Cancer risk assessment and source apportionment of the gas- and particulate-phase of the polycyclic aromatic hydrocarbons in a metropolitan region in Brazil.

A risk assessment and a source apportionment of the particulate- and gas-phase PAHs were conducted in a high vehicular traffic and industrialized region in southeastern Brazil. Higher concentrations of PAHs were found during summer, being likely driven by the contributions of PAHs in the vapor phase caused by fire outbreaks during this period. Isomer ratio diagnostic and Principal Component Analysis (PCA) identified four potential sources in the region, in which the Positive Matrix Factorization (PMF) model confirmed and apportioned as gasoline-related (31.8%), diesel-related (25.1%), biomass burning (23.4%), and mixed sources (19.6%). The overall cancer risk had a tolerable value, with ∑CR = 4.6 × 10-5, being ingestion the major via of exposure (64% of the ∑CR), followed by dermal contact (33% of the ∑CR) and inhalation (3%). Mixed sources contributed up to 45% of the overall cancer risk (∑CR), followed by gasoline-related (up to 35%), diesel-related (up to 15%), and biomass burning (up to 10%). The risk assessment for individual PAH species allowed identifying higher CR associated with BaP, DBA, BbF, BaA, and BkF, species associated with gasoline-related and industrial sources. Higher risks were associated with PM2.5-bound PAHs exposure, mainly via ingestion and dermal contact, highlighting the need for measures of mitigation and control of PM2.5 in the region.

Chemical characterization of PM2.5 from region highly impacted by hailstorms in South America.

The chemical composition of particulate material plays an important role in the atmosphere, providing cloud and ice nuclei for storm development. This study aims to evaluate and infer the sources of ions, metals, and metalloids in the fine atmospheric particulate matter (PM2.5) from triple border Paraná, Santa Catarina (Brazil), and northeastern Argentina, which is among those with the highest hail incidence in the world. Among the ions, the concentrations presented the following sequence in decreasing order: [Formula: see text]> K+> [Formula: see text]> [Formula: see text]> Ca2+> Cl-> Na+> Mg2+. Regarding the metals and metalloid concentrations, the order was of S > Si > Al > Fe > P > Ti, Cr, Cu, and Zn > Br > Mn, and Ni. The main sources, supported by positive matrix factorization results, are soil and agricultural activities, as well as vehicular emissions due to the agricultural machinery and the displacement of residents. Besides, the influence of aerosols from biomass burning and industrial activities was observed, possibly come from long-distance transport. The composition of PM2.5 presents one or more elements considered present ice nuclei (IN) activity, such as Al, Mn, Cu, Co, Ni, and V (in form of oxides), corroborating with other studies, also, with high hail incidence. However, further studies are needed to verify the role of aerosol characteristics in the formation of IN and, consequently, hail.

Polycyclic aromatic hydrocarbons (PAHs) in sediments of the amazon coast: Evidence for localized sources in contrast to massive regional biomass burning.

The Amazon coastal zone has become contaminated with organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs). However, information about their distribution and sources in this area is scarce, despite increasing deforestation and oil exploitation. Therefore, individual PAHs were analysed in the sediments of the Oyapock estuary, which is located in the Amazon coastal zone. This study provides information about the spatial and short-term temporal distributions of PAHs and discusses the major sources of PAHs to better understand the anthropogenic processes occurring in adjacent areas. The concentrations of all sixteen priority PAHs defined by the US EPA (United States Environmental Protection Agency, ∑16PAHs) ranged from 10.9 to 138.8 ng g-1 with a mean and standard deviation = 37.9 ± 20.5 and indicated that this estuary is not contaminated, while the mean levels were similar to those found in other Amazon regions and pristine areas along the coast of Brazil. No significant differences were found in the sedimentary PAHs levels between the wet and dry sampling campaigns, despite the different climatic conditions. Diagnostic ratios, positive matrix factorization (PMF) and cluster analysis have shown that the majority of the investigated PAHs were derived from combustion processes (at least 55.1%, as estimated by the PMF model). Localized source inputs from oil and its by-products concomitantly with natural/biogenic sources appear to be secondary sources. The PAH contribution from biomass and wood combustion was approximately 13.6% and was relatively lower than other regions of the Amazon that are undergoing massive biomass burning. As the first study of PAHs in this region, this study provides vital information on the healthy state of the estuary and can serve as a baseline for assessing the impacts of acute oil disasters or the chronic input of PAHs as a result of human settlements.

