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Article Distributions of Polychlorinated Naphthalenes in Sediments of the Yangtze River, China

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Article Distributions of Polychlorinated Naphthalenes in Sediments of the Yangtze River, China molecules Article Distributions of Polychlorinated Naphthalenes in Sediments of the Yangtze River, China Zhitong Liu 1, Ke Xiao 1,*, Jingjing Wu 1, Tianqi Jia 1,2, Rongrong Lei 1,2 and Wenbin Liu 1,2,3 1 State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; [email protected] (Z.L.); [email protected] (J.W.); [email protected] (T.J.); [email protected] (R.L.); [email protected] (W.L.) 2 College of Resources and Environment, University of Chinese Academy of Sciences, Beijing 100049, China 3 Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China * Correspondence: [email protected]; Tel.: +86-10-6284-9870; Fax: +86-10-62849339 Abstract: The pollution status of polychlorinated naphthalenes (PCNs) in the sediment of the Yangtze River Basin, Asia’s largest river basin, was estimated. The total concentrations of PCNs (mono- to octa-CNs) ranged from 0.103 to 1.631 ng/g. Mono-, di-, and tri-PCNs—consisting of CN-1, CN-5/7, and CN-24/14, respectively, as the main congeners—were the dominant homolog groups. Combustion indicators and principal component analysis showed that the emissions from halowax mixtures were the main contributor to PCNs in sediment, among most of the sampling sites. The mean total toxic equivalent (TEQ) was calculated to be 0.045 ± 0.077 pg TEQ/g, which indicates that the PCNs in sediments were of low toxicity to aquatic organisms. This work will expand the database on the distribution and characteristics of PCNs in the river sediment of China. Keywords: PCNs; spatial distribution; congener; environmental risk; sediment Citation: Liu, Z.; Xiao, K.; Wu, J.; Jia, T.; Lei, R.; Liu, W. Distributions of Polychlorinated Naphthalenes in Sediments of the Yangtze River, 1. Introduction China. Molecules 2021, 26, 5298. Polychlorinated naphthalenes (PCNs) have been synthesized since the 1930s, with 75 con- https://doi.org/10.3390/ geners based on the number and position of the chlorine(s) in the naphthalene ring system, in- molecules26175298 cluding 2 mono-chlorinated (CN-1–CN-2), 10 di-chlorinated (CN-3–CN-12), 14 tri-chlorinated (CN-13–CN-26), 22 tetra-chlorinated (CN-27–CN-48), 14 penta-chlorinated (CN-49–CN- Academic Editor: James Barker 62), 10 hexa-chlorinated (CN-64–CN-72), 2 hepta-chlorinated (CN-73–CN-74), and 1 octa- chlorinated (CN-75) [1]. Because of the properties of low water solubility, low vapor pressure, Received: 12 August 2021 and resistance to degradation, PCNs were widely used in various industries including cable Accepted: 27 August 2021 Published: 31 August 2021 insulation, wood preservation, graphite electrode lubrication, masking compounds for elec- troplating, dye manufacturing, capacitors, and refracting index testing oils [1,2]. In parallel, Publisher’s Note: MDPI stays neutral an increasing number of toxicological studies have demonstrated that PCNs exhibited the with regard to jurisdictional claims in potential risk to a variety of organisms, including dioxin-like toxic effects on mammals [3–5]. published maps and institutional affil- PCNs have been listed in Annexes A and C of the Stockholm Convention on Persistent iations. Organic Pollutants since May 2015, owing to their potential toxicity, persistence, bioaccu- mulation, and long-range transport [6,7]. Although, the production of PCNs was banned in the 1980s [2], unfortunately, products containing PCNs have been unlawfully used so far [8]. There are mainly four pathways of PCNs discharging into the environment, including his- torical use, historical and present use of polychlorinated biphenyl (PCBs), thermal and other Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. processes, and landfills [9]. Moreover, PCNs may also be formed unintentionally and emitted This article is an open access article into the environment via thermal processes involved in nonferrous metallurgical facilities, distributed under the terms and metal refineries, waste incineration, and cooking industries [9–11]. The possible sources of conditions of the Creative Commons PCNs released into the environment could be identified by analyzing homolog profiles and Attribution (CC BY) license (https:// ratios of several PCN congeners used as indicators of particular emission activities [11]. creativecommons.org/licenses/by/ PCNs have been found in various media such as soil, sediment, water, air, and biota, 4.0/). even in human breastmilk [12,13]. Sediment, as one of the most important pollutant sinks Molecules 2021, 26, 5298. https://doi.org/10.3390/molecules26175298 https://www.mdpi.com/journal/molecules Molecules 2021, 26, 5298 2 of 10 into the