Spatial Distributions, Source Apportionment and Ecological Risk of Svocs in Water and Sediment from Xijiang River, Pearl River Delta
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Environ Geochem Health DOI 10.1007/s10653-017-9929-2 ORIGINAL PAPER Spatial distributions, source apportionment and ecological risk of SVOCs in water and sediment from Xijiang River, Pearl River Delta Jiao Tang . Taicheng An . Guiying Li . Chaohai Wei Received: 10 January 2017 / Accepted: 27 February 2017 Ó Springer Science+Business Media Dordrecht 2017 Abstract Xijiang River is an important drinking the main sources for PAHs. The OCPs sources of each water source in Guangxi Province, China. Along the category were almost independent, whereas the new Xijiang River and surrounding tributary, the pollution input of HCHs and p,p0-DDTs probably existed in profile of three important groups of semi-volatile some areas. PAEs were mainly originated from organic compounds, including polycyclic aromatic personal care products of urban sewage, plastic and hydrocarbons (PAHs), organochlorine pesticides other industrial sources. Ecological risk through the (OCPs) and phthalate esters (PAEs), was analyzed. risk quotient analysis indicated a small or significant Relatively low levels of PAHs (64–3.7 9 102 ng L-1) potential adverse effect on fish, daphnia and green and OCPs (16–70 ng L-1), but high levels of PAEs algae. Nevertheless, the integrated risk of all pollu- (7.9 9 102–6.8 9 103 ng L-1) occurred in the water. tants should be taken into account in future study. Comparatively, low levels of OCPs (39–1.8 9 102 ng g-1) and PAEs (21–81 ng g-1), but high levels Keywords Xijiang River Á PAHs Á OCPs Á PAEs Á of PAHs (41–1.1 9 103 ng g-1) were found in sedi- Ecological risks ment. Principal component analyses for source iden- tification indicated petroleum-derived residues or coal and biomass combustion, and vehicular emission was Introduction Electronic supplementary material The online version of Polycyclic aromatic hydrocarbons (PAHs), composed this article (doi:10.1007/s10653-017-9929-2) contains supple- mentary material, which is available to authorized users. of two or more fused rings, are an important group of J. Tang J. Tang Á T. An University of Chinese Academy of Sciences, State Key Laboratory of Organic Geochemistry, Beijing 100049, China Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China C. Wei School of Environment and Energy, South China T. An Á G. Li (&) University of Technology, Guangzhou 510006, China Guangzhou Key Laboratory of Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou 510006, China e-mail: [email protected] 123 Environ Geochem Health environmental semi-volatile organic compounds improve their softness and flexibility in polyvinylchlo- (SVOCs) (Goswami et al. 2016). PAHs in environ- ride resins (Stales et al. 1997; Santhi and Mustafa ment were mainly originated from nature and anthro- 2013). Short-side-chain PAEs are mainly used in pogenic combustion process. Volcanic eruptions, cosmetics and personal care products, including forest as well as prairie fire are the main sources from perfumes and nail polishes, while most of the long- nature (Zhang et al. 2004). Anthropogenic sources or middle-side-chain PAEs are widely applied to principally included fossil fuel combustion, waste plasticizers (Zheng et al. 2014). Furthermore, several incineration, petroleum refining, coke and biomass PAEs have been reported with environmental hor- combustion, as well as other industrial activities (Yun mones, which can lead to the instability of internal et al. 2016). Owning to their mutagenicity and secretions and procreation ability (Fan et al. 2008). carcinogenicity, 16 unsubstituted PAHs were listed Besides, release of PAEs into the environment during as priority pollutants by the United States Environ- manufacture, use and disposal has caused increasing mental Protection Agency (USEPA) (Manoli et al. concerns, owning to be suspected as mutagens, 2000). What’s more, seven PAHs including hepatotoxic agents, carcinogens, especially endocrine benzo[a]anthracene (BaA), chrysene (Chry), disruptor chemicals (Yuan et al. 2010). benzo[b]fluoranthene (BbF), benzo[k]fluoranthene Currently, high levels of PAHs, OCPs and PAEs in (BkF), benzo[a]pyrene (BaP), dibenz[a,h]anthracene the surface water and sediment of Jialing River (Cai (DiB) and indeno[1,2,3-cd]pyrene (IncdP) were et al. 2012), East Lake (Yun et al. 2016), Tiber River regarded as carcinogens (Wang et al. 2010). Mean- (Montuori et al. 2016) had been driven much attention. while, they have bioaccumulation property because of Nevertheless, relative studies are relatively very rare their high lipophilicity. As a result, they might lead to for Xijiang River, the main tributary of Pearl River in both acute and chronic risks in aquatic plants, fish, China. During the past several decades, with the rapid waterfowls and other mammals that feed on aquatic increase of population, economic, urbanization and