Determination of n-alkanes, PAHs and nitro-PAHs in PM2.5 and PM1 sampled in the surroundings of a municipal waste incinerator

doi:10.1016/j.atmosenv.2016.11.016

Atmospheric Environment

Volume 149, January 2017, Pages 12-23

https://doi.org/10.1016/j.atmosenv.2016.11.016 Get rights and content

Highlights

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PM_2.5 and PM₁ were sampled in different sites close to a municipal waste incinerator.
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n-alkanes, PAHs and nitro-PAHs were determined in both PM collected fractions.
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Higher concentrations of PAHs and n-alkanes were measured in winter than in summer.

Abstract

This work investigates n-alkanes in the range C14-C32, polycyclic aromatic hydrocarbons (PAHs) and nitrated PAHs (nitro-PAHs) composition of PM_2.5 and PM₁ collected in the surroundings of a municipal waste incinerator close to Bologna (Northern Italy). The particulate matter was sampled in eight stations: one of these was located inside the urban area of Bologna, while the others were placed in a domain of 8 × 9 km² around the incinerator plant. Two monitoring campaigns were carried out, in summer 2008 and in winter 2009. In each campaign, two stations were placed in zones of maximum impact of plant emissions and other two ones as their controls. The study of n-alkanes in atmospheric particulate was performed to understand the contribution of anthropogenic and biogenic sources, PAHs and nitro-PAHs were selected to investigate PM composition near an incinerator plant. Higher concentrations of PAHs and, to a less extent, of n-alkanes were measured in the cold season. This can be due to several reasons, namely, an increased combustion of fossil fuel during wintertime, stagnant atmospheric conditions and lower temperatures that not only favour gas-to-particles partitioning but also reduce atmospheric reactivity. The impact of combustion in the cold season was also confirmed by the higher percentage content of PAHs in PM₁ than in PM_2.5. On the contrary, higher amount of nitro-derivatives were measured in summer than in winter, suggesting that the contribution of secondary aerosol is not negligible in the hot season. The most abundant n-alkanes were the long-chain homologues (>C27) deriving from anthropogenic sources as indicated by the Carbon Preference Indexes. In both seasons, the sites chosen as controls were characterized by higher concentrations of PAHs than the respective maxima suggesting that extra-incinerator sources, especially vehicles emissions, are the main responsible for PAHs in PM_2.5. On the contrary, in winter, PM₁ was enriched in PAHs in the site close to the incinerator with respect to its control.

Introduction

The incineration process can result in three potential sources of exposure: emissions to the atmosphere, solid ash residues and cooling water. Provided that solid ash residues and cooling water are appropriately handled and disposed of, atmospheric emissions remain the only significant route of exposure to people. The combustion gives rise to fine particles that can have negative effect on human health due to their size and composition (Laden et al., 2000, Morawska and Zhang, 2002). In particular, during incomplete combustion of fossil fuels and biomass, polycyclic aromatic hydrocarbons (PAHs) can be released into the atmosphere (Jedynska et al., 2014), partitioned between the vapour phase and the particle matter (the partition coefficient strongly depends on the PAH molecular weight) (Masiol et al., 2012, Cvetković et al., 2015). These compounds are of great concerns: the United States-Environmental Protection Agency (US-EPA) classified 16 PAHs as priority pollutants based on toxicity, potential for human exposure, frequency of occurrence at hazardous waste sites and the extent of available information (EPA, 2014). Among these 16 PAHs, US-EPA considers 7 (i.e. benzo[a]anthracene, chrysene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, dibenz[a,h]anthracene, and indeno[1,2,3-cd]pyrene) as probable human carcinogens (EPA, 2014).

Analogously, nitro-PAHs originate primarily as direct or indirect products of incomplete combustion, through nitration during combustion processes (e.g. in vehicle exhaust, aircraft emissions, industrial emissions, domestic residential heating/cooking, wood burning) (WHO, 2003). Nitro-PAHs can also originate through atmospheric formation either by gas-phase reactions or by heterogeneous gas-particle interaction of parent PAHs with nitrating agents (WHO (World Health Organization), 2003, Reisen and Arey, 2005).

Nitro-PAHs as well as their corresponding parent-PAHs are known to have toxic, carcinogenic and estrogenic properties (Bandowe et al., 2014). Furthermore, nitro-PAHs are direct acting mutagens and also produce reactive oxygen species which in turn are also toxic (WHO, 2003).

