Pollution Characteristics and Health Risk Assessment of Volatile Organic Compounds in Groundwater in the Lower Liaohe River Plain
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摘要:
挥发性有机物（VOCs）作为重要的化工原料、中间体和有机溶剂，随着人类工农业的发展，其对环境及人类健康的影响日益凸显。下辽河平原作为人口较密集、工业化程度较高的平原地区，地下水的污染随着人类活动不断加剧，对人体健康产生了潜在风险。为了研究下辽河平原地下水中VOCs的污染特征及对人体产生的健康风险，本文利用吹扫捕集-气相色谱-质谱法检测下辽河平原地下水样品中60种VOCs的含量及污染特征并分析其污染来源。通过经口饮用、洗浴呼吸吸入、洗浴皮肤接触三种VOCs的暴露途径计算污染物长期摄入量，采用CSOIL模型评价健康风险。结果表明：采集的24组地下水样品中有20个采样点检出VOCs，样品VOCs检出率为83.3%，在个别采样点萘、苯、1，2-二氯丙烷含量超过《地下水质量标准》（GB 14848—2017）Ⅲ类水的限值（100、10.0、5.0μg/L），工业源VOCs的排放是研究区地下水VOCs超标的主要来源。地下水样品中VOCs的总致癌风险指数在0~4.0×10-5之间，总非致癌风险指数在0~0.93之间，均低于US EPA推荐的健康风险评价标准；企业用地周边地下水中的健康风险指数高于农业用地地下水。本研究表明下辽河平原地下水中VOCs检出率相对较高，健康风险处于可接受水平，该结果可为地区地下水工业源VOCs污染监管和治理提供参考。
Abstract:BACKGROUND As important industrial chemicals, intermediates and organic solvents, volatile organic compounds (VOCs) have increased the impact on the environment and human health with the development of human industry and agriculture. As a densely populated and highly industrialized plain area, the concentration of VOCs in groundwater of the Lower Liaohe River Plain poses potential risks to human health as human activities constantly intensify.
OBJECTIVES To study the pollution characteristics of VOCs and the health risks in groundwater in the Lower Liaohe Plain.
METHODS The concentration of 60 VOCs in groundwater samples was determined by purge and trap-gas chromatography/mass spectrometry (PT-GC/MS) to investigate the VOCs pollution sources. By calculating the long-term intake of pollutants with three VOCs exposure routes via oral drinking, bath respiratory inhalation, and bath skin exposure, the health risk was assessed by the CSOIL health risk assessment model.
RESULTS The VOCs in 20 sampling sites were detectable from the whole 24 sampling sites, with a detection rate of 83.3%. The content of naphthalene, benzene, 1, 2-dichloropropane in some sites exceeded the limits of the standard for groundwater quality (GB 14848-2017, limit values of 100, 10.0, 5.0μg/L). The industrial sources were the main sources of groundwater VOCs in the study area. The total carcinogenic risk index of VOCs in groundwater samples was 0-4.0×10-5, and the total non-carcinogenic risk index was 0-0.93. Both were lower than the standard recommended by US EPA (United States Environmental Protection Agency). The health risk index in groundwater around enterprise land was higher than in the groundwater of agricultural land.
CONCLUSIONS The study shows that the VOCs detection rate is higher in groundwater in the lower Liaohe River Plain, however, the health risk is within acceptable levels for people. It provides reference for the control of VOCs pollution from regional groundwater industrial sources.
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表 1 研究区地下水中60种VOCs的总体检出情况
Table 1. Detection of 60 kinds of VOCs in groundwater in the study area
VOCs组分 样品检出个数 检出率(%) 检出的浓度(μg/L) 《地下水质量标准》 (GB 14848—2017) (Ⅲ)限值(μg/L) 超标个数 超标率(%) 最小值 最大值 平均值 二硫化碳 7 29.2 ND 3.36 0.72 - - - 1, 2-二氯丙烷 2 8.34 ND 9.17 0.75 5.0 2 8.33 1, 1, 2-三氯乙烷 1 4.20 ND 2.29 0.12 5.0 - - 1, 2, 3-三氯丙烷 2 8.30 ND 5.14 0.44 - - - 苯 6 25.0 ND 11.7 1.21 10.0 1 4.17 甲苯 2 8.32 ND 4.99 0.38 700 - - 乙苯 2 8.34 ND 1.47 0.11 300 - - 间+对-二甲苯 4 16.7 ND 3.90 0.42 500(总量) - - 邻-二甲苯 5 20.8 ND 28.0 1.75 - - 1, 3, 5-三甲基苯 2 8.31 ND 8.31 0.42 - - - 1, 2, 4-三甲基苯 4 16.7 ND 12.7 0.75 - - - 4-异丙基甲苯 1 4.20 ND 2.62 0.15 - - - 萘 12 50.0 ND 121 45.7 100 2 8.33 1, 3-二氯苯 1 4.20 ND 1.01 0.041 - - - 1, 4-二氯苯 6 25.0 ND 4.33 0.42 300 - - 1, 2-二氯苯 4 16.7 ND 5.77 0.48 1000 - - 1, 2, 3-三氯苯 2 8.31 ND 2.84 0.24 20.0(总量) - - 1, 2, 4-三氯苯 4 16.7 ND 7.54 0.53 - - 氯苯 4 16.7 ND 28.4 1.37 300 - - 注：表格中的“-”表示“无”，ND表示未检出。 
