Search Results (8)

In this work, a novel analytical methodology for the extraction and determination of polycyclic aromatic hydrocarbon derivatives, nitrated (NPAH) and oxygenated (OPAH), in bee honey samples was developed. The extraction approach resulted in being straightforward, sustainable, and low-cost. It was based on a salting-out assisted liquid-liquid extraction followed by liquid chromatography-tandem mass spectrometry determination (SALLE-UHPLC-(+)APCI-MS/MS). The following figures of merit were obtained, linearity between 0.8 and 500 ng g⁻¹ for NPAH and between 0.1 and 750 ng g⁻¹ for OPAH compounds, coefficients of determination (r2) from 0.97 to 0.99. Limits of detection (LOD) were from 0.26 to 7.42 ng g⁻¹ for NPAH compounds and from 0.04 to 9.77 ng g⁻¹ for OPAH compounds. Recoveries ranged from 90.6% to 100.1%, and relative standard deviations (RSD) were lower than 8.9%. The green assessment of the method was calculated. Thus, the Green Certificate allowed a classification of 87 points. This methodology was reliable and suitable for application in honey samples. The results demonstrated that the levels of nitro- and oxy-PAHs were higher than those reported for unsubstituted PAHs. In this sense, the production chain sometimes transforms foods as direct carriers of contaminants to consumers, representing a concern and demonstrating the need for routine control. Full article

Emissions of PAH, nitro-PAHs, and oxy-PAHs from a diesel engine fueled with diesel-biodiesel-ethanol blends need to be controlled and reduced, as they are unregulated emissions harmful to the environment and human health. The objective of this work was to investigate the effect of ethanol concentration on diesel engine emissions when fueled with diesel–biodiesel–ethanol blends. Ethanol was added with biodiesel–diesel blends. Diesel B7 and two ternary blends, B7E3 and B7E10, with 3% and 10% ethanol, were tested and studied in a diesel engine to determine engine performance characteristics and particulate matter emissions and to quantify polycyclic aromatic compounds (PACs) associated with PM_1.0 and PM_2.5. Under the same engine conditions, 18 PAHs, 27 nitro-PAHs, and 6 quinones (oxy-PAHs) were determined by GC–MS in real samples obtained from the engine. The mean concentrations of PACs found in the B7, B7E3, and B7E10 blends for PM_1.0 ranged from 0.1 µg m⁻³ (coronene) to 118.1 µg m⁻³ (2-nitrofluorene). The concentrations for PM_2.5 ranged from 0.1 µg m⁻³ (acenaphthylene) to 99.7 µg m⁻³ (2-nitrofluorene). Potent mutagens benzanthrone (BA) and 3-nitrobenzanthrone (3-NBA) were found at concentrations ranging from 0.10 µg m⁻³ to 1.9 µg m⁻³ and 0.3 µg m⁻³ to 1.6 µg m⁻³, respectively. Low molecular weight (LMW) PAHs were mainly PACs bounded to the PM_1.0 and PM_2.5 particles emitted by B7E10. Flow properties were improved by adding 3% and 10% ethanol to biodiesel. B7E3 and B7E10 blends presented low fuel consumption and a reduction in the emission factor (EF) by the engine. B7E10 blending showed a smaller total concentration of ∑PAH (26.8 µg m⁻³), ∑nitro-PAH (85.4 µg m⁻³), and ∑oxy-PAH (6.0 µg m⁻³) associated with PM_2.5 particles compared PM_1.0. Full article

