J. Cent. South Univ. (2019) 26: 3252-3260

DOI: https://doi.org/10.1007/s11771-019-4250-0

Surface water quality and potential health risk assessments in Changsha-Zhuzhou-Xiangtan section of Xiangjiang River, China

JIANG Dong-yi(蒋东益)¹, YANG Jin-qin(杨锦琴)², WANG Yun-yan(王云燕)^{1, 3},LIAO Qi(廖琪)^{1, 3}, LONG Zhe(龙哲)⁴, ZHOU San-yang(周三羊)⁵

1. School of Metallurgy and Environment, Central South University, Changsha 410083, China;

2. Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden;

3. Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, Changsha 410083, China;

4. School of Information Science and Engineering, Central South University, Changsha 410083, China;

5. Hunan Province Environmental Monitoring Centre, Changsha 410014, China

Central South University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract: The Changsha-Xiangtan-Zhuzhou City Group is a heavy industrial district and accepted as the serious pollution area in the Xiangjiang River basin. In this study, 7 metals (Pb, Hg, Cd, As, Zn, Cu and Se) and the river water quality parameters including pH, dissolved oxygen (DO), Escherichia coli (E. coli), potassium permanganate index (COD_Mn), dichromate oxidizability (COD_Cr), five-day biochemical oxygen demand (BOD₅), ammonia nitrogen (NH₄⁺-N), total nitrogen (TN), total phosphorus (TP) and fluoride (F^-) in 18 sampling sites of the Changsha-Xiangtan-Zhuzhou section are monthly monitored in 2016, which is the year to step into the second stage of the “Xiangjiang River Heavy Metal Pollution Control Implementation Plan”. It is found that E. coli, TN and TP are the main pollutants in the Changsha-Zhuzhou-Xiangtan section, and the pollution of heavy metal is not serious but As with potential risk to local people especially children should be concerned. In addition, Xiangtan city is mainly featured with heavy metal pollution, while Zhuzhou and Changsha city are both featured with other pollutants from municipal domestic sewage.

Key words: Xiangjiang River; surface water; heavy metal; water quality assessment; human health risk assessment

Cite this article as: JIANG Dong-yi, YANG Jin-qin, WANG Yun-yan, LIAO Qi, LONG Zhe, ZHOU San-yang. Surface water quality and potential health risk assessments in Changsha-Zhuzhou-Xiangtan section of Xiangjiang River, China [J]. Journal of Central South University, 2019, 26(12): 3252-3260. DOI: https://doi.org/10.1007/s11771-019-4250-0.

1 Introduction

The Xiangjiang River is a tributary of the middle Yangtze River in China and the biggest river in Hunan Province flowing through Hengyang, Zhuzhou, Xiangtan, Changsha, etc. The Xiangjiang River is commonly regarded as the Mother River by people living in Hunan Province due to its vital role in the process of economic developments [1]. With the promotion of industrialization and urbanization, the Xiangjiang River is bearing the dramatically increased population and much more serious pollution [2]. As one of the most important economic belts in Hunan Province, the Xiangjiang River basin has great influences on Dongting Lake’s flood storage capacity [3].

According to the monitoring data of water quality of the Xiangjiang River from 1981 to 2000 [4], the overall water quality has been deteriorating since 1990s, and more serious pollution occurs in the middle and lower reaches, flowing through the region of the Changsha-Xiangtan-Zhuzhou City Group, a heavy industrial district [5, 6]. Serving as an intermediate region in the Beijing-Guangzhou economic zone and between the Pearl River Delta economic zone and the Yangtze River Delta economic zone, the Changsha-Zhuzhou-Xiangtan region needs to move forward on sustainable development [7]. However, plenty of heavy metal pollutants are historically discharged into the Xiangjiang River from steel, nonferrous, chemical and other industrial plants gathering in the important industrial areas, such as the Qibaoshan (Changsha city), the Qingshuitang (Zhuzhou city) and the Zhubugang (Xiangtan city) [8, 9]. The river water quality deterioration and ecological environment depravation have received considerable attentions, and the State Council approved the Xiangjiang River Heavy Metal Pollution Control Implementation Plan in 2011 [10, 11]. The Hunan Provincial Government takes the protection and management of the Xiangjiang River as No. 1 Key Project and decides to implement three consecutive Three-Year Action Plan from 2013 to 2021 [12]. By the end of 2015, the first Three-Year Action Plan was successfully completed, and more than 1100 heavy metal-related pollution enterprises were shut down and withdrawn, basically blocking the source of pollution in the main stream of the Xiangjiang River [13].