PM2.5 monitoring during a 10-year period: relation between elemental concentration and meteorological conditions.

Four monitoring campaigns between the years 2009 and 2018 were conducted in Córdoba City, Argentina, to detect toxic metals in PM2.5 samples. The concentrations of As, Cd, Pb, Cu, Cr, Mn, Hg, Ni, and Zn, together with several other elements, were measured. The average metal concentrations followed the order: Zn > Cr > Cu > Mn > Pb > V > Ni > As ~ Sb > Cd > Tl > Pd > Hg > Pt. From the analysis of the temporal variation in the elemental concentration of PM2.5, results show seasonal variations that reach, in general, a maximum in the coldest seasons and a minimum in the warmer seasons. These differences could be explained by the different weather conditions during each season, the influence of the El Niño/La Niña regimen, and the presence of fires on certain sampling dates. The source apportionment analysis performed for the period 2017-2018 showed the contribution to PM2.5 of combustion of heavy fuel oil and diesel-powered vehicles, pet coke, metallurgical and nonferrous industries, paint plant factory, traffic, and natural sources like the soil and road dust. This last analysis completed the assignment of sources for the 10-year period of study. Thus, the results of this work contribute to the implementation of emission reduction strategies in order to decrease the impact of PM2.5 on the environment and the human health.

Hazardous trace elements in thoracic fraction of airborne particulate matter: Assessment of temporal variations, sources, and health risks in a megacity.

The deleterious health effects of thoracic fractions seem to be more related to the chemical composition of the particles than to their mass concentration. The presence of hazardous materials in PM10 (e.g., heavy metals and metalloids) causes risks to human health. In this study, twelve trace elements (Cd, Cr, Pb, Zn, Cu, Ni, Sn, Ba, Co, As, V, and Sb) in 315 samples of ambient PM10 were analyzed. The samples were collected at an urban background site in a Latin American megacity (Bogota, Colombia) for one year. The concentrations and temporal variabilities of these elements were examined. According to the results, Cu (52 ng/m3), Zn (44 ng/m3), Pb (25 ng/m3), and Ba (20 ng/m3) were the traces with the highest concentrations, particularly during the dry season (January to March), which was characterized by barbecue (BBQ) charcoal combustion and forest fires. In addition, the differences between the results of weekdays and weekends were identified. The determined enrichment factor (EF) indicated that Zn, Pb, Sn, Cu, Cd, and Sb mainly originated from anthropogenic sources. Moreover, a speciation analysis of inorganic Sb (EF > 300) was conducted, which revealed that Sb(V) was the main Sb species in the PM10 samples (>80%). Six causes for the hazardous elements were identified based on the positive matrix factorization (PMF) model: fossil fuel combustion and forest fires (60%), road dust (19%), traffic-related emissions (9%), copper smelting (8%), the iron and steel industry (2%), and an unidentified industrial sector (2%). Furthermore, a health risk assessment of the carcinogenic elements was performed. Accordingly, the cancer risk of inhalation exposure to Co, Ni, As, Cd, Sb(III), and Pb was negligible for children and adults at the sampling site. For adults, the adjusted Cr(VI) level was slightly higher than the minimal acceptable risk level during the study period (1.4 × 10-6).

Seasonal assessment and apportionment of surface water pollution using multivariate statistical methods: Sinos River, southern Brazil.

