Nitro-PAHs: Occurrences, ecological consequences, and remediation strategies for environmental restoration.

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are persistent pollutants that have been introduced into the environment as a result of human activities. They are produced when PAHs undergo oxidation and are highly resistant to degradation, resulting in prolonged exposure and significant health risks for wildlife and humans. Nitro-PAHs' potential to induce cancer and mutations has raised concerns about their harmful effects. Furthermore, their ability to accumulate in the food chain seriously threatens the ecosystem and human health. Moreover, nitro-PAHs can disrupt the normal functioning of the endocrine system, leading to reproductive and developmental problems in humans and other organisms. Reducing nitro-PAHs in the environment through source management, physical removal, and chemical treatment is essential to mitigate the associated environmental and human health risks. Recent studies have focused on improving nitro-PAHs' phytoremediation by incorporating microorganisms and biostimulants. Microbes can break down nitro-PAHs into less harmful substances, while biostimulants can enhance plant growth and metabolic activity. By combining these elements, the effectiveness of phytoremediation for nitro-PAHs can be increased. This study aimed to investigate the impact of introducing microbial and biostimulant agents on the phytoremediation process for nitro-PAHs and identify potential solutions for addressing the environmental risks associated with these pollutants.

Particulate matter from a tropical city in southeast Brazil: Impact of biomass burning on polycyclic aromatic compounds levels, health risks, and in vitro toxicity.

In the context of a rising global temperature, biomass burning represents an increasing risk to human health, due to emissions of highly toxic substances such as polycyclic aromatic hydrocarbon (PAHs). Size-segregated particulate matter (PM) was collected in a region within the sugarcane belt of São Paulo state (Brazil), where biomass burning is still frequent, despite the phasing out of manual harvesting preceded by fire. The median of the total concentration of the 15 PAHs determined was 2.3 ± 1.8 ng m-3 (n = 19), where 63% of this content was in PM1.0. Concentrations of OPAHs and NPAHs were about an order of magnitude lower. PM2.5 collected in the dry season, when most of the fires occur, presented PAHs and OPAHs total concentrations three times higher than in the wet season, showing positive correlations with fire foci number and levoglucosan (a biomass burning marker). These results, added to the fact that biomass burning explained 65% of the data variance (PCA analysis), evidenced the importance of this practice as a source of PAHs and OPAHs to the regional atmosphere. Conversely, NPAHs appeared to be mainly derived from diesel-powered vehicles. The B[a]P equivalent concentration was estimated to be 4 times higher in the dry season than in the wet season, and was greatly increased during a local fire event. Cytotoxicity and genotoxicity of PM1.0 organic extracts were assessed using in vitro tests with human liver HepG2 cells. For both types of tests, significant toxicity was only observed for samples collected during the dry season. Persistent DNA damage that may have impaired the DNA repair system was also observed. The results indicated that there was a health risk associated with the air particulate mixture, mainly related to biomass burning, demonstrating the urgent need for better remediation actions to prevent the occurrence of burning events.

Urinary Amino-PAHs in relation to diesel engine emissions and urinary mutagenicity.

Diesel exhaust has long been of health concern due to established toxicity including carcinogenicity in humans. However, the precise components of diesel engine emissions that drive carcinogenesis are still unclear. Limited work has suggested that nitrated polycyclic aromatic hydrocarbons (NPAHs) such as 1-nitropyrene and 2-nitrofluorene may be more abundant in diesel exhaust. The present study aimed to examine whether urinary amino metabolites of these NPAHs were associated with high levels of diesel engine emissions and urinary mutagenicity in a group of highly exposed workers including both smokers and nonsmokers. Spot urine samples were collected immediately following a standard work shift from each of the 54 diesel engine testers and 55 non-tester controls for the analysis of five amino metabolites of NPAHs, and cotinine (a biomarker of tobacco smoke exposure) using liquid chromatography-mass spectrometry. An overnight urine sample was collected in a subgroup of non-smoking participants for mutagenicity analysis using strain YG1041 in the Salmonella (Ames) mutagenicity assay. Personal exposure to fine particles (PM2.5) and more-diesel-specific constituents (elemental carbon and soot) was assessed for the engine testers by measuring breathing-zone concentrations repeatedly over several full work shifts. Results showed that it was 12.8 times more likely to detect 1-aminopyrene and 2.9 times more likely to detect 2-aminofluorene in the engine testers than in unexposed controls. Urinary concentrations of 1-aminopyrene were significantly higher in engine testers (p < 0.001), and strongly correlated with soot and elemental carbon exposure as well as mutagenicity tested in strain YG1041 with metabolic activation (p < 0.001). Smoking did not affect 1-aminopyrene concentrations and 1-aminopyrene relationships with diesel exposure. In contrast, both engine emissions and smoking affected 2-aminofluorene concentrations. The results confirm that urinary 1-aminopyrene may serve as an exposure biomarker for diesel engine emissions and associated mutagenicity.

