaigns carried out in summer and winter seasons in a complex pollution hotspot near a large park, El Retiro, in Madrid (Spain). These campaigns were aimed at understanding the microscale spatio-temporal variation of ambient concentration levels in areas with high pollution values to obtain data to validate models on the effect of urban trees on particulate matter concentrations. Two different measuring approaches have been used. The first one was static, with instruments continuously characterizing the meteorological variables and the particulate matter concentration outside and inside the park. During the summer campaign, the particulate matter concentration was clearly influenced by a Saharan dust outbreak during the period 23 June to 10 July 2016, when most of the particulate matter was in the fraction PM2.5-10. During the winter campaign, the mass concentrations were related to the meteorological conditions and the high atmospheric stability. The second approach was a dynamic case with mobile measurements by portable instruments. During the summer campaign, a DustTrak instrument was used to measure PM10 and PM2.5 in different transects close to and inside the park at different distances from the traffic lane. It was observed a decrease in the concentrations up to 25% at 20 m and 50% at 200 m. High PM10 values were linked to dust resuspension caused by recreational activities and to a Saharan dust outbreak. The highest PM values were measured at the Independencia square, an area with many bus stops and high traffic density. During the winter campaign, three microaethalometers were used for Black Carbon measurement. Both pollutants also showed a reduction in their concentrations when moving towards inside the park. For PM10 and PM2.5, reductions up to 50% were observed, while for BC this reduction was smaller, about 20%.

The relationship between aerosol particles chemical composition and optical properties to identify the biomass burning contribution to fine particles concentration: a case study for São Paulo city, Brazil.

The air quality in the Metropolitan Area of São Paulo (MASP) is primarily determined by the local pollution source contribution, mainly the vehicular fleet, but there is a concern about the role of remote sources to the fine mode particles (PM2.5) concentration and composition. One of the most important remote sources of atmospheric aerosol is the biomass burning emissions from São Paulo state's inland and from the central and north portions of Brazil. This study presents a synergy of different measurements of atmospheric aerosol chemistry and optical properties in the MASP in order to show how they can be used as a tool to identify particles from local and remote sources. For the clear identification of the local and remote source contribution, aerosol properties measurements at surface level were combined with vertical profiles information. Over 15 days in the austral winter of 2012, particulate matter (PM) was collected using a cascade impactor and a Partisol sampler in São Paulo City. Mass concentrations were determined by gravimetry, black carbon concentrations by reflectance, and trace element concentrations by X-ray fluorescence. Aerosol optical properties were studied using a multifilter rotating shadowband radiometer (MFRSR), a Lidar system and satellite data. Optical properties, concentrations, size distributions, and elemental composition of atmospheric particles were strongly related and varied according to meteorological conditions. During the sampling period, PM mean mass concentrations were 17.4 ± 10.1 and 15.3 ± 6.9 µg/m3 for the fine and coarse fractions, respectively. The mean aerosol optical depths at 415 nm and Ångström exponent (AE) over the whole period were 0.29 ± 0.14 and 1.35 ± 0.11, respectively. Lidar ratios reached values of 75 sr. The analyses of the impacts of an event of biomass burning smoke transport to the São Paulo city revealed significant changing on local aerosol concentrations and optical parameters. The identification of the source contributions, local and remote, to the fine particles in MASP can be more precisely achieved when particle size composition and distribution, vertical profile of aerosols, and air mass trajectories are analyzed in combination.

Five primary sources of organic aerosols in the urban atmosphere of Belgrade (Serbia).

Biomass burning and primary biological aerosol particles (PBAPs) represent important primary sources of organic compounds in the atmosphere. These particles and compounds are able to affect climate and human health. In the present work, using HPLC-orbitrapMS, we determined the atmospheric concentrations of molecular markers such as anhydrosugars and phenolic compounds that are specific for biomass burning, as well as the concentrations of sugars, alcohol sugars and d- and l-amino acids (D-AAs and L-AAs) for studying PBAPs in Belgrade (Serbia) aerosols collected in September-December 2008. In these samples, high levels of all these biomarkers were observed in October. Relative percentages of vanillic (V), syringic compounds (S) and p-coumaric acid (PA), as well as levoglucosan/mannosan (L/M) ratios, helped us discriminate between open fire events and wood combustion for domestic heating during the winter. L-AAs and D-AAs (1% of the total) were observed in Belgrade aerosols mainly in September-October. During open fire events, mean D-AA/L-AA (D/L) ratio values of aspartic acid, threonine, phenylalanine, alanine were significantly higher than mean D/L values of samples unaffected by open fire. High levels of AAs were observed for open biomass burning events. Thanks to four different statistical approaches, we demonstrated that Belgrade aerosols are affected by five sources: a natural source, a source related to fungi spores and degraded material and three other sources linked to biomass burning: biomass combustion in open fields, the combustion of grass and agricultural waste and the combustion of biomass in stoves and industrial plants. The approach employed in this work, involving the determination of specific organic tracers and statistical analysis, proved useful to discriminate among different types of biomass burning events.

Benchmark study on fine-mode aerosol in a big urban area and relevant doses deposited in the human respiratory tract.