organisms (Yun et al. 2016). Therefore, their extensive industrialization, city sewages and industrial wastew- distribution, potential risks to the health of human and ater are always dumped into the rivers. Furthermore, ecosystem have been the focus of much attention constructions of factories and cities along the river are (Manoli and Samara 1999). very common in China, which were further aggravated Organochlorine pesticides (OCPs), another impor- pollution of rivers. Thus, this work aims to investigate tant group of SVOCs, had been banned for decades, the pollution profile of PAHs, OCPs and PAEs caused but they still frequently occurred in various matrix, by different anthropogenic activities. Furthermore, such as sediment (Lin et al. 2016), lake (Hu et al. their spatial distributions, source apportionment and 2010), river (Zhang et al. 2012), air (Zheng et al. ecological risks were also investigated in this area. 2010). As known, OCPs can effectively control the pests and diseases in the agriculture plantations. For instance, dieldrin, heptachlor and lindane were used Materials and methods for controlling termites of wood, while dichlorodiphenyltrichloroethane (p,p0-DDT) and hep- Materials tachlor were used for malaria fumigation (Santhi and Mustafa 2013). Meanwhile, as important persistent Standard solutions for the quantification analysis and organic pollutants (POPs), OCPs had been paid a quality control experiments were achieved as men- serious attention due to their toxicity, persistence and tioned in our previous studies (Li et al. 2013; Sun et al. bioaccumulation (Kata et al. 2015). Furthermore, the 2014). The detailed information is provided in chemical properties of OCPs such a slow polarity and supporting information. high lipophilicity have the potential to accumulate in the food chain, posing a considerable harm to humans Study area and sampling sites and ecosystem (Kamel et al. 2015). Phthalate esters (PAEs) are another class of Total of 12 pairs of water and sediment were collected important SVOCs, which are widely used as industrial from Xijiang River using amber glass bottles and chemicals served as important additives aiming to stainless steel boxes, respectively (Fig. S1). 123 Environ Geochem Health Approximately 10 L water and 500 g surface sediment DCM for 72 h. Before extraction, activated cooper (depth 0–5 cm) were sampled at each site. Meanwhile, was added for the removal of element sulfur during 0.5 g sodium azide was spiked in the water and sediment pretreatment. The subsequent steps were sediment to prevent microbial degradation. During the identical as water sample pretreatment, except the last sampling, the pH value, temperature, conductivity and fractions were concentrated to 500 lL. Finally, known dissolved oxygen (DO) were measured in situ to amount of internal standard were spiked for instru- reflect the status of water (Table S1). The water and mental analysis. sediment were carried back to laboratory as soon as possible and stored at 4 and -20 °C, respectively, Instrument analysis until pretreatment. A 7890A gas chromatograph (GC) coupled with a Sample pretreatment 5975C mass spectrometer (MS) detector (Agilent Technologies, USA) and equipped with HP-5MS Sample pretreatment was performed as our previous silica-fused capillary column (30 m 9 250 lm 9 studies (Sun et al. 2014). The water samples were 0.25 lm) was used for quantifying analysis. The filtered through prebaked glass microfiber filters (GF/ column temperature for PAHs was executed from Fs, 142 mm in diameter, Whatman, England) to initial 80 to 280 °C at a rate of 3 °C min-1, then remove suspend particulate. Three categories surro- reached 300 °Cat10°C min-1 and held there for gate standards including five deuterated PAHs, 10 min. For OCPs, the temperature was held at 80 °C 2,4,5,6-tetrachloro-m-xylene (TMX) and 2,20,3,30,4, for 1 min and programmed to 140 °C at a rate of 15 °C 40,5,50,6,60-decachlorobiphenyl (PCB209), as well as min-1 and further to 280 °Cat4°Cmin-1, finally at diphenylphthalate (DphP), were added and then 10 °C min-1 to 300 °C for 10 min. For PAEs, the passed through the pretreated XAD-2 columns (Su- oven temperature program was as follows: initial pelco, Bellefonte, USA) to enrich the target com- 80 °C held for 1 min, increased to 180 °Cat10°C pounds. The enrichment of target compounds was min-1 and held there for 1 min, and then reached gradually eluted by using 50 mL menthol, 40 mL 260 °Cat2°C min-1, finally to 300 °Cat methanol/dichloromethane (DCM) = 4:1 (twice) and 10 °C min-1 and held there for 10 min. The injector 50 mL methanol/DCM = 1:1 (twice) and the remain- temperature for PAHs, OCPs and PAEs was 290, 250, ing XAD-2 resins using 90 and 50 mL 9 2 methanol/ 300 °C, respectively. The mass spectrometer was DCM = 1:1 with ultrasonication for 15 min, respec- performed in selective ion monitoring (SIM) mode by tively. The mixed solutions were further refined using using positive ion electron impact ionization (EI).