The concentration of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere has been continually monitored since their toxicity became known, whereas nitro-PAHs (NPAHs) and oxy-PAHs (OPAHs), which are derivatives of PAHs by primary emissions or secondary formations in the atmosphere, have gained attention more recently. In this study, a method for the quantification of 18 NPAH and OPAH congeners in the atmosphere based on combined applications of gas chromatography coupled with chemical ionization mass spectrometry is presented. A high sensitivity and selectivity for the quantification of individual NPAH and OPAH congeners without sample preparations from the extract of aerosol samples were achieved using negative chemical ionization (NCI/MS) or positive chemical ionization tandem mass spectrometry (PCI-MS/MS). This analytical method was validated and applied to the aerosol samples collected from three regions in Northeast Asia—namely, Noto, Seoul, and Ulaanbaatar—from 15 December 2020 to 17 January 2021. The ranges of the method detection limits (MDLs) of the NPAHs and OPAHs for the analytical method were from 0.272 to 3.494 pg/m³ and 0.977 to 13.345 pg/m³, respectively. Among the three regions, Ulaanbaatar had the highest total mean concentration of NPAHs and OPAHs at 313.803 ± 176.349 ng/m³. The contribution of individual NPAHs and OPAHs in the total concentration differed according to the regional emission characteristics. As a result of the aerosol samples when the developed method was applied, the concentrations of NPAHs and OPAHs were quantified in the ranges of 0.016~3.659 ng/m³ and 0.002~201.704 ng/m³, respectively. It was concluded that the method could be utilized for the quantification of NPAHs and OPAHs over a wide concentration range. Full article

To establish the risk of the endocrine disrupting activity of polycyclic aromatic compounds, especially oxygenated and nitrated polycyclic aromatic hydrocarbons (oxy-PAHs and nitro-PAHs, respectively), antiandrogenic and estrogenic activities were determined using chemically activated luciferase expression (CALUX) assays with human osteoblast sarcoma cells. A total of 27 compounds including 9 oxy-PAHs (polycyclic aromatic ketones and quinones) and 8 nitro-PAHs was studied. The oxy-PAHs of 7H-benz[de]anthracen-7-one (BAO), 11H-benzo[a]fluoren-11-one (B[a]FO), 11H-benzo[b]fluoren-11-one (B[b]FO), and phenanthrenequinone (PhQ) exhibited significantly the potent inhibition of AR activation. All nitro-PAHs exhibited high antiandrogenic activities (especially high for 3-nitrofluoranthene (3-NFA) and 3-nitro-7H-benz[de]anthracen-7-one (3-NBAO)), and the AR inhibition was confirmed as noncompetitive for 3-NFA, 3-NBAO, and 1,3-dinitropyrene (1,3-DNPy). Antiandrogenic activity of 3-NFA demonstrated characteristically a U-shaped dose–response curve; however, the absence of fluorescence effect on the activity was confirmed. The prominent estrogenic activity dependent on dose–response curve was confirmed for 2 oxy-PAHs (i.e., B[a]FO and B[b]FO). Elucidating the role of AR and ER on the effects of polycyclic aromatic compounds (e.g., oxy- and nitro-PAHs) to endocrine dysfunctions in mammals and aquatic organisms remains a challenge. Full article

The present study was aimed at determining airborne concentrations of PAHs, Nitro-/Oxy-PAHs and elements in industrial and urban areas of Taranto, a site of environmental risk in Southern Italy, after the issue of strategic measures for air pollution mitigation and control by the Italian Environment Ministry in 2012. A PM_2.5 sampling campaign was carried out from 9 to 28 December 2014 at eight receptor sites, two placed in the urban settlement and five included in the high spatial resolution fence monitoring network of the biggest European steel plant. The integration of collected data with meteorological parameters and source apportionment analysis by Positive Matrix Factorization and bivariate polar plots allowed to discriminate among emission sources and estimate their contributions. Evidence on the effect of distinct processes (homogenization, sintering) occurring inside the steel plant on airborne concentrations of PAHs and selected elements was provided. The impact of emissions from the steel plant “core” on the surrounding area was observed at receptor sites downwind to it. Moreover, the extent of the effectiveness of mitigation measures, partially applied at the moment of study’s beginning, was demonstrated by mean and peak pollutant concentrations at all receptor sites up to one order of magnitude lower than those documented prior to 2012. Full article