Determination of policyclic aromatic compounds, (PAH, nitro-PAH and oxy-PAH) in soot collected from a diesel engine operating with different fuels.

A qualitative and quantitative analysis of polycyclic aromatic compounds (PACs; polycyclic aromatic hydrocarbons (PAHs), oxygenated and nitrated polycyclic aromatic hydrocarbons (OPAHs and NPAHs)) present in the soluble organic fraction (SOF) of different soot samples has been carried out to determine the effect of soot-generation conditions on their composition and health effects. The soot samples were generated using a diesel engine bench powered by diesel (DS) and biodiesel (BS) fuels under different combustion conditions. To optimize the procedure, a surrogate soot (Printex-U) and a certified reference material (SRM1650b) were also tested. Different extraction methods were used to extract the PAHs, OPAHs and NPAHs, and the Soxhlet technique using pyridine:acetic acid 1 % was found to be the most suitable procedure to extract the highest concentration (ng mg-1) and more types of PAHs and OPAHs from the soot. The results show that the PACs identified, and their concentrations, depend on the formation and collection conditions. The predominant compounds in all soot samples studied were fluorene (Flo), phenanthrene (Phe), fluoranthene (Fla), pyrene (Pyr), 9-fluorenone (9Flo) and 9,10-anthraquinone (9,10Anq). As such, the presence of these PACs in the atmosphere of urban and rural areas can mainly be attributed to the emissions from diesel vehicles. The percentage of OPAHs with respect to total PACs was highest in the soot generated from a biofuel. These oxidized compounds favor regeneration of the diesel particulate filter (DPF). The results also indicate that the carcinogenicity of the soot depends on the combustion conditions and type of fuel.

PM-bound polycyclic aromatic compounds (PACs) in two large-scale petrochemical bases in South China: Spatial variations, sources, and risk assessment.

Polycyclic aromatic compounds (PACs) are potential pollutants emitted from the petrochemical industry, whereas their occurrence and sources in petrochemical regions are still poorly known. The present study revealed the spatial variations, compositional profiles, sources and contributions, and health risks of PM-bound PACs in two large-scale petrochemical bases (GDPB and HNPB) in South China. The concentrations of parent polycyclic aromatic hydrocarbons (PAHs) were 7.14 ± 3.16 ng/m3 for ∑18PAHs and 0.608 ± 0.294 ng/m3 for the PAHs with molecular weight of 302 amu (MW302 PAHs) in the GDPB base and 2.55 ± 1.26 ng/m3 and 0.189 ± 0.088 ng/m3 in the HNPB base. Oxygenated PAHs (OPAHs) showed comparable concentrations to the parent PAHs in both the bases and nitrated PAHs (NPAHs) had the lowest mean levels (260 pg/m3 and 59.4 pg/m3 in the two regions). Coronene, 2,8-dinitrodibenzothiophene, and dibenzo[a,e]fluoranthene showed remarkably higher contributions to the PAC and can be PAC markers of the petrochemical industry source. Five sources of PACs were identified respectively in both petrochemical bases by the positive matrix factorization (PMF) model. The vehicle (and ship) traffic exhaust was the primary source of PACs (contributed 33% to the ∑PACs), and the sources related to the coking of coal and heavy petroleum and refinery exhaust were identified in both bases, with contributions of 10-20%. PACs in GDPB also contributed from secondary atmospheric reactions (17.3%) and the usage of sulfur-containing fuels (20.9%), while the aromatics industry made a significant contribution (20.1%) to the PACs in the HNPB region. The cumulative incremental lifetime cancer risks (ILCRs) induced by inhalation of PM-bound PACs in both petrochemical bases were low (10-8-10-6). For the sources related to the petrochemical industry, coking activities and the aromatic industry were the significant contributors to the ∑ILCRs in GDPB and HNPB, respectively. This research has implications for further source-targeted control and health risk reduction of PACs in petrochemical regions.

