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矿物颗粒是大气颗粒物的重要组成部分,约占大气对流层颗粒物质量浓度的50%,据估算全球每年进入大气的矿物颗粒约有
1000 —3000 Tg[1 − 3]. 值得指出的是,在沙尘暴期间,北京大气中矿物颗粒的质量浓度在颗粒物中的占比可高达74%[4]. 矿物颗粒具有较长的大气寿命(数天到数周)[5],其在风力作用下在大气中能够迁移数千米. 在矿物颗粒迁移的过程中,由于其具有巨大的比表面积和较高的化学活性(表面活性位点、金属离子等),可以为大量的污染物提供丰富的吸附位点,因此,大量污染物可能吸附在矿物颗粒表面. 吸附在矿物颗粒表面的污染物的反应活性可能会与气相不同,导致其可能会存在与气相不同的反应机制,最终影响其大气归趋及影响[6 − 10]. 例如,Ji等[7]发现,相比甲醛和NO2的气相反应,吸附在二氧化硅矿物颗粒表面的甲醛与NO2反应生成HONO的能垒较低. Liu等[9]发现吸附在MgO颗粒表面的SO2,通过与NO形成不同于气相反应的独特[SO4−NO]络合物机制,促进NO向NO2转化. 因此,了解污染物在矿物颗粒表面的吸附行为对于评估其大气归趋及影响具有指导意义.芳香族污染物是大气中一类重要的污染物,其中芳香烃在城市大气中占总挥发性有机物浓度的20%—30%[11]. 它们通常来自含碳材料的不完全燃烧,石油裂解,森林火灾和火山喷发等[12 − 13],不但具有致癌和致畸作用,而且可能会在大气中经历一系列的转化过程生成比自身毒性更大的产物,多种芳香族污染物已被我国生态环境部和美国环保署列为优先控制污染物[14 − 15]. 芳香族污染物由于具有较高的持久性和长距离迁移性,因此很可能会吸附在矿物颗粒表面. 例如,在北京和天津地区的矿物颗粒表面上已检出芳香族污染物[16 − 17]. 然而,目前仅有个别研究考察了芳香族污染物(萘、蒽、菲、甲苯、苯酚、氟苯、氯苯、溴苯)在矿物颗粒表面的吸附行为[18 − 20],还有大量的芳香族污染物在矿物颗粒表面的吸附行为是未知的,严重阻碍了全面认识芳香族污染物的大气影响. 因此,亟需全面探究芳香族污染物在矿物颗粒表面的吸附行为.
吸附能(Eads)是描述污染物在矿物颗粒表面吸附行为的一个重要参数[21 − 22]. 鉴于大气中存在大量的芳香族污染物,逐一揭示芳香族污染物在矿物颗粒表面的Eads值,需要极大的工作量. 因此,亟需建立一种高通量的预测模型来预测芳香族污染物在矿物颗粒表面的Eads值. 定量结构-活性关系(QSAR)模型是目前最有效的模型之一,已被广泛应用于预测污染物在不同表面的Eads值[23 − 26]. 例如,Wang等[26]构建了预测水相和气相中有机污染物在石墨烯上Eads值的QSAR模型;Su等[24]建立了预测有机污染物在黑磷纳米颗粒上Eads值的多参数线性自由能关系(pp-LFERs)模型. 然而,由于目前缺乏芳香族污染物在矿物颗粒表面上Eads值的数据,未见报道用于预测芳香族污染物在矿物颗粒表面上Eads值的QSAR模型.
三水铝石(Al(OH)3)是地球表面最丰富且最常见的矿物颗粒之一[27 − 28],也是最稳定的一种氢氧化铝矿物形态[29]. 它是由OH—Al—OH配位八面体周期性排列而形成的薄的扁平六边形晶体,可以为大气中的芳香族污染物提供丰富的—OH吸附位点,进而影响芳香族污染物的环境行为. 本研究采取“吸附机制研究-QSAR模型构建”的两步策略,首先选取21个代表性芳香族污染物作为模型化合物,使用第一性原理的方法探究它们在三水铝石(001)面上的吸附行为,并计算相应的Eads值. 随后,基于计算得到的21个Eads值,采用多元线性回归(MLR)方法,建立预测芳香族污染物在三水铝石(001)面上Eads值的QSAR模型. 研究结果对于增强芳香族污染物在矿物颗粒表面上吸附行为的理解具有重要意义,并且为进一步揭示芳香族污染物在三水铝石(001)面上的大气转化奠定了基础.
