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首页> 外文期刊>Environmental Science & Technology >Advanced Oxidation Kinetics Of Aqueous Trialkyl Phosphate Flame Retardants And Plasticizers
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Advanced Oxidation Kinetics Of Aqueous Trialkyl Phosphate Flame Retardants And Plasticizers

机译：磷酸三烷基酯阻燃剂和增塑剂的高级氧化动力学

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摘要

Trialkyl phosphate esters are a class of anthropogenic organics commonly found in surface waters of Europe and North America, due to their frequent application as flame retardants, plasticizers, and solvents. Four trialkyl phosphate esters were evaluated to determine second-order rates of reaction with ultraviolet- and ozone-generated ·OH in water. Tris(2-butoxyethyl) phosphate (TBEP) was fastest to react with ·OH (k_(OH.TBEP) = 1.03 × 10~10 M~(-1) s~(-1)), followed sequentially by tributyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), and tris(2-chloroisopropyl) phosphate (TCPP) (k(OH.TBP) = 6.40 × 10~9, k(COH.TCEP) = 5.60 × 10~8, and k(oh,tcpp = 1 98 × 10~8 M~(-1) s~(-1)). A two-stage process was used to test the validity of the determined k(OH)for TBEP and the fastest reacting halogenated alkyl phosphate, TCEP. First, ·OH oxidation of TCEP and TBEP, in competition with nitrobenzene was measured in ozonated hydrogen peroxide solutions. Applying multiple regression analysis, it was determined that the UV/H_2O_2 and LV H_2O_2 data sets were statistically identical for each compound. The subsequent validated k(OH) were used to predict TCEP and TBEP photodegradation in neutral pH, model surface water after chemical oxidant addition and UV irradiation (up to 1000 mJ/cm~2). The insignificant difference between the predicted TBEP and TCEP photodegradation and a best-fit of the first-order exponential decay function to the observed TBEP and TCEP concentrations with increasing UV fluence was further evidence of the validity of the determined k(OH). TBEP oxidation rates were similar in the surface waters tested. Substantial TCEP oxidation in the model surface water required a significant increase in initial H_2O_2.
机译：磷酸三烷基酯是一类人为有机物，通常由于其作为阻燃剂，增塑剂和溶剂的应用而广泛存在于欧洲和北美的地表水中。对四种磷酸三烷基酯进行了评估，以确定与紫外线和臭氧产生的·OH在水中的二级反应速率。磷酸三（2-丁氧基乙基）酯（TBEP）与·OH反应最快（k_（OH.TBEP）= 1.03×10〜10 M〜（-1）s〜（-1）），随后依次是磷酸三丁酯（ TBP），磷酸三（2-氯乙基）酯（TCEP）和磷酸三（2-氯异丙基）酯（TCP（k（OH.TBP）= 6.40×10〜9，k（COH.TCEP）= 5.60×10〜） 8，k（oh，tcpp = 1 98×10〜8 M〜（-1）s〜（-1））。采用两步法测试了确定的TBEP和k（OH）的有效性。反应最快的卤代磷酸烷基酯TCEP。首先，在臭氧化的过氧化氢溶液中测量TCEP和TBEP与硝基苯竞争的·OH氧化，应用多元回归分析，确定UV / H_2O_2和LV H_2O_2数据集为每种化合物在统计学上都相同，随后验证的k（OH）用来预测TCEP和TBEP在中性pH下的光降解，模拟添加化学氧化剂和UV照射（最高1000 mJ / cm〜2）后的地表水。预测的TBEP和TCEP的光降解以及随着紫外线通量的增加，一阶指数衰减函数与观察到的TBEP和TCEP浓度的最佳拟合进一步证明了所确定的k（OH）的有效性。在测试的地表水中，TBEP氧化速率相似。模型表面水中的大量TCEP氧化需要显着增加初始H_2O_2。

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  • 来源
    《Environmental Science & Technology》 |2009年第8期|2937-2942|共6页
  • 作者

    MICHAEL J. WATTS; KARL G. LINDEN;

  • 作者单位

    Department of Civil and Environmental Engineering, Florida State University, Tallahassee, Florida 32310;

    Department of Civil, Environmental, and Architectural Engineering, 428 UCB, University of Colorado-Boulder, Boulder, Colorado 80309;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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