Development of Quantitative Chemical Ionization Using Gas Chromatography/Mass Spectrometry and Gas Chromatography/Tandem Mass Spectrometry for Ambient Nitro- and Oxy-PAHs and Its Applications.

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.

Molecular Basis and Evolutionary Origin of 1-Nitronaphthalene Catabolism in Sphingobium sp. Strain JS3065.

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) enter the environment from natural sources and anthropogenic activities. To date, microorganisms able to mineralize nitro-PAHs have not been reported. Here, Sphingobium sp. strain JS3065 was isolated by selective enrichment for its ability to grow on 1-nitronaphthalene as the sole carbon, nitrogen, and energy source. Analysis of the complete genome of strain JS3065 indicated that the gene cluster encoding 1-nitronaphthalene catabolism (nin) is located on a plasmid. Based on the genetic and biochemical evidence, the nin genes share an origin with the nag-like genes encoding naphthalene degradation in Ralstonia sp. strain U2. The initial step in degradation of 1-nitronaphthalene is catalyzed by a three-component dioxygenase, NinAaAbAcAd, resulting in formation of 1,2-dihydroxynaphthalene which is also an early intermediate in the naphthalene degradation pathway. Introduction of the ninAaAbAcAd genes into strain U2 enabled its growth on 1-nitronaphthalene. Phylogenic analysis of NinAc suggested that an ancestral 1-nitronaphthalene dioxygenase was an early step in the evolution of nitroarene dioxygenases. Based on bioinformatic analysis and enzyme assays, the subsequent assimilation of 1,2-dihydroxynaphthalene seems to follow the well-established pathway for naphthalene degradation by Ralstonia sp. strain U2. This is the first report of catabolic pathway for 1-nitronaphthalene and is another example of how expanding the substrate range of Rieske type dioxygenase enables bacteria to grow on recalcitrant nitroaromatic compounds. IMPORTANCE Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) have been widely detected in the environment and they are more toxic than their corresponding parent PAHs. Although biodegradation of many PAHs has been extensively described at genetic and biochemical levels, little is known about the microbial degradation of nitro-PAHs. This work reports the isolation of a Sphingobium strain growing on 1-nitronaphthalene and the genetic basis for the catabolic pathway. The pathway evolved from an ancestral naphthalene catabolic pathway by a remarkably small modification in the specificity of the initial dioxygenase. Data presented here not only shed light on the biochemical processes involved in the microbial degradation of globally important nitrated polycyclic aromatic hydrocarbons, but also provide an evolutionary paradigm for how bacteria evolve a novel catabolic pathway with minimal alteration of preexisting pathways for natural organic compounds.

Atmospheric chemistry and cancer risk assessment of Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs over a semi-arid site in the Indo-Gangetic plain.

Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs were collected over a year at a traffic dominated site in Agra, to determine the dominant partitioning mechanism. During the entire sampling period, total PAHs and Nitro-PAHs were 3465 ± 3802 and 26.1 ± 25.9 ng m-3 respectively. The gas-particle partitioning behavior of PAHs was studied by applying the Pankow model, Absorption model, and Dual model. Amongst all the partitioning models, the Dual model fits well and indicates that the partitioning of PAHs at the traffic site in Agra depends on both the physical adsorption of PAHs on the Total Suspended Particulate (TSP) surface and absorption of PAHs into the organic layer present on the TSP surface. Pankow model indicates that PAHs are emitted from the source close to the sampling point and due to this PAHs do not get enough time to get partitioned in between both the phases. Incremental lifetime Cancer Risk (ILCR) shows that adults and children are more prone to cancer risk in comparison to infants for both PAHs and Nitro-PAHs. Cancer risk by inhalation was minimum in comparison to both ingestion and dermal exposure. Nitro-PAHs in the particulate phase were high enough to exceed the minimum permissible limit (10-6) of causing cancer by ingestion and dermal exposure.