Assessment of surface water quality is an issue of currently high importance, especially in polluted rivers which provide water for treatment and distribution as drinking water, as is the case of the Sinos River, southern Brazil. Multivariate statistical techniques allow a better understanding of the seasonal variations in water quality, as well as the source identification and source apportionment of water pollution. In this study, the multivariate statistical techniques of cluster analysis (CA), principal component analysis (PCA), and positive matrix factorization (PMF) were used, along with the Kruskal-Wallis test and Spearman's correlation analysis in order to interpret a water quality data set resulting from a monitoring program conducted over a period of almost two years (May 2013 to April 2015). The water samples were collected from the raw water inlet of the municipal water treatment plant (WTP) operated by the Water and Sewage Services of Novo Hamburgo (COMUSA). CA allowed the data to be grouped into three periods (autumn and summer (AUT-SUM); winter (WIN); spring (SPR)). Through the PCA, it was possible to identify that the most important parameters in contribution to water quality variations are total coliforms (TCOLI) in SUM-AUT, water level (WL), water temperature (WT), and electrical conductivity (EC) in WIN and color (COLOR) and turbidity (TURB) in SPR. PMF was applied to the complete data set and enabled the source apportionment water pollution through three factors, which are related to anthropogenic sources, such as the discharge of domestic sewage (mostly represented by Escherichia coli (ECOLI)), industrial wastewaters, and agriculture runoff. The results provided by this study demonstrate the contribution provided by the use of integrated statistical techniques in the interpretation and understanding of large data sets of water quality, showing also that this approach can be used as an efficient methodology to optimize indicators for water quality assessment.

Chemical composition and source apportionment of PM10 at an urban background site in a high-altitude Latin American megacity (Bogota, Colombia).

Bogota registers frequent episodes of poor air quality from high PM10 concentrations. It is one of the main Latin American megacities, located at 2600 m in the tropical Andes, but there is insufficient data on PM10 source contribution. A characterization of the chemical composition and the source apportionment of PM10 at an urban background site in Bogota was carried out in this study. Daily samples were collected from June 2015 to May 2016 (a total of 311 samples). Organic carbon (OC), elemental carbon (EC), water soluble compounds (SO42-, Cl-, NO3-, NH4+), major elements (Al, Fe, Mg, Ca, Na, K, P) and trace metals (V, Cd, Pb, Sr, Ba, among others) were analyzed. The results were interpreted in terms of their variability during the rainy season (RS) and the dry season (DS). The data obtained revealed that the carbonaceous fraction (∼51%) and mineral dust (23%) were the main PM10 components, followed by others (15%), Secondary Inorganic Compounds (SIC) (11%) and sea salt (0.4%). The average concentrations of soil, SIC and OC were higher during RS than DS. However, peak values were observed during the DS due to photochemical activity and forest fires. Although trace metals represented <1% of PM10, high concentrations of toxic elements such as Pb and Sb on RS, and Cu on DS, were obtained. By using a PMF model, six factors were identified (∼96% PM10) including fugitive dust, road dust, metal processing, secondary PM, vehicles exhaust and industrial emissions. Traffic (exhaust emissions + road dust) was the major PM10 source, accounting for ∼50% of the PM10. The results provided novel data about PM10 chemical composition, its sources and its seasonal variability during the year, which can help the local government to define control strategies for the main emission sources during the most critical periods.

Air pollution, PM2.5 composition, source factors, and respiratory symptoms in asthmatic and nonasthmatic children in Santiago, Chile.