environment could be identified by analyzing homolog profiles and ratios of sev- eral PCN congeners used as indicators of particular emission activities [11]. Molecules 2021, 26, 5298 PCNs have been found in various media such as soil, sediment, water, air, and biota,2 of 9 even in human breastmilk [12,13]. Sediment, as one of the most important pollutant sinks among the environmental media, can hold the contemporary PCNs from aquatic and ter- among the environmental media, can hold the contemporary PCNs from aquatic and restrial sources and release them to environment again. Thus, it is essential to monitor terrestrial sources and release them to environment again. Thus, it is essential to monitor PCNs in sediment as secondary pollution sources in order to examine their ecological risk. PCNs in sediment as secondary pollution sources in order to examine their ecological In fact, detectable PCNs have been reported in numerous sediment samples collected in risk. In fact, detectable PCNs have been reported in numerous sediment samples collected rivers, lakes, and coastal waters of China [7,14–18], even though PCNs have not been in- in rivers, lakes, and coastal waters of China [7,14–18], even though PCNs have not been tentionally produced in China. For example, in Zhang’s study, the PCN concentration was intentionally produced in China. For example, in Zhang’s study, the PCN concentration wasup to up 4610 to 4610ng/g, ng/g, highest highest among among all the allsediment the sediment samples samples of China of reported China reported [16]. Moreo- [16]. Moreover,ver, these pollutants these pollutants tend to tendlong- torange long-range transport transport in the atmosphere in the atmosphere and finally and deposit finally to depositsediments. to sediments. Therefore, Therefore, it is necessary it is necessaryto conduct to comprehensive conduct comprehensive research on research the whole on theval- wholeley for valley accurate for assessment accurate assessment of the extent of the of extentpollute. of pollute. TheThe YangtzeYangtze River, River, Asia’s Asia’s longest longest river river and and the the third third longest longest river river in in the the world, world, serves serves asas anan importantimportant resourceresource forfor drinkingdrinking water,water, aquaculture aquaculture and and industrial industrial use. use.With With a a rapid rapid increaseincrease inin populationpopulation andand economiceconomic developmentdevelopment aroundaround thethe river,river, therethere are are numerous numerous inputsinputs fromfrom industrialindustrial wastewater, municipal municipal sewage, sewage, atmospheric atmospheric deposition, deposition, as as well well as asagricultural agricultural soils soils containing containing fertilizers, fertilizers, pest pesticides,icides, herbicides, herbicides, andand heavy heavy metals metals [19]. [Pre-19]. Preservingserving the the river’s river’s water water quality quality is iscritical critical for for sustainable sustainable development development as well asas thethe healthhealth and and survival survival of of residents. residents. In thisIn this study, study, sediment sediment samples samples of the of Yangtze the Yangtze River BasinRiver wereBasin collected were collected from the from cradle the tocrad thele estuary,to the estuary, including including the reservoirs, the reservoirs, industrial industrial zones andzones residential and residential areas. areas. The samples The samples spanned spanned more more than than 6000 6000 km acrosskm across six provincessix provinces at differentat different levels levels of economicof economic development. development. Our Our aims aims were were to to provide provide fundamental fundamental data data forfor quantifyingquantifying PCNPCN concentrationsconcentrations inin thethe sediments,sediments, establishingestablishing theirtheir distributionsdistributions and and characteristics,characteristics, andand evaluatingevaluating theirtheir potentialpotential ecological ecological risks. risks. 2.2. ResultsResults andand DiscussionDiscussion 2.1.2.1. SpatialSpatial DistributionsDistributions ofof PCNsPCNs inin SedimentsSediments TheThe PCNPCN concentrations concentrations of of the the sampling sampling sites sites from from the Yangtze the Yangtze River basinRiver are basin shown are inshown Figure in1 .Figure 1. FigureFigure 1.1.The The PCNPCN concentrationsconcentrations ofof thethe samplingsamplingsites sitesfrom from the the Yangtze Yangtze River River Basin. Basin. TheThe PCNPCN concentrationsconcentrations inin thethe sedimentsediment samples samples ranged ranged from from 0.103 0.103 to to1.631 1.631 ng ng g −g1−1.. TheThe lowestlowest concentration of of PCNs PCNs was was found found at atS7 S7 located located in Minjiang in Minjiang River River which which
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