Evaluating the adsorption performance of Tenax TA® in different containers: An isolation tool to study the bioaccessibility of nitro-PAHs in spiked soil.

The improved in vitro gastrointestinal simulation methods, with the addition of the adsorption sink, are considered as a promising tool for predicting the bioaccessibility of contaminants. However, the problem associated with the recovery of the adsorption sink from the complex matrix needs more understand. Although previous studies tried to solve this shortcoming by using the containers (a vessel to hold the adsorption sink), there is no systematic comparison study on the impact of containers on bioaccessibility till now, especially for nitro-polycyclic aromatic hydrocarbons (nitro-PAHs). In order to understand the problem, commonly used containers in previous studies (dialysis bags and stainless-steel screen) were selected and deployed in the Fed Organic Estimation Human Simulation Test (FOREhST) method to compare the effects of these containers on the bioaccessibility of nitro-PAHs desorbed from the five different types of soils into the gastrointestinal fluid (GIF). Results showed that in order to maintain a constant sorptive gradient for the high molecular weight (MW) nitro-PAHs, 0.25 g of Tenax TA® were required in FOREhST. Compared with Tenax TA® encapsulated in dialysis bag (Tenax-EDBG), the use of Tenax TA® encapsulated in dissolution basket (Tenax-EDBT) significantly increased the bioaccessibility of nitro-PAHs in the soil from 5.6-31.4% to 17.2-70.6%, due to the better diffusion performance. The bioaccessibility of nitro-PAHs by FOREhST extraction with Tenax-EDBT showed a significant negative correlation with soil total organic carbon (TOC), whereas a weak correlation with pH. This study provides the researchers with a more standardized in vitro method to quantify the bioaccessibility of PAHs and their derivatives in soil.

Fine particle-bound PAHs derivatives at mountain background site (Mount Tai) of the North China: Concentration, source diagnosis and health risk assessment.

Ten nitrated polycyclic aromatic hydrocarbons (nPAHs) and 4 oxygenated polycyclic aromatic hydrocarbons (oPAHs) in fine particulate matter (PM2.5) samples from Mount Tai were analyzed during summer (June to August), 2015. During the observation campaign, the mean concentration of total nPAHs and oPAHs was 31.62 pg/m3 and 0.15 ng/m3, respectively. Two of the monitored compounds, namely 9-nitro-anthracene (9N-ANT) (6.86 pg/m3) and 9-fluorenone (9FO) (0.05 ng/m3) were the predominant compounds of nPAHs and oPAHs, respectively. The potential source and long-range transportation of nPAHs and oPAHs were investigated by the positive matrix factorization (PMF) method and the potential source contribution function (PSCF) methods. The results revealed that biomass/coal burning, gasoline vehicle emission, diesel vehicle emission and secondary formation were the dominant sources of nPAHs and oPAHs, which were mainly from Henan province and Beijing-Tianjin-Hebei region and Bohai sea. The incremental life cancer risk (ILCR) values were calculated to evaluate the exposure risk of nPAHs and oPAHs for three group people (infant, children and adult), and the values of ILCR were 7.02 × 10-10, 3.49 × 10-9 and 1.41 × 10-8 for infant, children and adults, respectively. All these values were lower than the standard of EPA (Environmental Protection Agency) (<10-6), indicating acceptable health risk of nPAHs and oPAHs.

Urinary Amino-Polycyclic Aromatic Hydrocarbons in Urban Residents: Finding a Biomarker for Residential Exposure to Diesel Traffic.