Renewable diesel fuels have the potential to reduce net CO₂ emissions, and simultaneously decrease particulate matter (PM) emissions. This study characterized engine-out PM emissions and PM-induced reactive oxygen species (ROS) formation potential. Emissions from a modern heavy-duty diesel engine without external aftertreatment devices, and fueled with petroleum diesel, hydrotreated vegetable oil (HVO) or rapeseed methyl ester (RME) biodiesel were studied. Exhaust gas recirculation (EGR) allowed us to probe the effect of air intake O₂ concentration, and thereby combustion temperature, on emissions and ROS formation potential. An increasing level of EGR (decreasing O₂ concentration) resulted in a general increase of equivalent black carbon (eBC) emissions and decrease of NO_x emissions. At a medium level of EGR (13% intake O₂), eBC emissions were reduced for HVO and RME by 30 and 54% respectively compared to petroleum diesel. In general, substantially lower emissions of polycyclic aromatic hydrocarbons (PAHs), including nitro and oxy-PAHs, were observed for RME compared to both HVO and diesel. At low-temperature combustion (LTC, O₂ < 10%), CO and hydrocarbon gas emissions increased and an increased fraction of refractory organic carbon and PAHs were found in the particle phase. These altered soot properties have implications for the design of aftertreatment systems and diesel PM measurements with optical techniques. The ROS formation potential per mass of particles increased with increasing engine O₂ concentration intake. We hypothesize that this is because soot surface properties evolve with the combustion temperature and become more active as the soot matures into refractory BC, and secondly as the soot surface becomes altered by surface oxidation. At 13% intake O₂, the ROS-producing ability was high and of similar magnitude per mass for all fuels. When normalizing by energy output, the lowered emissions for the renewable fuels led to a reduced ROS formation potential. Full article

This study aims to establish the influence of primary emission sources and atmospheric transformation process contributing to the concentrations of quinones associated to particulate matter of less than 2.5 µm (PM_2.5) in three sites within the Metropolitan Area of Guadalajara (MAG), namely Centro (CEN), Tlaquepaque (TLA) and Las Águilas (AGU). Environmental levels of quinones extracted from PM_2.5 filters were analyzed using Gas Chromatography coupled to Mass Spectrometry (GC-MS). Overall, primary emissions in combination with photochemical and oxidation reactions contribute to the presence of quinones in the urban atmosphere of MAG. It was found that quinones in PM_2.5 result from the contributions from direct emission sources by incomplete combustion of fossil fuels such as diesel and gasoline that relate mainly to vehicular activity intensity in the three sampling sites selected. However, this also suggests that the occurrence of quinones in MAG can be related to photochemical transformation of the parent Polycyclic Aromatic Hydrocarbons (PAHs), to chemical reactions with oxygenated species, or a combination of both routes. The higher concentration of 1,4-Chrysenequinone during the rainy season compared to the warm-dry season indicates chemical oxidation of chrysene, since the humidity could favor singlet oxygen collision with parent PAH present in the particle phase. On the contrary, 9,10-Anthraquinone/Anthracene and 1,4-Naftoquinone/Naphthalene ratios were higher during the warm-dry season compared to the rainy season, which might indicate a prevalence of the photochemical formation during the warm-dry season favored by the large solar radiation typical of the season. In addition, the estimated percentage of photochemical formation of 9,10-Phenanthrenequinone showed that the occurrence of this compound in Tlaquepaque (TLA) and Las Águilas (AGU) sites is mainly propagated by conditions of high solar radiation such as in the warm-dry season and during long periods of advection of air masses from emission to the reception areas. This was shown by the direct association between the number hourly back trajectories arriving in the TLA and AGU from Centro and other areas in MAG and the highest photochemical formation percentage. Full article

Excavation followed by landfilling is the most common method for treating soils contaminated by metals. However, as this solution is not sustainable, alternative techniques are required. Chemical soil washing is one such alternative. The aim of this experimental lab-scale study is to develop a remediation and metal recovery method for Cu contaminated sites. The method is based on the washing of soil or ash (combusted soil/bark) with acidic waste liquids followed by electrolytic Cu recovery by means of bioelectrochemical systems (BES). The results demonstrate that a one- or two-step acidic leaching process followed by water washing removes >80 wt. % of the Cu. Copper with 99.7–99.9 wt. % purity was recovered from the acidic leachates using BES. In all experiments, electrical power was generated during the reduction of Cu. This clearly indicates that Cu can also be recovered from dilute solutions. Additionally, the method has the potential to wash co-pollutants such as polycyclic aromatic hydrocarbons (PAHs) and oxy-PAHs. Full article