Besides industrial pollution, domestic sewages are also the main pollution sources of the Xiangjiang River. During the first Three-Year Action Plan (2013-2015), 64 sewage treatment plants were built, and the capacity of domestic sewage treatment increased by 2.55 million t/d. The second Three-Year Action Plan starts from 2016 targeting at improving water quality of mainstream and main tributaries to Grade III or above and increasing monitoring sections of water quality above Grade II by 30%. In the Changsha- Zhuzhou-Xiangtan region, the dense population and developed economy lead to large demand for water resources. Therefore, more attention should be paid to the Changsha-Zhuzhou-Xiangtan section of the Xiangjiang River, and the river water quality needs to be assessed by comprehensively considering heavy metals and other pollutants. In this study, water samples are monthly collected in the Changsha-Zhuzhou-Xiangtan section of the Xiangjiang River in 2016, and multiple assessment methods are conducted to analyze the water quality and heavy metals human health risk, which would have a major guiding significance on the rational arrangement of water quality monitoring points and the formulation of environmental protection rules and regulations.

2 Materials and methods

2.1 Study areas and samples collection

The Changsha-Zhuzhou-Xiangtan urban agglomeration is the core of the economic development pole of Hunan Province, China, and its economical sustainable development is closely interrelated with the current conditions of ecological environments. The water quality and ecological risk of the Xiangjiang River should be paid more attention, especially in the Changsha- Zhuzhou-Xiangtan section of middle and lower reaches. The river water quality is monthly monitored at total 18 sites in the Changsha- Zhuzhou-Xiangtan section, i.e., 8 sites (S11-S18) in Changsha, 5 sites (S1-S5) in Zhuzhou and 5 sites (S6-S10) in Xiangtan (Figure 1). Quality assurance and control are enabled in the process from sample collection to sample analysis. National standard (GB/T 5750.2-20), issued by the National Health Commission of the People’s Republic of China and the Standardization Administration of the People’s Republic of China are implanted during the sample collecting and preserving process. Different published national standards (see Table 1) ensures the standardization and exactness for the determination of each element. Besides, triplicate samples are collected, as their standard deviations are within 5%.

2.2 Statistical analysis method

2.2.1 Principal component analysis (PCA)

Principal component analysis (PCA) has been widely applied in water quality data analysis [14], which is a powerful pattern recognition tool to identify the underlying factors or variables from a large dataset [15]. PCA extracted a smaller number of factors that attempt to explain the original dataset by data reduction techniques [16, 17]. In this study, PCs with eigenvalue over 1 are retained, and the Kaiser-Meyer-Olkin values are more than 0.5 and Bartlett’s test are significant (results below 0.001) [18]. Loadings values over 0.75, and values between 0.75 and 0.50 are corresponding to strong and moderate factor loading, therefore, loading values greater than 0.50 are retained [19].

Figure 1 Study area of sampling sites in Changsha-Zhuzhou-Xiangtan section of Xiangjiang River (The map was generated by ArcGIS 10.2)

Table 1 Variables used and method of determination

2.2.2 Dual hierarchical cluster analysis (DHCA)

DHCA is an integration of a combined two hierarchical cluster analysis about metals and sites, and a thermodynamic analysis diagram. Hierarchical cluster analysis in DHCA is performed on the normalized dataset (Z-scores) by Euclidean and Ward method to reveal the cluster relationship between metals and between sites, and a cut-off line was determined to define the cluster [20-22]. The Pearson’s correlation matrix is also implemented to demonstrate the correlations of each metal. IBM SPSS Statistics 22.0 and Microsoft Excel 2016 are applied in the processing of the above analysis.