Despite substantial evidence of marked exposure to and ill-health effects from diesel exhaust (DE) emissions among occupational population (e.g., miners, truck drivers, and taxi drivers), it is less understood to what extent non-occupational population was exposed to DE among various combustion sources, largely due to the lack of biomarkers that would indicate specific exposure to DE. We evaluated whether urinary amino-polycyclic aromatic hydrocarbons (APAHs), such as major metabolites of DE-specific nitrated PAHs, can be used as DE exposure biomarkers in residential settings. We measured five urinary APAHs in 177 urine samples from 98 UK residents, 89 (91%) of them were London residents, and estimated their residential proximity to various traffic indicators (e.g., the road type, road length, traffic flow, and traffic volume). Participants living within 100 m of major roads exhibited increased levels of all five APAHs, among which 2-amino-fluorene (2-AFLU) reached statistical significance (p < 0.05). We estimated that a 10 m increase in the length of nearby major roads (<100 m) was associated with a 4.4% (95% CI of 1.1 to 7.6%) increase in 2-AFLU levels. Levels of 2-AFLU were significantly associated with the traffic flow of nearby buses and heavy-duty vehicles but not motorbikes, taxis, or coaches. We did not observe a significant association between distance to major roads or the sum of the major road length within 100 m with the other four biomarker concentrations. These results suggest the use of urinary 2-AFLU as a biomarker of DE exposure in urban residents.

Similar polycyclic aromatic hydrocarbon and genotoxicity profiles of atmospheric particulate matter from cities on three different continents.

The extractable organic material (EOM) from atmospheric total suspended particles (TSP) contains several organic compounds including non-substituted polycyclic aromatic hydrocarbons (PAHs), alkyl-PAHs, and nitro-PAHs. These chemicals seem to be among the key drivers of TSP genotoxicity. We have shown previously that the mutagenic potencies of the EOM from Limeira, Stockholm, and Kyoto, cities with markedly different meteorological conditions and pollution sources are similar. Here we compare the profiles of non-substituted PAHs (27 congeners), alkyl-PAHs (15 congeners), and nitro-PAHs (7 congeners) from the same EOM samples from these cities. We also compared the genotoxicity profiles using comet and micronucleus assays in human bronchial epithelial cells. The profiles of PAHs, as well as the cytotoxic and genotoxic potencies when expressed in EOM, were quite similar among the studied cities. It seems that despite the differences in meteorological conditions and pollution sources of the cities, removal, mixing, and different atmospheric transformation processes may be contributing to the similarity of the PAHs composition and genotoxicity profiles. More studies are required to verify if this would be a general rule applicable to other cities. Although these profiles were similar for all three cities, the EOM concentration in the atmospheres is markedly different. Thus, the population of Limeira (∼10-fold more EOM/m3 than Stockholm and ∼6-fold more than Kyoto) is exposed to higher concentrations of genotoxic pollutants, and Kyoto's population is 1.5-fold more exposed than Stockholm's. Therefore, to reduce the risk of human exposure to TSP genotoxins, the volume of emissions needs to be reduced.

Emission characteristics and temporal variation of PAHs and their derivatives from an ocean-going cargo vessel.

Polycyclic aromatic hydrocarbons (PAHs), nitro- (NPAHs) and oxy-derivatives (OPAHs) are of considerable concern due to their toxicity and carcinogenic hazards. Ships are recognized as an important emission source of these compounds. Marine diesel oil (MDO) and heavy fuel oil (HFO) are the two most commonly used fuels. The emission characteristics and toxicities of PM2.5-bound PAHs, NPAHs and OPAHs due to HFO and MDO combustion in atypical ocean-going vessel were investigated. The EF variability of polycyclic aromatic compounds (PACs) varied considerably with the fuel formulation (HFO and MDO) and engine loading (20%-100%). The concentration of ΣPACs was 0.63 mg/kWh for MDO and ranged from 2.14 to 9.80 mg/kWh for HFO. Compared to HFO-20%, the EFs of ΣPAHs, ΣNPAHs and ΣOPAHs from MDO-20% were reduced by 97%, 77% and 73%, respectively. As identified through the coefficient of divergence, the profile of HFO-20% was notably different from those under the other three engine loadings for HFO. In addition, the emissions of ΣPAHs and ΣOPAHs showed a significant correlation with PM2.5, while they were relatively weak for ΣNPAHs. However, the CO and PAC emissions were not highly correlated. Furthermore, the BaPeq-ΣPAHs values were 0.010 mg/g for MDO and ranged from 0.092 mg/g to 0.306 mg/g for HFO, and the reduction ranged from 89% to 97% by substituting MDO for HFO. These data highlight the importance of improving fuel quality in close proximity to port areas and are useful for enhancing relevant databases.

