Open Access Article
Pan Qin
ab,
Fengmei Cao
b,
Shaoyong Lu*ab,
Linlin Liab,
Xiaochun Guob,
Bin Zhaoc,
Zhengfen Wanb and
Bin Bib
aCollege of Water Sciences, Beijing Normal University, Beijing 100875, China. E-mail: lushy2000@163.com; Tel: +86-10-84935064
bState Environmental Protection Scientific Observation and Research Station for Lake Dongtinghu (SEPSORSLD), National Engineering Laboratory for Lake Pollution Control and Ecological Restoration, State Key Laboratory of Environmental Criteria and Risk Assessment, Research Centre of Lake Environment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
cYuxi Normal University, Yuxi, Yunan 653100, China
First published on 22nd July 2019
An investigation into the occurrence of volatile organic compounds (VOCs) in the surface water of Poyang Lake was conducted. The determination of 54 different kinds of VOCs was performed with a purge and trap-gas chromatography-mass spectrometry method at 28 sampling points. Twenty-two types of VOCs were detected; methylene chloride had the highest mean concentration of 708.19 ng L−1, followed by 1,2-dichloroethane and chloroform, with mean concentrations of 376.78 and 187.26 ng L−1, respectively. The distribution of VOCs in the areas of Poyang Lake from low to high was as follows: west and south < east and central; the highest ∑VOC concentration occurred at the sample site of Zhangsihe. The health risks of VOCs in Poyang Lake were also determined by calculating the cancer and non-cancer risk from the two exposure routes of ingestion and dermal adsorption. The results showed that VOCs have no carcinogenicity risk, while only methylene chloride has a certain carcinogenic risk to the human body.
Poyang Lake, the largest freshwater lake in China, is located in the northern part of Jiangxi Province and plays an important role in regulating the Yangtze River water level, conserving water sources, improving the local climate and maintaining the ecological balance of the surrounding areas.16 VOC pollution in Poyang Lake probably poses a substantial threat to the health of humans and ecosystems.17,18 Additionally, there has been no research reported on the occurrence and risk assessment of VOCs in Poyang Lake. In this paper, to provide a basis and suggestions for the treatment and management of VOCs in Poyang Lake, the occurrence and distribution characteristics of VOCs were analysed, and a health risk assessment was carried out at the same time. The results will contribute to the knowledge on potential hazards from various VOCs in Poyang Lake in China, and these results will lead to developments in the urgently needed management of contaminant loading and corresponding policies.
The samples were collected using 40 mL glass bottles that had screw caps with rubber-polytetrafluoroethylene gaskets, ensuring that there was no gap between the sample and the cap. Samples were returned to the laboratory using an insulated box and stored in a refrigerator free of organic reagents. Then, the samples were fixed using hydrochloric acid and analysed within 24 hours.
:
1); inlet temperature: 220 °C; carrier gas: high-purity helium (purity > 99.99%), flow rate: 1.0 mL min−1, constant current mode; temperature program: starting temperature of 35 °C (hold 2 min), ramp at 5 °C min−1 to 120 °C, then ramp at 10 °C min−1 to 220 °C (hold 2 min).An Agilent MS5975 mass spectrometer was used, and the conditions were set as follows: ion source temperature: 230 °C; ion source: EI source; scanning method: selective ion scanning; ionization energy: 70 eV; scanning range: m/z 35–270 amu.
Risk (cancer risk value) represents the incidence of cancer beyond the normal level of exposure to carcinogenic contaminants and is divided into low-dose exposure risk and high-dose exposure risk. The corresponding formula is as follows:
| Risk = CDI × SF, Risk < 0.01 |
| Risk = 1 − exp(−CDI × SF), Risk ≥ 0.01 |
Non-carcinogenic risk is generally measured as a reference dose; i.e., an exposure level higher than the reference dose value may be risky, whereas an exposure level equal to or lower than the reference dose value is within the acceptable risk range. The hazard value (HI) is usually used to represent the reference dose value and is calculated as follows:
The main routes of contaminant exposure to the human body are ingestion and skin contact.
When daily exposure to the human body is through ingestion, CDI is calculated as follows:
When daily exposure to the human body is through the skin, CDI is calculated as follows:
| CDI = I × Asd × EF × FE × ED/(BW × AT × f) |
According to the literature,23 the values of the above formula parameters are as follows: human exposure frequency (EF): 365 d a−1; exposure event frequency (FE): 0.3 times per d; carcinogenic and non-carcinogenic exposure delay (ED): 70 a and 30 a, respectively; mean body weight (BW): 60 kg; average exposure time to carcinogens and non-carcinogens: 25
550 d and 10
950 d, respectively; intestinal adsorption ratio (f): 1; skin adsorption parameter (k): 0.001 cm h−1; daily ingestion (U): 2 L d−1; and exposure event time (TE) and delay time: 0.4 h and 1 h, respectively.