The objective of this study was to determine the association of respiratory symptoms and medication use and exposure to various air pollutants, PM2.5 components, and source factors in a panel of asthmatic and nonasthmatic children in Santiago, Chile. To this end, 174 children (90 asthmatics and 84 nonasthmatics) were followed throughout the winter months of 2010 and 2011. During the study period, children filled out daily diaries to record respiratory symptoms and medication use. Air pollution data were obtained from government central site measurements and a PM2.5 characterization campaign. PM2.5 source factors were obtained using positive matrix factorization (PMF). Associations of symptoms and exposure to pollutants and source-factor daily scores were modeled separately for asthmatic and nonasthmatic children using mixed logistic regression models with random intercepts, controlling for weather, day of the week, year, and viral outbreaks. Overall, high concentrations of air pollutants and PM2.5 components were observed. Six source factors were identified by PMF (motor vehicles, marine aerosol, copper smelter, secondary sulfates, wood burning, and soil dust). Overall, single pollutant models showed significant and strong associations between 7-day exposures for several criteria pollutants (PM2.5, NO2, O3), PM2.5 components (OC, K, S, Se, V), and source factors (secondary sulfate) and coughing, wheezing and three other respiratory symptoms in both in asthmatic and nonasthmatic children. No associations were found for use of rescue inhalers in asthmatics. Two-pollutant models showed that several associations remained significant after including PM2.5, and other criteria pollutants, in the models, particularly components and source factors associated with industrial sources. In conclusion, exposure to air pollutants, especially PM2.5, NO2, and O3, were found to exacerbate respiratory symptoms in both asthmatic and nonasthmatic children. Some of the results suggest that PM2.5 components associated with a secondary sulfate source may have a greater impact on some symptoms than PM2.5. In general, the results of this study show important associations at concentrations close or below current air quality standards.

Molecular view of the interaction of S-methyl methanethiosulfonate with DPPC bilayer.

We present molecular dynamics (MD) simulation studies of the interaction of a chemo preventive and protective agent, S-methyl methanethiosulfonate (MMTS), with a model bilayer of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). We analyzed and compared its diffusion mechanisms with the related molecule dimethyl sulfoxide (DMSO). We obtained spatially resolved free energy profiles of MMTS partition into a DPPC bilayer in the liquid-crystalline phase through potential of mean force (PMF) calculations using an umbrella sampling technique. These profiles showed a minimum for MMTS close to the carbonyl region of DPPC. The location of MMTS molecules in the DPPC bilayer observed in the MD was confirmed by previous SERS studies. We decomposed PMF profiles into entropic and enthalpic contributions. These results showed that the driving force for the partitioning of MMTS into the upper region of DPPC is driven by a favorable entropy change while partitioning into the acyl chains is driven by enthalpy. On the other hand, the partition of DMSO into the membrane is not favored, and is driven by entropy instead of enthalpy. Free diffusion MD simulations using all atom and coarse grained (CG) models of DPPC in presence of MMTS were used to analyze the effect of DPPC-MMTS interaction. Density profiles showed that MMTS locates preferentially in the carbonyl region, as expected according to the PMF profile and the experimental evidence. MMTS presented two differential effects over the packing of DPPC hydrocarbonate chains at low or at high molar ratios. An ordering effect was observed when a CG MMTS model was used. Finally, free diffusion MD and PMF decomposition for DMSO were used for comparison.

Interactions of the fatty acid-binding protein ReP1-NCXSQ with lipid membranes. Influence of the membrane electric field on binding and orientation.

The regulatory protein of the squid nerve sodium calcium exchanger (ReP1-NCXSQ) is a 15kDa soluble, intracellular protein that regulates the activity of the Na(+)/Ca(2+) exchanger in the squid axon. It is a member of the cellular retinoic acid-binding proteins family and the fatty acid-binding proteins superfamily. It is composed of ten beta strands defining an inner cavity and a domain of two short alpha helix segments. In this work, we studied the binding and orientation of ReP1-NCXSQ in anionic and zwitterionic lipid membranes using molecular dynamics (MD) simulations. Binding to lipid membranes was also measured by filtration binding assay. ReP1-NCXSQ acquired an orientation in the anionic membranes with the positive end of the macrodipole pointing to the lipid membrane. Potential of mean force calculations, in agreement with experimental measurements, showed that the binding to the anionic interfaces in low ionic strength was stronger than the binding to anionic interfaces in high ionic strength or to zwitterionic membranes. The results of MD showed that the electrostatic binding can be mediated not only by defined patches or domains of basic residues but also by a global asymmetric distribution of charges. A combination of dipole-electric field interaction and local interactions determined the orientation of ReP1-NCXSQ in the interface.