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表 2 不同暴露途径的长期日摄入剂量数据
Table 2. Long-term intake dose data sheets for different exposure pathways
采样点编号 长期日摄入剂量 经口饮用[mg/(kg·d)] 洗浴呼吸(mg/m3) 洗浴皮肤接触[mg/(kg·d)] S1 6.2×10-3 8.9×10-5 2.2×10-3 S2 4.0×10-3 5.9×10-5 1.9×10-3 S3 8.1×10-5 1.2×10-6 1.1×10-4 S4 4.3×10-5 6.3×10-7 5.9×10-5 S5 5.6×10-4 8.1×10-6 7.6×10-4 S6 5.6×10-5 8.2×10-7 7.8×10-5 S7 4.2×10-4 6.1×10-6 5.7×10-4 S8 2.8×10-4 4.1×10-6 3.9×10-4 S9 5.2×10-5 7.6×10-7 7.2×10-5 S10 3.8×10-5 5.6×10-7 5.3×10-5 S11 3.5×10-4 5.1×10-6 4.8×10-4 S12 2.0×10-4 2.9×10-6 2.6×10-4 S13 0 0 0 S14 0 0 0 S15 1.4×10-5 2.0×10-7 1.8×10-5 S16 0 0 0 S17 2.3×10-5 3.4×10-7 3.0×10-5 S18 0 0 0 S19 9.0×10-6 1.3×10-7 1.2×10-5 S20 3.1×10-5 4.5×10-7 4.0×10-5 S21 5.2×10-4 7.5×10-6 3.2×10-4 S22 2.8×10-4 4.2×10-6 3.9×10-4 S23 5.1×10-5 7.5×10-7 5.0×10-5 S24 2.0×10-5 2.9×10-7 2.7×10-5
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表 3 研究区地下水致癌风险评价
Table 3. Carcinogenic risk assessment of groundwater in the study area
采样点编号 总致癌风险指数 风险类别 风险等级 风险等级说明 风险值区间 S1 3.4×10-5 疑似致癌风险 Ⅱ级 作为饮用水源需引起注意 [1.0×10-5，5.0×10-5] S2 4.0×10-5 疑似致癌风险 Ⅱ级 作为饮用水源需引起注意 [1.0×10-5，5.0×10-5] S3 3.1×10-6 疑似致癌风险 Ⅰ级 基本适合作为饮用水源 [1.0×10-6，1.0×10-5] S4 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S5 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S6 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S7 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S8 1.6×10-6 疑似致癌风险 Ⅰ级 基本适合作为饮用水源 [1.0×10-6，1.0×10-5] S9 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S10 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S11 5.9×10-6 疑似致癌风险 Ⅰ级 基本适合作为饮用水源 [1.0×10-6，1.0×10-5] S12 4.8×10-6 疑似致癌风险 Ⅰ级 基本适合作为饮用水源 [1.0.×10-6，1.0×10-5] S13 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S14 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S15 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S16 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S17 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S18 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S19 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S20 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S21 1.5×10-5 疑似致癌风险 Ⅱ级 作为饮用水源需引起注意 [1.0×10-5，5.0×10-5] S22 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S23 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6 S24 0 无致癌风险 忽略 适合作为饮用水源 ＜1.0×10-6
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表 4 各采样点VOCs的非致癌风险指数
Table 4. Non-carcinogenic risk of VOCs for each sampling point
采样点编号 非致癌风险指数 经口饮用 洗浴呼吸 洗浴皮肤接触 总非致癌风险指数 S1 0.3224 0.4819 0.127 0.93 S2 0.2125 0.4671 0.107 0.79 S3 0.0086 0.0065 0.0119 0.027 S4 0.0022 0.0048 0.0029 0.010 S5 0.0154 0.0226 0.0212 0.059 S6 0.0028 0.0062 0.0038 0.013 S7 0.0200 0.0438 0.0272 0.091 S8 0.0168 0.0303 0.0229 0.070 S9 0.0023 0.0050 0.00323 0.011 S10 0.0019 0.0043 0.00267 0.0089 S11 0.0239 0.0246 0.0320 0.081 S12 0.0153 0.0103 0.0203 0.046 S13 0 0 0 0 S14 0 0 0 0 S15 0.00014 0 0.000183 0.00032 S16 0 0 0 0 S17 0.00024 0 0.000306 0.00055 S18 0 0 0 0 S19 0 0 0 0 S20 0.0003 0 0.000402 0.00070 S21 0.0442 0.0020 0.0580 0.104 S22 0.0014 0.0009 0.00189 0.0042 S23 0.0010 0 0.00137 0.0024 S24 0.0003 0.0001 0.000379 0.00078
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