The carcinogenic slope factor (SF) and the reference dose (RfD) of the contaminants used in the calculation were obtained from the USEPA database (https://www.epa.gov/sites/production/files/201603/documents/summary_of_inputs_final_revised_3.24.16.pdf) and the literature;24 the specific values are listed in Table S2 (in the ESI†).
| Contaminants | FOD, % | Minimum (ng L−1) | Maximum (ng L−1) | Mean (ng L−1) |
|---|---|---|---|---|
| a ND: not detected. | ||||
| 1,1-Dichloroethylene | 78.6 | ND | 23.81 | 9.13 |
| Methylene chloride | 100.0 | 78.75 | 2809.94 | 708.19 |
| trans-1,2-Dichloroethylene | 82.1 | ND | 23.78 | 10.27 |
| cis-1,2-Dichloroethylene | 53.6 | ND | 11.28 | 3.33 |
| Chloroform | 100.0 | 11.84 | 1379.83 | 187.26 |
| Benzene | 100.0 | 7.11 | 96.44 | 27.13 |
| 1,2-Dichloroethane | 100.0 | 51.5 | 807.39 | 376.78 |
| Trichloroethylene | 17.9 | ND | 7.91 | 6.49 |
| 1,2-Dichloropropane | 82.1 | ND | 111.54 | 30.14 |
| Bromodichloromethane | 57.1 | 11.58 | 91.31 | 31.79 |
| Toluene | 100.0 | 37.51 | 590.23 | 131.99 |
| Tetrachloroethene | 3.6 | 5.98 | 5.98 | 5.98 |
| Dibromochloromethane | 39.3 | ND | 10.71 | 5.62 |
| Chlorobenzene | 21.4 | ND | 15.51 | 6.26 |
| Ethylbenzene | 89.3 | 7.17 | 203.37 | 28.02 |
| m-Xylene | 46.4 | ND | 191.67 | 59.27 |
| p-Xylene | 10.7 | 64.62 | 108.98 | 82.45 |
| o-Xylene | 53.6 | ND | 129.02 | 31.06 |
| 1,3,5-Trimethylbenzene | 10.7 | ND | 44.11 | 15.80 |
| 1,3-Dichlorobenzene | 7.1 | ND | 3.60 | 2.53 |
| 1,2-Dichlorobenzene | 3.6 | 1.53 | 1.53 | 1.53 |
| Naphthalene | 21.4 | 38.87 | 67.02 | 54.30 |
Methylene chloride had the highest mean concentration among the 22 kinds of VOCs, which was 708.19 ng L−1, followed by 1,2-dichloroethane and chloroform, with mean concentrations of 376.78 and 187.26 ng L−1, respectively. In addition, the highest concentration of methylene chloride was 2809.94 ng L−1, which was the largest among all VOCs. Methylene chloride is mainly used in film production and medicine in China.25 1,2-Dichloroethane is mainly used in the production of tetrachloroethylene and vinyl chloride and is also used as a solvent for lipids, rubber and paint; this compound is one of the 58 priority control pollutants in the water environment in China.26 Chloroform may also be derived from chlorine disinfection by-products from drinking water treatment processes.27 According to the literature,28 the industrial development plan around Poyang Lake includes the construction of petrochemical and pharmaceutical industries, which may increase the emissions of VOCs in Poyang Lake. Poyang Lake is the most important water transportation hub in Jiangxi Province. It is very likely that accidents such as leakage will occur during the transportation of chemical products, causing VOCs to enter Poyang Lake. Furthermore, according to the literature,29 toluene might be the most ubiquitous common VOC pollutant in Chinese water bodies. This is consistent with the 100% FOD of toluene in Poyang Lake. It is worth noting that although the mean concentration of benzene was only 27.13 ng L−1, which is well below its LC50,30 its FOD was 100%. Therefore, due to the wide distribution of benzene, it is still necessary to consider the health risks caused by long-term exposure.