三水铝石矿物颗粒表面吸附芳香族污染物的计算模拟与预测
Computational simulation and prediction for adsorption of aromatic pollutants on gibbsite mineral particle surface
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摘要: 了解芳香族污染物在矿物颗粒表面的吸附行为对于评估其大气归趋及影响具有重要意义. 吸附能(Eads)是描述芳香族污染物在矿物颗粒表面吸附行为的重要参数,然而,目前该数据十分匮乏. 考虑到大气中存在大量的芳香族污染物,逐个揭示芳香族污染物在矿物颗粒表面的Eads值需要巨大的计算资源和工作量. 因此,亟需建立一种能够快速预测芳香族污染物在矿物颗粒表面Eads值的预测模型. 本研究采取第一性原理的方法,探究了21个芳香族污染物在矿物颗粒三水铝石(001)面上的吸附机制. 结果发现,21个芳香族污染物与三水铝石(001)面主要形成氢键、O—H···π键以及O—H···X (X = Cl/Br)相互作用,其Eads值的范围在−12 kcal·mol−1至−30 kcal·mol−1之间. 基于计算得到的21个Eads值,采用多元线性回归分析方法,建立了预测芳香族污染物在三水铝石(001)面上Eads值的定量结构-活性关系模型. 该模型具有很好的拟合优度、稳健性和预测能力,能够用来预测含有—CH3、—OH、—COOH、—NO2、—NH2、—CHO、—F、—Cl、—Br官能团的芳香族污染物. 本研究结果对于提高目前对芳香族污染物在矿物颗粒表面上吸附行为的理解具有重要意义,并且为进一步揭示芳香族污染物在三水铝石(001)面上的大气转化奠定了基础.
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关键词:
- 芳香族污染物 /
- 三水铝石 /
- 吸附能 /
- 第一性原理计算 /
- 定量结构-活性关系.
Abstract: Understanding the adsorption behavior of aromatic pollutants on the surface of mineral particles is significant for evaluating their atmospheric fate and impacts. The adsorption energy (Eads) is a crucial parameter to describe the adsorption behavior of aromatic pollutants on the surface of mineral particles. However, only limited aromatic pollutants (i.e., naphthalene, anthracene, toluene, phenol, et al.) have so far been studied. In view of the large amounts of aromatic pollutants in the atmosphere, it takes lots of work to evaluate the Eads values of aromatic pollutants on the surface of mineral particles one by one. Therefore, it is necessary to establish a high-throughput prediction model to predict the Eads values of aromatic pollutants on the surface of mineral particles. Herein, we employed first-principles calculations to investigate the adsorption mechanism of 21 aromatic pollutants on gibbsite (001) surface. Results indicated that three types of interactions including hydrogen bonds, O—H···π bonds and O—H···X (X = Cl/Br) are formed between 21 aromatic pollutants and gibbsite (001) surface. The calculated Eads values are in the range of −12—−30 kcal·mol−1. Based on the calculated 21 Eads values, a quantitative structure-activity relationship (QSAR) model for predicting the Eads values of aromatic pollutants on gibbsite (001) surface was established. The model has good goodness of fit, robustness and predictive ability, which can be used to predict the Eads values of aromatic pollutants containing —CH3, —OH, —COOH, —NO2, —NH2, —CHO, —F, —Cl and —Br functional groups. The results expand current understanding of the adsorption mechanism of aromatic pollutants on the surface of mineral particles, and provide a foundation for investigating the atmospheric transformation of aromatic pollutants on gibbsite (001) surface in the further. -
表 1 21个芳香族污染物的分类、名称、分子式和CAS号
Table 1. Classification, name, molecular formula and CAS number of the 21 aromatic pollutants
分类
Classification名称
Name分子式