2.2.3 Human health risk assessment

The heavy metals human health risks assessment has been proved to be an effective tool to demonstrate the ecosystem health by USEPA [23]. Exposure of human being to metals in river water could occur through pathways including direct ingestion and dermal absorption through exposure skin [24]. The doses received are determined using equations from Table 3, adapted from USEPA and other references [25, 26]. Risk characterization is quantified by carcinogenic risk and non-carcinogenic risk [18]. The involved parameters and its values are presented in Table 2, and the involved equations are depicted in Table 3.

Table 2 Specific values of parameters in risk assessment and references

where W_b is the body weight; D_e is the exposure duration; T_a is the average time; R_i is the ingestion rate; A_s is the exposed skin surface area; F_e is the exposure frequency; T_e is the exposure time; ABS_GI is the gastrointestinal absorption factor; F_cs is cancer slope factor; C_w is the average concentration of the heavy metals in water, units in μg/L; K_p is the dermal permeability coefficient in water, cm/h and the chemical-specific value are presented in Table 2; ABS_GI is gastrointestinal absorption factor, unitless.

Table 3 Summarized equations of human health risk assessment recommended by USEPA

R_c is the carcinogenic risk, unitless; F_cs represents cancer slope factor of a carcinogen, (μg·kg·d^-1). The hazard quotient values greater than 1 imply that there are potential side effects on human health, and the acceptable range of carcinogenic risks recommended by the USEPA is 10^-6 to 10^-4 [26].

3 Results and discussion

3.1 Study area and samples collection

The water quality in the Changsha- Zhuzhou-Xiangtan section of the Xiangjiang River is monthly monitored for parameters including heavy metals, nutrients, and biochemical indexes. The floating range and the annual average of each item are presented in Table 4. The annual average values show that only E. coli, TN and TP exceed the China limit for surface water. Additionally, Pb is much lower than the China limit, and other heavy metal contents are all under the national limit. This reveals that the notorious heavy metal pollution is not serious in the Changsha-Zhuzhou-Xiangtan section. In addition, COD, BOD and NH4⁺-N items are all under the national limit for surface water. Therefore, pollutants in the Changsha- Zhuzhou-Xiangtan section are mainly E. coli, TN and TP, which are probably from municipal domestic sewage.

Table 4 Water quality variables in Changsha-Zhuzhou-Xiangtan section of Xiangjiang River

3.2 PCA and DHCA

PCA analysis are conducted based on the annual average value of the 17 water quality parameters. The results in Table 5 reveal that there are five principal components (PCs) with the explanation of 90.46% of the total variance. In particular, PC1 represents 28.17% to the total variance with a high loading on Cd (0.96), Se (0.79), Cu (0.65), Pb (0.97), Hg (0.51), COD_Mn (0.70) and BOD₅ (0.67), which may attribute to a mixed factor of anthropogenic activities containing metal, chemical and organic effects. PC2 represents 20.89% to the total variance with a high loading on F^- (0.53) and TN (0.78). PC3 represents 16.04% to the total variance with a high loading on TP (0.82) and NH₄⁺-N (0.96). PC2 together with PC3 seems to be attributed to nutrient input. PC4 represents 14.05% to the total variance with a high loading on Zn (0.77) and PC5 represents 11.31% to the total variance with a high loading on DO (0.95) which might originate from the mixed sources of the natural erosions. Three main factors are ultimately identified as anthropogenic activities, nutrient input, and natural erosions in PCA analysis. PCA roughly explains the possible causes of each PC, so further exploration is needed to reveal the internal connection of parameters.