Mutagenic and genotoxic effects induced by PM0.5 of different Italian towns in human cells and bacteria: The MAPEC_LIFE study.

Particulate matter (PM) is considered an atmospheric pollutant that mostly affects human health. The finest fractions of PM (PM2.5 or less) play a major role in causing chronic diseases. The aim of this study was to investigate the genotoxic effects of PM0.5 collected in five Italian towns using different bioassays. The role of chemical composition on the genotoxicity induced was also evaluated. The present study was included in the multicentre MAPEC_LIFE project, which aimed to evaluate the associations between air pollution exposure and early biological effects in Italian children. PM10 samples were collected in 2 seasons (winter and spring) using a high-volume multistage cascade impactor. The results showed that PM0.5 represents a very high proportion of PM10 (range 10-63%). PM0.5 organic extracts were chemically analysed (PAHs, nitro-PAHs) and tested by the comet assay (A549 and BEAS-2B cells), MN test (A549 cells) and Ames test on Salmonella strains (TA100, TA98, TA98NR and YG1021). The highest concentrations of PAHs and nitro-PAHs in PM0.5 were observed in the Torino, Brescia and Pisa samples in winter. The Ames test showed low mutagenic activity. The highest net revertants/m3 were observed in the Torino and Brescia samples (winter), and the mutagenic effect was associated with PM0.5 (p < 0.01), PAH and nitro-PAH (p < 0.05) concentrations. The YG1021 strain showed the highest sensitivity to PM0.5 samples. No genotoxic effect of PM0.5 extracts was observed using A549 cells except for some samples in winter (comet assay), while BEAS-2B cells showed light DNA damage in the Torino, Brescia and Pisa samples in winter, highlighting the higher sensitivity of BEAS-2B cells, which was consistent with the Ames test (p < 0.01). The results obtained showed that it is important to further investigate the finest fractions of PM, which represent a relevant percentage of PM10, taking into account the chemical composition and the biological effects induced.

Methodology to examine polycyclic aromatic hydrocarbons (PAHs) nitrated PAHs and oxygenated PAHs in sediments of the Paraguaçu River (Bahia, Brazil).

Conventional methods for determination of polycyclic aromatic compounds (PACs) in sediments usually require large sample sizes (grams) and solvent volumes (at least 100 mL) through the employment of Soxhlet extraction, which is both time (hours) and energy consuming, among other disadvantages. We developed a new analytical protocol for the determination of PACs in sediments using microextraction, which requires small sample masses (25 mg), 500 µL of acetonitrile-dichloromethane mix and sonication for 23 min, followed by GC-MS analysis. The method was validated using the certified reference material SRM 1941b - NIST organic marine sediment, as well as internal deuterated standards. Seventeen PAHs, seven nitro-PAHs and one quinone were detected and quantified. The mean concentrations were 90.4 ng g-1 for PAHs, 179.2 ng g-1 for nitro-PAHs and 822.5 ng g-1 for quinones. The proposed method showed good sensitivity, linearity, precision and accuracy for the determination of PAC in sediments samples.

Polycyclic Aromatic Hydrocarbons (PAHs) and nitrated analogs associated to particulate matter emission from a Euro V-SCR engine fuelled with diesel/biodiesel blends.