Molecular formulaCAS 苯和PAHs 苯 C6H6 00071-43-2 萘 C10H8 00091-20-3 蒽 C14H10 00120-12-7 菲 C14H10 00085-01-8 芴 C13H10 00086-73-7 取代苯 甲苯 C7H8 00108-88-3 苯酚 C6H6O 00108-95-2 苯甲酸 C7H6O2 00065-85-0 硝基苯 C6H5NO2 00098-95-3 苯胺 C6H7N 00062-53-3 苯甲醛 C7H6O 00100-52-7 氟苯 C6H5F 00462-06-6 溴苯 C6H5Br 00108-86-1 氯苯 C6H5Cl 00108-90-7 1,2-二氯苯 C6H4Cl2 00095-50-1 1,2,4-三氯苯 C6H3Cl3 00120-82-1 1,2,4,5-四氯苯 C6H2Cl4 00095-94-3 二噁英 二苯并对二噁英 C12H8O2 00262-12-4 2,7-二氯代二苯并对二噁英 C12H6Cl2O2 33857 -26-02,3,7,8-四氯代二苯并对二噁英 C12H4Cl4O2 01746-01-6 2,6-二氯代二苯并呋喃 C12H6Cl2O 60390 -27-4表 2 21个芳香族污染物在三水铝石(001)面上的吸附能(Eads)、相互作用类型以及Bader电荷分析得到的各种芳香族污染物的电荷转移(Q)
Table 2. Adsorption energies (Eads), interaction types of 21 aromatic pollutants on gibbsite (001) surface and charge transfer (Q) of each aromatic pollutant obtained by Bader charge analysis
化合物
CompoundEads/
(kcal·mol−1)O—H···π键
O—H···π bond氢键
Hydrogen bondO—H···X
(X = Cl/Br)Q/e 苯 −12.13 ● ○ ○ 0.030 萘 −19.34 ● ○ ○ 0.057 蒽 −25.21 ● ○ ○ 0.056 菲 −24.83 ● ○ ○ 0.049 芴 −23.33 ● ○ ○ 0.042 甲苯 −15.25 ● ○ ○ 0.025 苯酚 −23.31 ● ● ○ −0.003 苯甲酸 −26.40 ● ● ○ −0.039 硝基苯 −19.61 ● ● ○ 0.015 苯胺 −17.94 ● ● ○ 0.005 苯甲醛 −16.13 ● ● ○ 0.015 氟苯 −12.92 ● ● ○ 0.021 溴苯 −15.50 ● ○ ● 0.052 氯苯 −15.20 ● ○ ● 0.037 1,2-二氯苯 −18.01 ● ○ ● 0.045 1,2,4-三氯苯 −18.12 ● ○ ● 0.050 1,2,4,5-四氯苯 −18.84 ● ○ ● 0.041 二苯并对二噁英 −23.76 ● ● ○ 0.031 2,7-二氯代二苯并对二噁英 −27.70 ● ● ● 0.037 2,3,7,8-四氯代二苯并对二噁英 −29.16 ○ ● ● 0.056 2,6-二氯代二苯并呋喃 −24.67 ● ● ● 0.056 注:正数Q表示芳香族污染物向三水铝石(001)面的电荷转移;●和○分别表示相互作用类型的有无.
Note: The positive number Q represents the charge transfer of each aromatic pollutant to gibbsite (001) surface; symbols ● and ○ indicate the presence and absence of interaction types, respectively.表 3 模型中涉及的分子描述符的含义及其方差膨胀因子(VIF)、t检验值和显著性水平P值
Table 3. Molecular descriptors involved in the model and their variable inflation factor (VIF), t-statistics, and significance-level P Values.
描述符
Descriptor含义
DefinitionVIF t P lgKOA 正辛醇-空气分配系数 2.600 −14.11 <0.001 Am 由质量测量的WHIM描述符 2.600 2.357 <0.040 表 4 QSAR模型中所涉及的描述符lgKOA和Am的值以及通过QSAR模型预测得到的吸附能(Eads_pre)
Table 4. Values of lgKOA and Am descriptors involved in the QSAR model and predicted adsorption energies (Eads_pre) by the QSAR model
化合物
CompoundlgKOA Am Eads_pre/(kcal·mol−1) 苯 2.7801) 1.289 −13.27 萘 5.1901) 4.034 −19.31 蒽 7.5501) 8.271 −25.01 菲 7.5701) 9.009 −24.96 芴 6.7901) 7.234 −23.13 甲苯 3.3101) 2.207 −14.55 苯酚 6.3262) 1.990 −22.66 苯甲酸 7.6782) 3.795 −26.00 硝基苯 4.8582) 3.736 −18.48 苯胺 4.9832) 2.021 −19.04 苯甲醛 4.4422) 2.902 −17.47 氟苯 2.8632) 2.114 −13.36 溴苯 3.9862) 3.238 −16.22 氯苯 3.3101) 2.921 −14.45 1,2-二氯苯 4.3601) 6.883 −16.69 1,2,4-三氯苯 4.9501) 8.160 −18.08 1,2,4,5-四氯苯 5.6301) 10.42 −19.57 二苯并对二噁英 6.6432) 7.322 −22.72 2,7-二氯代二苯并对二噁英 8.3601) 13.245 −26.46 2,3,7,8-四氯代二苯并对二噁英 10.0501) 26.200 −29.11 2,6-二氯代二苯并呋喃 8.3601) 15.394 −26.15 注:1)和2)分别表示EPI suite 4.0软件得到芳香族污染物的lgKOA的实验值和预测值.
Note: 1) and 2) represent the experimental and predicted lgKOA values of aromatic pollutants obtained by EPI suite 4.0, respectively. -
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