Table 5 Principal components analysis (PCA) for physical–chemicals of Xiangjiang River in Changsha- Zhuzhou-Xiangtan section

In order to further figure out the relationship of water quality parameters, DHCA are subsequently followed. As shown in Figure 2, both water parameters and sampling sites are divided into 3 categories. For water parameters, Cluster 1 contains Cd, Pb, Se, Cu, COD_Mn and BOD₅, Cluster 2 contains COD_Cr, DO, F^-, TN and As, and Cluster 3 contains E. coli, pH, Hg, TP, NH₄⁺-N and Zn. It is found that Cluster 1 mainly represents heavy metal pollutants of Cd, Pb, Se and Cu, which possibly originates from industrial wastewaters. Clusters 2 and 3 probably come from municipal domestic sewage accompanied by As, Hg and Zn. It seems like that the pollution source of Cd, Pb, Se and Cu is different from that of As, Hg and Zn. For sampling sites, Cluster 1 covers S6, S7, S8, S9, S11 and S16, Cluster 2 covers S1-S5 and S17, and Cluster 3 covers S10, S12-S15 and S18. It is obvious that sampling sites of Cluster 1 are mainly located in Xiangtan city; sampling sites of Cluster 2 are mainly located in Zhuzhou city; and sampling sites of Cluster 3 are mainly in Changsha city. It is believable that different cities have distinct water quality features. Subsequently, the water quality is respectively evaluated in Changsha, Zhuzhou and Xiangtan city.

Figure 2 Dual hierarchical cluster analysis results of water parameters and sampling sites

Comparing the annual average value of water parameters (Table 6) in Changsha, Zhuzhou and Xiangtan city, it is found that Changsha is featured with highest pH, DO, E. coli, NH₄⁺-N and TP, Zhuzhou city is featured with the highest COD_Cr, TN, As and Se and Xiangtan city is featured with the highest COD_Mn, BOD₅, Pb, Hg, Cd, Zn and Cu. Therefore, the main pollutants in Xiangtan city are probably heavy metals, and the pollution in Changsha and Zhuzhou city mainly comes from municipal domestic sewage. It is well known that metallurgy, electromechanical and chemical textiles are the pillar industry in Xiangtan city and thus the heavy metal pollution is relatively serious. Zhuzhou city is dominated by nonferrous metallurgy and traffic machinery industries and is populated due to its unique advantage of the transportation hub in southern transport network of China. Similarly, as provincial capital, Changsha city is densely populated and the pollution from municipal domestic sewage should be concerned.

Nutrient elements such as NH₄⁺-N and TP as well as biochemical parameters like E. coli and BOD₅ can be degraded under the action of sunlight,air and microorganisms, thus the capacity of domestic sewage treatment should be further increased in the second Three-Year Action Plan to improve water quality of the Xiangjiang River. Different from nutrient elements, heavy metals cannot be eliminated but accumulated in sediments and food chain threatening ecological safety and human health. It is very essential to focus on the potential human health risk caused by Pb, Hg, Cd, As, Zn, Cu and Se. Here, different scenarios are discussed for adults and children in rainy and dry season, and Q_h, I_h and R_c values in Table 7 present the hazard quotient, hazard index and the carcinogenic risk, respectively.

Table 6 Annual average value of water parameters in Changsha, Zhuzhou and Xiangtan city

3.3 Human health risk assessment of heavy metals

The hazard quotient is specifically evaluated for the oral ingestion and dermal absorption pathways, corresponding to Q_h,ingestion and Q_h,dermal. As listed in Table 7, Q_h,ingestion of As is close to 1 for adult and higher than 1 for children. Followed by Cd, its Q_h,ingestion reaches 10^-2 order of magnitude for children and 10^-3 order of magnitude for adults. Q_h,ingestion of other metals all reaches 10^-3 order of magnitude for both children and adults. These indicate that As and Cd may cause adverse health effects and potential non-carcinogenic concern. In addition, Q_h,dermal values of all metals including Pb, Hg, Cd, As, Zn, Cu and Se are far below 1, indicating little hazards for both adults and children via dermal absorption. It is noticed that for both adults and children, Q_h,dermal of As is of 10^-3 order of magnitude, Hg and Cd are of 10^-4, Cu and Se are of 10^-5, Pb and Zn are of 10^-6 order of magnitude. This shows the hazards via dermal absorption follow the order of As>Hg, Cd>Cu, Se>Pb, Zn. It can be concluded that As poses serious health concerns to the local residents via oral intake, while other metals via oral intake and all metals via dermal absorption have little or no health threat.

