Analysis of the limits of air pollutants at enterprise boundary based on ambient multimedia environmental goals estimation
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摘要:
从40余项国家大气固定污染源污染物排放标准以及地方恶臭污染物排放标准中筛选出已制定企业边界限值的36种大气污染物，提出适用于限值分析的方法，基于周围环境目标值（AMEG）设置了参考区间，对比分析了我国与美国化学有害因素职业接触限值时间加权平均容许浓度（TWA）的差异。结果表明，36种大气污染物可分为3类：1）出现在国家大气污染物综合排放标准等制定和发布年限较长标准中且限值较为宽松的8种污染物；2）限值未受嗅阈值影响的13种污染物，其中12种污染物的限值与AMEG估算结果的8.4倍较为接近；3）限值受嗅阈值影响的15种污染物，其中部分污染物的限值接近AMEG估算结果，部分限值接近嗅阈值。参与对比分析的255种化学有害因素中，我国和美国的TWA相等的有44种，占比不超过20%，差异在±1倍之内的约占85%，在±5倍以上的约占7%。研究显示，现行大气污染物排放标准中的企业边界限值有效保护了人体健康和生态环境，应对制定和发布年限较长且限值较为宽松的标准，以及限值高于嗅阈值的标准开展研究，分析限值的合理性。在制定企业边界大气污染物限值时，应广泛收集更多来源的职业接触限值数据并分析其适用性。
Abstract:Thirty-six air pollutants with established enterprise boundary limits were screened out from more than 40 national emission standards for stationary air pollutants sources and local emission standards for odor pollutants. A method suitable for limit analysis was proposed, and a reference interval was set based on the ambient multimedia environmental goals (AMEG). The difference in the occupational exposure limits time-weighted average allowable concentration (TWA) of chemical harmful factors between China and the United States was compared and analyzed. The results showed that the 36 air pollutants could be divided into three categories. Firstly, there were 8 pollutants that appeared in the national integrated emission standards for air pollutants and other standards that had been formulated and published for a long time with loose limits. Secondly, there were 13 pollutants whose limits were not affected by olfactory thresholds, among which the limits of 12 pollutants were close to 8.4 times of AMEG estimation. Thirdly, there were 15 pollutants whose limits were affected by olfactory thresholds, among which the limits of some pollutants were close to AMEG estimation, and some were close to olfactory thresholds. Among the 255 chemical harmful factors involved in the comparative analysis, there were 44 chemical harmful factors with TWA equivalent in China and the United States, accounting for no more than 20 percent, nearly 85 percent with a difference within ±1 time, and 7 percent with a difference of more than ±5 times. The research showed that the enterprise boundary limits in the current air pollutant emission standards had effectively protected human health and ecological environment. However, the standards that had been formulated and published for a long time with loose limits, as well as limits of the standards higher than olfactory thresholds, should be studied to analyze the reasonableness of the limits. Occupational exposure limits data from more sources should be widely collected and their applicability should be analyzed when formulating the limits of air pollutants at enterprise boundaries.
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图 1 未受嗅阈值影响的大气污染物的企业边界限值分布
注：未受嗅阈值影响的大气污染物中有相应嗅阈值的污染物分别为甲苯、丙烯酸乙酯、苯乙烯、丙烯酸甲酯、苯、氯气，嗅阈值折算值分别为0.29、−0.13、0.03、−0.10、82.82、8.06。
Figure 1. Distribution of enterprise boundary limits for air pollutants not affected by olfactory thresholds
图 2 受嗅阈值影响大气污染物的企业边界限值分布
Figure 2. Distribution of enterprise boundary limits for air pollutants affected by olfactory thresholds
表 1 本研究涉及的标准及污染物
Table 1. Emission standards and air pollutants involved in this study
标准 涉及行业 具有企业边界限值的大气污染物 国家大气固定污染源污染物
排放标准系列黑色金属矿采选业、黑色金属冶炼和压延加工业、有色金属矿采选业、有色金属冶炼和压延加工业、化学原料和化学制品制造业、非金属矿物制品业等 氯化氢、甲苯、二甲苯、氯气、苯、氰化氢、氯乙烯、乙醛、二甲基甲酰胺、氯苯类、酚类、硝基苯类、二氯乙烷、苯胺类、甲醛、丙烯腈、光气、丙烯醛、甲醇等 DB 31/1025—2016《恶臭（异味）污染物排放标准》 通用型污染物排放标准 氨、硫化氢、甲硫醇、甲硫醚、二甲二硫、二硫化碳、苯乙烯、三甲胺、乙苯、丙醛、正丁醛、正戊醛、乙酸乙酯、乙酸丁酯、甲基异丁基酮、2-丁酮、丙烯酸、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、一甲胺、二甲胺等 DB 12/059—2018《恶臭污染物排放标准》 
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表 2 36种大气污染物企业边界限值汇总
Table 2. Summary of enterprise boundary limits for 36 air pollutants
mg/m3 污染物 职业接触限值 嗅阈值 企业边界限值 苯胺类 3 0.4 甲醛 0.51) 0.623) 0.2 丙烯腈 1 19.413) 0.6 光气 0.51) 0.08 丙烯醛 0.31) 0.008 43) 0.4 甲醇 25 43.973) 12 二硫化碳 5 0.54 0.5 二甲二硫 2.102) 0.043 0.05 氯乙烯 10 0.15 二甲苯 50 0.8 丙烯酸 6 0.11 氯化氢 7.51) 0.15 二甲基甲酰胺 20 0.4 硝基苯类 2 0.04 二氯乙烷 7 0.15 甲苯 50 0.38 0.8 苯 6 8.773) 0.1 丙烯酸乙酯 22.352) 0.001 13) 0.4 苯乙烯 50 0.15 1 丙烯酸甲酯 20 0.0133) 0.4 氯气 11) 0.143) 0.02 三甲胺 13.192) 0.022 0.05 甲硫醇 1 0.000 13 0.002 乙酸丁酯 200 0.038 0.4 硫化氢 101) 0.001 7 0.02 酚类 10 0.0223) 0.02 丙醛 51.862) 0.039 0.065 乙醛 451) 0.033 0.04 甲硫醚 27.742) 0.005 2 0.02 正戊醛 192.252) 0.005 7 0.04 乙酸乙酯 200 3.08 3 乙苯 100 0.753) 1 氨 20 0.21 0.2 一甲胺 5 0.0453) 0.03 甲基异丁基酮 89.432) 0.713) 1.2 2-丁酮 300 1.323) 1.4 1)为GBZ 2.1—2019中的MAC；2)为美国ACGIH公布的TLV-TWA；3)为日本环境卫生中心测得的嗅阈值。
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表 3 PC-TWA和TLV-TWA差异性累计占比
Table 3. Cumulative proportion of differences between PC-TWA and TLV-TWA
ΔR<0 ΔR≥0 ΔR ΔR区间/% 污染物数量/种 ΔR区间/% 污染物数量/种 ΔR区间/% 污染物数量/种 占比/% −10~0 43 0~10 21 −10~10 108 42.4 −20~0 62 0~20 29 −20~20 135 52.9 −50~0 87 0~50 33 −50~50 164 64.3 −100~0 128 0~100 44 −100~100 216 84.7 −200~0 128 0~200 55 −200~200 227 89.0 −500~0 128 0~500 65 −500~500 237 92.9 −1 000~0 128 0~1 000 75 −1 000~1 000 247 96.9 总计 128 83 255 100
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