Thermochemical Formation of Polybrominated Dibenzo-p-Dioxins and Dibenzofurans Mediated by Secondary Copper Smelter Fly Ash, and Implications for Emission Reduction
Thermochemical Formation of Polybrominated Dibenzo-p-Dioxins and Dibenzofurans Mediated by Secondary Copper Smelter Fly Ash, and Implications for Emission Reduction
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二次铜冶炼厂飞灰介导的多溴二苯并对二恶英和二苯并呋喃的热化学形成及其对减排的影响
DOI：
10.1021/acs.est.6b02119
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发表时间：
2016
影响因子：
11.4
通讯作者：
Jin Rong
中科院分区：
文献类型：
--
作者：
Wang Mei;Liu Guorui;Jiang Xiaoxu;Zheng Minghui;Yang Lili;Zhao Yuyang;Jin Rong
飞灰介导的非均相反应对于多氯二苯并-对-二恶英和二苯并呋喃 (PCDD/Fs) 的形成很重要。然而，通过非均相反应形成多溴二苯并-对-二恶英和二苯并呋喃（PBDD/Fs）尚不清楚。进行了实验，研究通过二次铜冶炼厂飞灰的非均相反应在 150–450 °C 下热化学形成 PBDD/F。飞灰中 PBDD/F 的最大浓度比初始 PBDD/F 浓度高 325 倍。 150℃实验后PBDD/F浓度比初始浓度高出5倍。此前尚未发现 PBDD/F 在如此低的温度下形成。二次铜冶炼厂粉煤灰明显促进了 PBDD/F 的形成，这一结论得到了阿伦尼乌斯定律计算中发现的低活化能的支持。由工业设施中沉积的飞灰介导的 PBDD/F 的热化学形成可以解释工业设施中释放的 PCDD/F 和类似化合物的“记忆效应”。通过飞灰介导的反应形成的大量多溴二苯醚 (PBDE) 可能是通过飞灰介导的反应形成的 PBDD/F 的重要前体。通过飞灰介导的反应形成的多溴联苯醚的量表明，二次铜冶炼厂可能是重整的多溴二苯醚的重要来源。
Heterogeneous reactions mediated by fly ash are important to polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) formation. However, the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) through heterogeneous reactions is not yet well understood. Experiments were performed to investigate the thermochemical formation of PBDD/Fs at 150–450 °C through heterogeneous reactions on fly ash from a secondary copper smelter. The maximum PBDD/F concentration was 325 times higher than the initial PBDD/F concentration in the fly ash. The PBDD/F concentration after the experiment at 150 °C was five times higher than the initial concentration. PBDD/Fs have not previously been found to form at such a low temperature. Secondary-copper-smelter fly ash clearly promoted PBDD/F formation, and this conclusion was supported by the low activation energies that were found in Arrhenius’s law calculations. Thermochemical formation of PBDD/Fs mediated by fly ash deposited in industrial facilities could explain “memory effects” that have been found for PCDD/Fs and similar compounds released from industrial facilities. Abundant polybrominated diphenyl ethers (PBDEs) that were formed through fly ash-mediated reactions could be important precursors for PBDD/Fs also formed through fly ash-mediated reactions. The amounts of PBDEs that formed through fly ash-mediated reactions suggested that secondary copper smelters could be important sources of reformed PBDEs.