I_h results suggest that only As gives a value higher than 1 for children. Besides, I_h of As for adult reaches 10^-1 order of magnitude, I_h of Cd for child reaches 10^-2 order of magnitude, and I_h of other metals for both adults and children are of 10^-3 order of magnitude. Therefore, As is the most important hazard in the Changsha-Zhuzhou- Xiangtan section of the Xiangjiang River. Additionally, R_c of As for children is higher than that for adult, but is in the acceptable range (10^-6-10^-4) of carcinogenic risks regulated by the USEPA (USEPA, 2004). Leave aside carcinogenic risks, the adverse health effects of As include hypertension, neuropathy, diabetes, skin lesions, and cardiovascular and cerebrovascular diseases through high arsenic intake. Therefore, concerns should be raised to local people especially children to alleviate As content in the Xiangjiang River. As found above, comparing with Changsha and Xiangtan city, Zhuzhou city shows a little higher As content in 2016, and thus much more attention should be paid in Zhuzhou area.

4 Conclusions

In the present study, water quality of the Xiangjiang River is monthly monitored in 2016 based on a total 17 parameters in the Changsha- Zhuzhou-Xiangtan section. Except E. coli, TN, TP and Pb, all other parameters meet the China standard for surface water and the WHO standard. PCA analysis reveals five principal components (PCs) with the explanation of 90.46% of the total variance. DHCA results show that the water parameters are divided into heavy metal cluster and two clusters of other parameters. Besides, the sampling sites are divided into 3 clusters, i.e., Changsha, Zhuzhou and Xiangtan. Comparing these three cities, Xiangtan is mainly featured with heavy metal pollution, while Changsha and Zhuzhou are both featured with other pollutants from municipal domestic sewage. Human health risk assessment indicates that As poses serious health concerns to the local residents via oral intake and As is the most important hazard in the Changsha-Zhuzhou- Xiangtan section of the Xiangjiang River, although its carcinogenic risk is in the acceptable range (10^-6-10^-4) regulated by USEPA.

Table 7 Human health risk assessment results

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(Edited by FANG Jing-hua)

中文导读

中国湘江流域长株潭段表层水质分析与潜在健康风险测评

摘要：长株潭城市群是重金属工业区，并且在湘江流域中属于严重受污染区域。本研究中的水质数据按月采自于2016年湘江流域长株潭段的18个采样点，其中包括7个主要金属元素 (Pb, Hg, Cd, As, Zn, Cu, Se)以及相关水质参数(pH, DO, E. coli, COD_Mn, COD_Cr, BOD₅, NH₄⁺-N, TN, TP, F^-)。2016年也正是《湘江流域水污染综合整治实施方案》进行的第二个重要阶段。经数据调研发现，长株潭流域的主要污染物是大肠杆菌、总氮和总磷，该流域受重金属污染较轻微，而流域中的砷含量对当地居民尤其是儿童，存在一定的健康风险。同时，在污染源上，湘潭地区水质污染主要来自重金属污染，而株洲和长沙的水质污染主要来自于城市生活污染水中的其他污染物。

关键词：湘江；表层水；重金属；水质测评；人类健康风险

Foundation item: Projects(2018YFC1903301, 2018YFC1801805) supported by the National Key R&D Program of China

Received date: 2019-03-26; Accepted date: 2019-08-03

Corresponding author: WANG Yun-yan, PhD, Professor; Tel: +86-13975808192; E-mail: wang.yunyan@outlook.com; ORCID: 0000- 0001-5842-2781