Particle size distributions and health risks of polychlorinated dibenzo-p-dioxin/furans, polychlorinated biphenyls, and polychlorinated naphthalenes in atmospheric particles around two secondary copper smelters in Shandong Province, China
Graphical abstract
Introduction
Polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) are listed in the Stockholm Convention as persistent organic pollutants (POPs) that show environmental persistence, bioaccumulation, and long-range transport, and have high toxicities (WHO, 1997; UNEP, 2009; Gioia et al., 2011; Zhang et al., 2014). PCDD/Fs are only intentionally produced when they are used for scientific research (Meng et al., 2016). Industrial production of PCBs and PCNs has been banned worldwide since the 1970s (Noma et al., 2006). However, many industrial processes and human activities, such as waste incineration, iron ore sintering, secondary nonferrous metal smelting, and power generation, emit these POPs into the surrounding environment unintentionally (Xu et al., 2009; Du et al., 2010; Nie et al., 2012; Liu and Zheng, 2013; UNEP, 2013; Nguyen et al., 2017). Secondary nonferrous metal smelting, which includes secondary copper smelting, zinc smelting, aluminum smelting, and lead smelting, is considered one of the main source of PCDD/Fs and PCNs in China (Ba et al., 2009, 2010; Liu et al., 2015; Jiang et al., 2019).
The secondary copper smelting industry has developed rapidly in China since the 1970s (Jiang et al., 2019). In China, Ba et al. (2009) found that the levels of PCDD/Fs discharged from a secondary copper smelter (14.8 μg toxic equivalent quantity (TEQ) per ton) were five times those discharged from a secondary aluminum smelter (2.7 μg TEQ per ton). Yang et al. (2020) collected 25 stack gas samples from three secondary copper smelters, two secondary zinc smelters, and two secondary lead smelters, and found that the PCDD/F levels emitted from the secondary copper smelters were up to 2.7 ng I-TEQ Nm−3, and were much higher than those from the other secondary metal smelters. As one of the largest emission sources of PCDD/Fs in China (Li et al., 2019), secondary copper smelters have attracted increasing attention. Most previous studies have focused on the concentrations and homolog profiles of PCDD/Fs, PCBs, and PCNs in stack gases from secondary copper smelters and the formation processes of these POPs from different raw materials during the various smelting stages (Ba et al., 2009; Nie et al., 2012; Hu et al., 2014; Jiang et al., 2019). When these pollutants are discharged from secondary copper smelters, they may cause environmental pollution because of their persistence (Nie et al., 2012) and pose a threat to the health of exposed populations through maternal transmission, biomagnification, and bioconcentration (Batter et al., 2009; Li et al., 2014). Research by Yang et al. (2017) showed that workers and residents downwind of a secondary copper smelter had twice the respiratory exposure to PCDD/Fs, PCBs, and PCNs of those upwind of the smelter, and their carcinogenic risk reached 2.4 × 10−4, exceeding the threshold (10−4) which may cause high carcinogenic risk. Therefore, PCDD/F, PCB, and PCN pollution around secondary copper smelters deserves our attention.
As an important medium in the atmosphere, particulate matter is closely related to environmental and human health (Englert, 2004; Walgraeve et al., 2009). Particles with diameters of less than 2.5 μm are major contributors to poor environmental quality (Xu et al., 2018), and 90% of these particles can penetrate deep into the alveoli, causing heart disease, lung disease, and even death (Englert, 2004). Moreover, because of the large specific surface areas and strong adsorption capacities of these particles, POPs such as PCDD/Fs and PCNs can accumulate in them (Barbas et al., 2018; Zhu et al., 2017; Wang et al., 2010). Passive intake of POPs by inhalation of atmospheric particles has been recognized as one of the main sources of POPs in the human body (Paatero et al., 1994). However, few investigations have been conducted on the particle size distributions of PCDD/Fs, PCBs, and PCNs in atmospheric particles near secondary copper smelters. Further research on atmospheric particles and associated pollutants is necessary to improve our knowledge of pollution and the potential health risks around secondary copper smelters.
In this study, we collected samples of atmospheric particles in four particle size fractions around two secondary copper smelters in Shandong Province, China, and determined the concentrations of 17 PCDD/Fs, 12 dioxin-like PCBs (dl-PCBs), and 75 PCNs in the samples. The homolog profiles and particle size distribution of the three categories of POPs were characterized, and their potential carcinogenic risks were evaluated. The results improve our understanding of particle-bound PCDD/Fs, dl-PCBs, and PCNs around secondary copper smelters, and provide useful information for developing effective measures to reduce potential health risks.
Section snippets
Sample collection
Two typical secondary copper smelters (A and B) located in a coastal city (YT) and an inland city (LY) in Shandong Province, China, were selected for this study (Fig. 1). Both smelters are bordered by railways and several highways. Smelter A uses reverberator furnaces, which are widely used in China for secondary copper smelting, and smelter B uses NGL (Nanchang Gutiyelian Lu) furnaces, which combine a titling furnace and a rotary furnace. Smelter B is equipped with bag filters, but smelter A
Particle concentrations
The total mass concentrations of all particles were 215.5, 244.2, 183.9 and 164.5 μg m−3 at the sampling point A1, A2, B1 and B2, respectively. (Fig. 2). Most (37%–54% of the mass concentration) of the particles had diameters of <2.5 μm. The concentration range for these particles was 79.1–99.4 μg m−3 and the average concentration was 89.8 μg m−3, which exceeded the national ambient air quality standard (75 μg m−3) (CNS, 2012). According to current technical regulations on the ambient air
Conclusions
This study explored the concentrations and size distributions of PCDD/Fs, dl-PCBs, and PCNs in the atmospheric particles around two secondary copper smelters in Shandong Province, China. All three types of POPs, and especially the PCDD/Fs, mainly accumulated in the particles with diameters of <2.5 μm. The distribution characteristics of PCDD/Fs congener in four particle size fractions were similar to each other and were consistent with their congener profiles in stack gas samples from the two
Credit author statement
Xinrui Yang: Conceptualization, Formal analysis, Validation, Writing-Original Draft, Writing-Review & Editing, Investigation, Visualization, Data Curation. Jing Wu: Validation, Formal analysis, Data Curation, Resources, Investigation, Software. Meihong Li: Investigation. Min Qi: Investigation. Ran Wang: Investigation. Jicheng Hu: Conceptualization, Validation, Writing-Review & Editing, Visualization, Supervision, Project administration. Jun Jin: Resources.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This study was supported by the National Natural Science Foundation of China [grant number 21407185]. We thank Gabrielle David, PhD, from Liwen Bianji, Edanz Editing China (www.liwenbianji.cn/ac), for editing the English text of a draft of this manuscript.
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