Because of the possible presence of these contaminants in the incinerator emissions and of their toxicity, there is a high perception of health risk, especially for people living nearby these plants. Although this is a very felt issue, many studies state that “modern, well managed incinerators make only a small contribution to local concentrations of air pollutants. It is possible that such small additions could have an impact on health but such effects, if they exist, are likely to be very small and not detectable” (HPA, 2009). However, it should also be considered that location, meteorological conditions and plant characteristics can play an important role on the emissions characteristics. Moreover, in the literature the works concerning the PAHs and nitro-PAHs composition of PM collected in area close to an incinerator are relatively scarce, especially in Italy, and only few of them deal with PM₁, which is generally known as harmful for human health (Chen et al., 2016). In order to acquire new knowledge about the air quality in the proximity of incinerators, the local Emilia Romagna (ER) Administration promoted a wide research project called MONITER (http://www.arpae.it/moniter/). In particular this work, which is a part of the MONITER project, reports the content of PAHs and nitro-PAHs in PM₁ and PM_2.5 collected in the neighbourhood of a Municipal Waste to Energy Incinerator (WTE) located in the ER region. Additionally, to differentiate the potential sources of these contaminants, the composition in n-alkanes of the particulate was also evaluated. It is well known that n-alkanes can be emitted from anthropic or natural (mostly vegetal) sources and, for this reason, they are considered useful in tracking the origin of atmospheric aerosol (Simoneit, 1989, Duan et al., 2010). In particular, the abundance distribution of the odd/even terms is a key diagnostic parameter in discriminating between the biogenic and anthropogenic nature of n-alkanes sources (Pietrogrande et al., 2010).

The aim of this work is to evaluate the effect of a WTE on PM composition by comparing the concentrations of organic compounds (i.e. n-alkanes, PAHs and nitro-PAHs) in the aerosol collected at different sites in a domain of about 10 km² around WTE location, in two different seasons.

Section snippets

Sampling of particulate matter

The incineration plant under study is located in a suburban–farming area, less than 10 km away from northeast of Bologna (Italy), in the Po Valley, which is a well–known polluted critical area. The plant has the following main features: 600 tons day⁻¹ of incinerating capacity, two 80 m–high stacks and BAT (Best Available Technique) purification devices. In particular, the gas treatment system consists of a bag filter dedusting and an oxygen content controlled post-combustion chamber

Results

In previous works (Rossi et al., 2012, Sarti et al., 2015), the concentrations of particulate matter (PM₁ and PM_2.5) and their seasonal and spatial variations in the sampling sites of the domain have been reported. Some relevant results are herein briefly recalled: the PM_2.5 amount is higher in winter than in summer (averaged values of 33.7 ± 1.9 μg m⁻³ and 19.68 ± 0.78 μg m⁻³ respectively) and the PM₁ fraction accounts for the 79% in summer and for the 66% in winter of PM_2.5. In the following

Conclusions

In this study the concentrations of n-alkanes in the range C14-C32, PAHs and nitro-PAHs were measured in PM_2.5 and PM₁ collected at 8 sampling sites around a municipal waste incinerator located near Bologna, in Emilia Romagna region (Northern Italy). The analysis of PM composition over the studied domain has been accomplished to investigate the similarities and differences between the various monitoring stations. This is the first step to bring out any evidence of impact of the different and

Acknowledgements

This work was conducted as part of the “MONITER” project, which was supported and financed by Emilia Romagna Region and Emilia Romagna - Regional Agency for Prevention, Environment and Energy. The authors wish to thank all the members of the MONITER project and in particular Vanes Poluzzi, Fabiana Scotto, Dimitri Bacco, Arianna Trentini and Giovanni Bonafè.

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Determination of n-alkanes, PAHs and nitro-PAHs in PM2.5 and PM1 sampled in the surroundings of a municipal waste incinerator

Highlights

Abstract

Introduction

Section snippets

Sampling of particulate matter

Results

Conclusions

Acknowledgements

Atmos. Environ.

Atmos. Environ.

Chemosphere

Sci. Total Environ.

Atmos. Environ.

J. Chromatogr. A

Atmos. Environ.

Chemosphere

Atmos. Environ.

J. Environ. Sci.

Atmos. Environ.

Atmos. Environ.

Atmos. Environ.

J. Hazard. Mater.

Atmos. Environ.

Chemosphere

Atmos. Environ.

Sci. Total Environ.

Atmos. Environ.

Atmos. Environ.

Atmos. Environ.

Atmos. Environ.

Atmos. Pollut. Res.

Atmos. Environ.

Atmos. Environ.

Atmos. Environ.

Atmos. Environ.

Determination of n-alkanes, PAHs and nitro-PAHs in PM_2.5 and PM₁ sampled in the surroundings of a municipal waste incinerator