The VOC composition in Poyang Lake is shown in Fig. 3b. The substances with the highest percentages among the 22 VOCs were methylene chloride, accounting for up to 44.60%, nearly half; followed by 1,2-dichloroethane and chloroform, accounting for 23.73% and 11.79%, respectively. A comparison of the FODs of the VOCs shows that contaminants accounting for a large percentage were detected at each point, demonstrating that VOCs are widely distributed in Poyang Lake. Methylene chloride, chloroform, benzene, 1,2-dichloroethane and toluene are the main VOC contaminants in Poyang Lake. Consequently, because methylene chloride has the highest concentration and the highest content in Poyang Lake, the Chinese government should focus on the production of pollution from the film industry in the Poyang Lake basin.31,32 Based on this, we mainly focused on the distribution of methylene chloride in Poyang Lake. Fig. 2 clearly shows that methylene chloride was mainly found in Zhangsihe (2809.94 ng L−1); this value was higher than that (108.86 ng L−1) in Raohe, that (115.27 ng L−1) in Kangshanhe, that (78.75 ng L−1) in Junshanhu, and those (97.81, 88.01, and 871.07 ng L−1) in Gangjiang. Methylene chloride originating from Zhangsihe was reduced in Dajishan (293.47 ng L−1) after passing through Baishazhou (2785.29 ng L−1) and Hehexiang (2190.25 ng L−1). This may be because Dajishan is located at the entrance of the southern rivers into the northern area of Poyang Lake, where the water flow is turbulent and methylene chloride is strongly volatilized and degraded. After that, methylene chloride entered the northern part of the lake in Xinchixiang (672.37 ng L−1) and Laoyemiao (1510.1 ng L−1) and was then reduced in Pingfen (222.92 ng L−1). Finally, methylene chloride flowed into the Yangtze River through Xieshan (506.2 ng L−1).
| Author | Lake/river | Number of VOCs detected | Concentration range (μg L−1) |
|---|---|---|---|
| a ND: not detected. | |||
| Liu Y., et al.36 | Baitabao River | 14 | ND ∼ 35.98 |
| Chen X. C., et al.29 | Yangtze River | 50 | ND ∼ 4.03 |
| Huaihe River | ND ∼ 22.21 | ||
| Yellow River | 1.94–42.78 | ||
| Haihe River | 0.48–2.75 | ||
| Liaohe River | 1.10–20.85 | ||
| Nikolaou A. D., et al.35 | 10 rivers and 7 lakes in Greece | 15 | ND ∼ 3.90 |
| Nystrom E. A.19 | Groundwater in Lake Champlain basin | 6 | ND ∼ 11.8 |
| Han F. A., et al.37 | 21 water sampling points in Jiangsu, Zhejiang, and Shandong provinces | 19 | ND ∼ 27.79 |
| Baehr A. L. & Zapecza O. S.33 | Cranberry Lake and Lackawanna Lake | 6 | ND ∼ 29.0 |
| Kostopoulou M. N., et al.34 | 4 rivers and 5 lakes in the region of northern Greece | 6 | ND ∼ 40.0 |
| Fengmei Cao, et al.38 | Dongting Lake | 22 | ND ∼ 1.06 |
Compared to other studies, the reported levels of VOCs varied substantially. In Dongting Lake,38 the concentrations of detected VOCs varied from 0.012 (1,1-dichloroethane) to 1.06 μg L−1 (bromodichloromethane), and the concentrations of methylene chloride were 61.8–106.7 ng L−1. This result is nearly 28 times lower than the concentration of methylene chloride (2809.94 ng L−1) in Poyang Lake. In addition, methylene chloride was not detected in the rivers associated with the Baitabao River36 and in the urban rivers of Shandong, Jiangsu and Zhejiang provinces.37 The top 10 most frequently detected common VOCs in typical drinking water sources from 5 major river basins in China were 1,2,4-trichlorobenzene, toluene, m-xylene, p-xylene, o-xylene, naphthalene, 1,2-dichloropropane, bromochloromethane, ethylbenzene, and 1,2,3-trichlorobenzene, and for these compounds, the FODs were above 27%.29 This is consistent with the FODs of toluene (100%) and 1,2-dichloropropane (82.1%) in Poyang Lake. Chloroform has been classified as a probable human carcinogen on the basis of inadequate evidence in humans, but there is sufficient evidence for carcinogenicity in animals; chloroform had 100% FODs in both Poyang Lake (11.84–1379.83 ng L−1) and Dongting Lake (100.0–278.3 ng L−1). The concentration range of chloroform in Greece was ND-417 ng L−1 in rivers and ND-174 ng L−1 in lakes,34 which was lower than that in Poyang Lake.
