International Joint Research Center for Persistent Toxic Substances (IJRC-PTS), College of Environmental Science and Engineering, Dalian Maritime University, Dalian, PR China.
Environ Sci Technol. 2013 Aug 6;47(15):8978-84. doi: 10.1021/es4022409. Epub 2013 Jul 22.
Air samples were concurrently collected using high volume air samplers for 24 h every week from September 2008 to August 2009 at 15 sites (11 urban, 1 suburban, and 3 background/rural) across China. Twelve polybrominated diphenyl ether (PBDE) congeners (BDE-17, -28, -47, -66, -85, -99, -100, -138, -153, -154, -183, and -209) were measured. Total PBDE concentrations (∑12PBDEs) in air (gas + particle phases) were in the range of 11.0-838 pg m(-3) with a mean of 232 ± 72 (mean ± SE) pg m(-3). The site with the highest concentration was Guangzhou (838 ± 126 pg m(-3)), followed by Beijing (781 ± 107 pg m(-3)). Significant positive correlations were found between PBDEs levels and urban population (R = 0.69, P < 0.05) and gross industrial output values (R = 0.87, P < 0.001) as well. BDE-209 was the dominating congener with the contribution of 64 ± 23% to ∑12PBDEs, followed by BDE-47(8 ± 8%) and -99(6 ± 5%) at all urban and suburban sites. At background/rural sites, however, BDE-47 was the dominating congener, followed by BDE-99, together accounting for 52 ± 21% of ∑12PBDEs, while BDE-209 was only 11 ± 2%. It was found that PBDEs at the 15 sites showed a primary distribution and fractionation pattern. This study produced more than 700 pairs of air samples in gaseous and particulate phases with a wide temperature range of ∼60 °C, providing a good opportunity to investigate gas-particle partitioning for individual PBDE congeners. The results of gas-particle partitioning analysis for PBDEs using both subcooled-liquid-vapor pressure (PL)-based and octanol-air partition coefficient (KOA)-based models indicated that PBDEs in air at all sampling sites had not reached equilibrium because the slope values (mO) in the KOA-based equation and the opposite slope values (mP) in the PL-based equation at all 15 sampling sites were less than 1. It also found that both mO and -mP were significantly and positively correlated with the annual average temperatures of sampling sites and also significantly and negatively correlated with the mole masses of PBDE congeners, indicating a general trend that the higher the temperature at the sampling site and the lower the mole mass of the PBDE congeners are, the closer to the equilibrium the congeners approach and vice versa. To our knowledge, this is the first study to report the correlations of the slope values for both the KOA-based and PL-based equations with temperatures at sampling sites and mole masses for individual PBDE congeners.
于 2008 年 9 月至 2009 年 8 月，在中国 15 个地点（11 个城市、1 个郊区和 3 个背景/农村），使用高容量空气采样器，每周 24 小时采集空气样本。共测量了 12 种多溴二苯醚（PBDE）同系物（BDE-17、-28、-47、-66、-85、-99、-100、-138、-153、-154、-183 和 -209）。空气中（气相和颗粒相）的总 PBDE 浓度（∑12PBDEs）范围为 11.0-838 pg m(-3)，平均值为 232 ± 72（平均值 ± SE）pg m(-3)。浓度最高的地点是广州（838 ± 126 pg m(-3))，其次是北京（781 ± 107 pg m(-3))。PBDEs 水平与城市人口（R = 0.69，P < 0.05）和工业总产值（R = 0.87，P < 0.001）之间存在显著正相关。在所有城市和郊区地点，BDE-209 是占比最高的同系物，对∑12PBDEs 的贡献为 64 ± 23%，其次是 BDE-47（8 ± 8%）和 -99（6 ± 5%）。然而，在背景/农村地区，BDE-47 是占比最高的同系物，其次是 BDE-99，两者共占∑12PBDEs 的 52 ± 21%，而 BDE-209 仅占 11 ± 2%。研究发现，15 个地点的 PBDEs 呈现出主要的分布和分馏模式。本研究共采集了超过 700 对气态和颗粒态的空气样本，温度范围约为 60°C，为研究单个 PBDE 同系物的气-粒分配提供了良好的机会。使用亚冷却液体-蒸气压力（PL）和辛醇-空气分配系数（KOA）模型对 PBDEs 气-粒分配分析的结果表明，由于所有 15 个采样点的 KOA 方程中的斜率值（mO）和 PL 方程中的相反斜率值（mP）均小于 1，因此所有采样点空气中的 PBDEs 尚未达到平衡。还发现，mO 和-mP 均与采样点的年平均温度呈显著正相关，与 PBDE 同系物的摩尔质量呈显著负相关，表明一般来说，采样点温度越高，PBDE 同系物的摩尔质量越低，同系物越接近平衡，反之亦然。据我们所知，这是首次报道 KOA 基础和 PL 基础方程的斜率值与采样点温度和单个 PBDE 同系物摩尔质量之间的相关性。