It is well-known that the health effects of PM increase as particle size decreases: particularly, great concern has risen on the role of UltraFine Particles (UFPs). Starting from the knowledge that the main fraction of atmospheric aerosol in Rome is characterized by significant levels of PM2.5 (almost 75% of PM10 fraction is PM2.5), the paper is focused on submicron particles in such great urban area. The daytime/nighttime, work-/weekdays and cold/hot seasonal trends of submicron particles will be investigated and discussed along with NOx and total PAH drifts demonstrating the primary origin of UFPs from combustion processes. Furthermore, moving from these data, the total dose of submicron particles deposited in the respiratory system (i.e., head, tracheobronchial and alveolar regions in different lung lobes) has been estimated. Dosimeter estimates were performed with the Multiple-Path Particle Dosimetry model (MPPD v.2.1). The paper discusses the aerosol doses deposited in the respiratory system of individuals exposed in proximity of traffic. During traffic peak hours, about 6.6 × 10(10) particles are deposited into the respiratory system. Such dose is almost entirely made of UFPs. According to the greater dose estimated, right lung lobes are expected to be more susceptible to respiratory pathologies than left lobes.

Mass distributions and morphological and chemical characterization of urban aerosols in the continental Balkan area (Belgrade).

This work presents characteristics of atmospheric aerosols of urban central Balkans area, using a size-segregated aerosol sampling method, calculation of mass distributions, SEM/EDX characterization, and ICP/MS analysis. Three types of mass distributions were observed: distribution with a pronounced domination of coarse mode, bimodal distribution, and distribution with minimum at 1 µm describing the urban aerosol. SEM/EDX analyses have shown morphological difference and variation in the content of elements in samples. EDX spectra demonstrate that particles generally contain the following elements: Al, Ca, K, Fe, Mg, Ni, K, Si, S. Additionally, the presence of As, Br, Sn, and Zn found in air masses from southeast segment points out the anthropogenic activities most probably from mining activities in southeastern part of Serbia. The ratio Al/Si equivalent to the ratio of desert dust was associated with air masses coming from southeastern and southwestern segments, pointing to influences from North Africa and Middle East desert areas whereas the Al/Si ratio in other samples is significantly lower. In several samples, we found high values of aluminum in the nucleation mode. Samples with low share of crustal elements in the coarse mode are collected when Mediterranean air masses prevailed, while high share in the coarse mode was associated with continental air masses that could be one of the approaches for identification of the aerosol origin. Graphical abstract ᅟ.

ROS production and gene expression in alveolar macrophages exposed to PM(2.5) from Baghdad, Iraq: Seasonal trends and impact of chemical composition.

The objective of this study was to assess the impact of changes in atmospheric particulate matter (PM) composition on oxidative stress markers in an in-vitro alveolar macrophage (AM) model. Fifty-three PM2.5 samples were collected during a year-long PM sampling campaign in Baghdad, Iraq, a semi-arid region of the country. Monthly composites were analyzed for chemical composition and for biological activity using in-vitro measurements of ROS production and gene expression in the AM model. Twelve genes that were differentially expressed upon PM exposure were identified and their co-associations with the composition of PM2.5 were examined. Ten of those genes were up-regulated in January and April composites; samples which also exhibited high ROS activity and relatively high PM mass concentration. ROS production was statistically correlated with total PM2.5 mass, levoglucosan (a wood burning tracer) and several trace elements of the PM (especially V and Ni, which are associated with oil combustion). The expression of several cytokine genes was found to be moderately associated with PM mass, crustal materials (indication of dusty days or dust storms) and certain metals (e.g. V, Fe and Ni) in the PM. Thus, the ROS activity association with PM2.5, may, in part, be driven by redox-active metals. The antioxidant response genes (Nqo1 and Hmox1) were moderately associated with polyaromatic hydrocarbons (PAHs) and showed a good correlation (r-Pearson of >0.7) with metals linked to vehicle-related emissions (i.e. Cu, Zn and Sb). Examining these associations in a larger sample pool (e.g. daily samples) would improve the power of the analysis and may strengthen the implication of these chemicals in the oxidative stress of biological systems, which could aid in the development of new metrics of PM toxicity.

Spatio-temporal variations of black carbon concentrations in the Megacity Beijing.

The spatial and temporal distribution and the flux of black carbon (BC) concentration in Beijing were continuously investigated over a two-year period at five sites to highlight the relative influence of contributing sources. The results demonstrate firstly that there is significant spatio-temporal variability of BC in Beijing. Highest concentrations occurred during winter primarily due to stagnant meteorological conditions, and seasonal BC sources, such as coal combustion for heating purposes. Biomass burning was identified as a minor seasonal source during the summer months. BC also varied spatially with higher concentrations in the SE of Beijing and lower concentrations in the NW, due to the differing emission intensity of various local BC sources such as traffic and industry. Frequently, overnight BC concentrations were higher due to specific meteorological conditions, such as the lower urban mixing layer height and various anthropogenic activities, such as exclusive night-time heavy duty vehicle traffic in the inner-city.