The lowest concentration range of VOCs in the literature is ND ∼ 3.90 μg L−1, except for the highest concentrations in Haihe River and Dongting Lake. The highest concentration of VOCs in Poyang Lake was 2.81 μg L−1, which is lower than the concentrations in other lakes/rivers, except Haihe River and Dongting Lake. The concentrations of VOCs detected in lakes were lower than those in rivers. This conclusion is similar to the results of Kostopoulou et al.34 and Cao et al.38 The solubility of VOCs in water is affected by turbulence. Stronger turbulence can naturally increase the amount of VOCs dissolved in water. The turbulence in rivers is stronger than that in lakes, resulting in lower concentrations of VOCs in lakes than in rivers. It is inferred that the concentrations of VOCs in the atmosphere are higher than the concentrations in the water. Therefore, the atmosphere may be the source of VOCs in water. Based on this, VOC pollution in Poyang Lake was at a low level.
According to the risk assessment formula in Section 2.5, the risk of VOCs in Poyang Lake was calculated. The results are shown in Table 3. It can be concluded that the risk value of the human body via skin exposure (dermal risk) is much smaller than that caused by ingestion. It can be inferred that pollutants enter the body mainly through ingestion. This is similar to literature reports.39,40 According to the relevant definition of non-carcinogenic risk from the USEPA, when the risk index of a pollutant exceeds 1, the pollutant is considered to be harmful to human health. The non-carcinogenic risk of 10 kinds of VOCs detected ranged from 6.29 × 10−5 to 1.11 × 10−1, which is much smaller than 1. As a result, the detected contaminants do not pose significant non-carcinogenic health risks to the human body, which is consistent with the results of Chen29 and Cao.38 The acceptable carcinogenic risk index recommended by the USEPA is 1.0 × 10−6, which means that lower values are acceptable. As we can see, the ingestion risk and total risk index of methylene chloride are 1.32 × 10−6 and 1.33 × 10−6, both higher than the standard limit. Therefore, it is believed that methylene chloride may cause cancer risk in Poyang Lake. The production, discharge and treatment of methylene chloride in Poyang Lake should receive greater focus. In Chen's study,29 crotonaldehyde in the Yangtze River basin, Huaihe River basin, Yellow River basin, Haihe River basin, and Liaohe River basin posed a low carcinogenic risk via drinking. However, some researchers have conducted health risk assessments of VOCs emitted during e-waste dismantling.41–44 The results showed that both cancer and non-cancer risks exist for workers due to exposure to on-site emitted VOCs at all e-waste dismantling workshops, which is different from our findings. This may be because the concentration of VOCs in indoor air is much higher than the concentration of VOCs in rivers and lakes. Therefore, source water may pose a potential carcinogenic risk because of the presence of methylene chloride if used for drinking.
| Contaminants | Carcinogenic risk | Non-carcinogenic risk | ||||
|---|---|---|---|---|---|---|
| Ingestion risk | Dermal risk | Total risk | Ingestion risk | Dermal risk | Total risk | |
| 1,1-Dichloroethylene | 1.28 × 10−4 | 5.36 × 10−7 | 1.28 × 10−4 | |||
| Methylene chloride | 1.32 × 10−6 | 5.55 × 10−9 | 1.33 × 10−6 | 1.10 × 10−1 | 4.62 × 10−4 | 1.11 × 10−1 |
| cis-1,2-Dichloroethylene | 8.33 × 10−5 | 3.50 × 10−7 | 8.37 × 10−5 | |||
| Chloroform | 1.75 × 10−2 | 7.33 × 10−5 | 1.76 × 10−2 | |||
| Benzene | 7.60 × 10−7 | 3.19 × 10−9 | 7.63 × 10−7 | 5.06 × 10−2 | 2.13 × 10−4 | 5.09 × 10−2 |
| Bromodichloromethane | 5.76 × 10−7 | 2.42 × 10−9 | 5.79 × 10−7 | 5.65 × 10−2 | 2.37 × 10−4 | 5.68 × 10−2 |
| Toluene | 1.27 × 10−2 | 5.33 × 10−5 | 1.28 × 10−2 | |||
| Dibromochloromethane | 8.24 × 10−8 | 3.46 × 10−10 | 8.27 × 10−8 | 1.03 × 10−4 | 4.32 × 10−7 | 1.03 × 10−4 |
| Chlorobenzene | 6.26 × 10−5 | 2.63 × 10−7 | 6.29 × 10−5 | |||
| Ethylbenzene | 1.06 × 10−4 | 4.45 × 10−7 | 1.07 × 10−4 | |||
Footnote |
| † Electronic supplementary information (ESI) available. See DOI: 10.1039/c9ra02450f |
| This journal is © The Royal Society of Chemistry 2019 |