Among the new technologies developed for the heavy-duty fleet, the use of Selective Catalytic Reduction (SCR) aftertreatment system in standard Diesel engines associated with biodiesel/diesel mixtures is an alternative in use to control the legislated pollutants emission. Nevertheless, there is an absence of knowledge about the synergic behaviour of these devices and biodiesel blends regarding the emissions of unregulated substances as the Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs, both recognized for their carcinogenic and mutagenic effects on humans. Therefore, the goal of this study is the quantification of PAHs and Nitro-PAHs present to total particulate matter (PM) emitted from the Euro V engine fuelled with ultra-low sulphur diesel and soybean biodiesel in different percentages, B5 and B20. PM sampling was performed using a Euro V - SCR engine operating in European Stationary Cycle (ESC). The PAHs and Nitro-PAHs were extracted from PM using an Accelerated Solvent Extractor and quantified by GC-MS. The results indicated that the use of SCR and the largest fraction of biodiesel studied may suppress the emission of total PAHs. The Toxic Equivalent (TEQ) was lower when using 20% biodiesel, in comparison with 5% biodiesel on the SCR system, reaffirming the low toxicity emission using higher percentage biodiesel. The data also reveal that use of SCR, on its own, suppress the Nitro-PAHs compounds. In general, the use of larger fractions of biodiesel (B20) coupled with the SCR aftertreatment showed the lowest PAHs and Nitro-PAHs emissions, meaning lower toxicity and, consequently, a potential lower risk to human health. From the emission point of view, the results of this work also demonstrated the viability of the Biodiesel programs, in combination with the SCR systems, which does not require any engine adaptation and is an economical alternative for the countries (Brazil, China, Russia, India) that have not adopted Euro VI emission standards.

Nitro and oxy-PAHs bounded in PM2.5 and PM1.0 under different weather conditions at Mount Tai in Eastern China: Sources, long-distance transport, and cancer risk assessment.

Fourteen nitro-PAHs and five oxy-PAHs associated with PM2.5 and PM1.0 were analyzed by GC-MS/MS at Mount Tai, China. 85% of the nitro-PAHs and 65% of oxy-PAHs were found in PM1.0. The combined concentration of nitro-PAHs in PM2.5 was highest in air masses associated with biomass burning (270.50pg/m3) compared with measurements from heavily polluted days (93.21pg/m3) and clean days (81.22pg/m3). A similar trend was also reflected in measurements of PM1.0. 9-FO, 9,10-ANQ, and 1-NALD were the most abundant oxy-PAHs in both PM2.5 and PM1.0 at Mount Tai. The concentration of 2+3N-FLA was markedly increased compared with other species on heavily polluted days and biomass burning days, and 9N-ANT was more concentrated in measurements from days with biomass burning emissions. Secondary generation of nitro-PAHs was also more active during periods with biomass burning. The main formation pathway of nitro-PAHs during the sampling campaign was through reactions with OH radicals, but NO3 radicals also played a significant role at night. The incremental lifetime cancer risk (ILCR) was highest during periods with biomass burning, indicating that biomass burning has a significant impact on human health. By analyzing the results of back trajectory clustering under different meteorological conditions, we determined that a large area of straw burning in the North China Plain (NCP) was the dominant source of nitro and oxy-PAHs at Mount Tai during the measurement campaign.

Residue characteristics of sludge from a chemical industrial plant by microwave heating pyrolysis.

Sludge from biological wastewater treatment procedures was treated using microwave heating pyrolysis to reduce the environmental impact of a chemical plant. In this study, major elements, trace elements, PAHs and nitro-PAHs in raw sludge, and pyrolysis residues were investigated. The contents of major element from raw sludge were carbon 46.7 ± 5.9%, hydrogen 5.80 ± 0.58%, nitrogen 6.81 ± 0.59%, and sulfur 1.34 ± 0.27%. Trace elemental concentrations including Zn, Mn, Cr, Cd, As, and Sn were 0.410 ± 0.050, 0.338 ± 0.008, 0.063 ± 0.006, 0.019 ± 0.001, 0.004 ± 0.001, and 0.003 ± 0.002 mg/g, respectively. For various pyrolysis temperatures, Ca, Fe, Sr, Cr, and Sn contents remained at almost the same level as those in raw sludge. Results indicated that these elements did not easily volatilize. The content of 16 PAH species was about 4.78 µg/g in the raw sludge and 23-65 µg/g for pyrolysis residues associated with various temperatures. The content of ten nitro-PAHs was about 58 ng/g for the raw sludge and 141-744 ng/g for pyrolysis residues. The total nitro-PAH content was highest at 600 °C and then decreased when the temperature was over 600 °C. Total nitro-PAH content was about 247 ng/g at 800 °C.

Biomass burning particles in the Brazilian Amazon region: Mutagenic effects of nitro and oxy-PAHs and assessment of health risks.

Emissions from burning of biomass in the Amazon region have adverse effects on the environment and human health. Herein, particulate matter (PM) emitted from biomass burning in the Amazon region during two different periods, namely intense and moderate, was investigated. This study focused on: i) organic characterization of nitro- and oxy-polycyclic aromatic hydrocarbons (PAHs); ii) assessment of the excess lifetime cancer risk (LCR); and iii) assessment of the in vitro mutagenic effects of extractable organic matter (EOM). Further, we compared the sensitivity of two mutagenicity tests: Salmonella/microsome test and cytokinesis-block micronucleus (CBMN) with human lung cells. Among the nitro-PAHs, 2-nitrofluoranthene, 7-nitrobenz[a]anthracene, 1-nitropyrene, and 3-nitrofluoranthene showed the highest concentrations, while among oxy-PAHs, 2-metylanthraquinone, benz[a]anthracene-7,12-dione, and 9,10-anthraquinone were the most abundant. The LCR calculated for nitro-PAH exposure during intense biomass burning period showed a major contribution of 6-nitrochrysene to human carcinogenic risk. The EOM from intense period was more mutagenic than that from moderate period for both TA98 and YG1041 Salmonella strains. The number of revertants for YG1041 was 5-50% higher than that for TA98, and the most intense responses were obtained in the absence of metabolic activation, suggesting that nitroaromatic compounds with direct-acting frameshift mutagenic activity are contributing to the DNA damage. Treatment of cells with non-cytotoxic doses of EOM resulted in an increase in micronuclei frequencies. The minimal effective dose showed that Salmonella/microsome test was considerably more sensitive in comparison with CBMN mainly for the intense burning period samples. This was the first study to assess the mutagenicity of EOM associated with PM collected in the Amazon region using Salmonella/microsome test. The presence of compounds with mutagenic effects, particularly nitro- and oxy-PAHs, and LCR values in the range of 10-5 indicate that the population is potentially exposed to an increased risk of DNA damage, mutation, and cancer.

Genotoxicity of airborne PM2.5 assessed by salmonella and comet assays in five cities of the Emilia-Romagna (Italy) mutagenicity monitoring network.

Airborne particulate matter (PM) has long been recognized as a potential health hazard and in 2013 was classified as carcinogenic to humans by the International Agency for Research on Cancer. In this study we evaluate and compare mutagenic and genotoxic potencies of PM2.5 collected in three seasons, from 2012 to 2015, in five Italian cities. Mutagenicity was evaluated through the Ames test on TA98 and TA100 strains and, for the measurement of PM clastogenicity, Comet assay was carried out on cultured human lung cells (A549). Organic matter, extracted from urban particulate matter, was also characterized for polycyclic aromatic hydrocarbons (PAHs) and their derivatives content. Samples collected in the colder seasons show the presence of both base pair substitution and frameshift mutagens, with enhanced mutagenic response in the absence of enzyme activation. The highest DNA damage detected with the Comet assay was induced by winter extracts, but different from Salmonella, the relative increase per cubic meter in comet tail for November samples was comparable to July ones. Comparing mutagenicity and genotoxicity with chemical concentrations we found that data from the Salmonella assay correlate with mass concentration and, to a lesser extent, with PAHs, but no association was found with their derivatives, whereas DNA damage correlate only with PAHs measured at one site. These findings demonstrate that to assess the mutagenicity and genotoxicity of complex mixtures it's necessary to use bioassays and that the chemical analysis of pollutants does not take into account the possible inhibitory or synergic effects of exposure. Environ. Mol. Mutagen. 58:719-729, 2017. © 2017 Wiley Periodicals, Inc.