新型有机磷阻燃剂RDP及其副产物TPHP在水环境中的分布及水-沉积物界面行为

Resorcinol bis(diphenylphosphate)(RDP) is a halogen-free organophosphorus flame retardant (OPFRs) that are considered to be suitable replacements for the banned brominated flame retardants (BFRs). After the phase-out of some BFRs, RDP have been increasingly used to comply with flammability standards in consumer products. The environmental problem caused by RDP should be paid more attentions. Triphenyl phosphate (TPHP) is a major by-product in RDP productions. TPHP as well as RDP have high aquatic toxicity. The existing of TPHP could not be neglect when we study the environmental behaviors of RDP. Therefore, we selected RDP and TPHP as objectives.. The presence of RDP and TPHP in environmental samples or in products has been scarcely reported. Since no enough data could be found in the literature on environmental levels of RDP and TPHP, it is impossible to calculate their environmental risk. So this study investigate the distribution of RDP and TPHP in water environment to provides data support for further study on their environmental risk.. The water-sediment interfacial behavior of organic compounds is very important to predict the migration and transformation of them and formulate reasonable regulatory program. Therefore, we will study the adsorption and desorption mechanism of RDP and TPHP to reveal their water-sediment interfacial behavior. Besides the influence mechanism of environmental factors, we will deduce the expression of surface fractal dimension (SFD) for size fractions of the sediment. Based on the expression, the SFD value of different size fractions of the sediment will be calculated. Combine these with the distribution characteristics of RDP and TPHP in different size fractions of the sediment，we will conclude the influence mechanism of particle size on adsorption and desorption. Meanwhile, the adsorption and desorption of RDP and TPHP on different humus and humus-sediment complexes will be investigated. Characterization of the humus-sediment complexes and suspensions will be conducted by utilizing multiple analytical techniques to reveal the influence of humus on the adsorption and desorption mechanism of RDP and TPHP. This study contributes to predict the migration and transformation of RDP and TPHP. It is very helpful to evaluate the environmental risk and formulate a reasonable regulatory program of RDP and TPHP.

间苯二酚双(二苯基磷酸酯)(RDP)是溴代阻燃剂(BFRs)最适合的替代品之一，磷酸三苯酯(TPHP)是RDP产品的主要副产物。随着BFRs逐渐被禁用，RDP及其副产物将被大量生产和使用，从而被引入环境，造成环境问题。因此，我们选择RDP和TPHP为研究目标。. 目前关于RDP和TPHP水环境行为的研究很少。本项目将对二者在水环境多界面中的分布进行调查，为评价其生态风险提供数据支持。另外还将针对RDP和TPHP在沉积物中的吸附解吸机制展开研究。除了考察环境因素的影响之外，运用分形分维理论对吸附模型进行校正，以更真实的反映微界面吸附过程，结合二者在不同粒径沉积物上的分配特征，揭示沉积物粒径对界面行为的影响。同时结合吸附解吸实验结果和各种表征技术，揭示腐殖质对沉积物吸附目标物的影响机制，为揭示RDP和TPHP的水-沉积物界面行为，预测二者迁移转化规律、制定合理的监管政策提供帮助。

随着相关产品的生产和使用，OPEs大量释放到环境中，其可能造成的环境问题应引起广泛注意。但是目前对OPEs环境行为的研究还相对较少，尤其是对一些新型的有机磷阻燃剂的环境行为的研究就更为少见。RDP及其副产物TPHP和BDP作为溴代阻燃剂最适合的替代品之一，其生产和使用量必将大幅增长，应引起重视。但是目前关于RDP，BDP的水环境分布和水-沉积物界面分配行为的研究非常少见。因此，本项目在优化RDP，BDP和TPHP环境样品检测方法的基础上，对包括这三种物质在内的多种OPEs在海河和太湖流域的分布和分配行为，以及其可能来源进行了分析，并对其吸附行为进行了初步探讨。为进一步研究OPEs的迁移行为和准确评估OPEs的生态风险提供数据支撑。目前本项目获得的主要结论如下：. 1) 建立了检测包括RDP和BDP在内的多种OPEs的样品前处理方法，空白加标回收率为水相43.5-125%，沉积物74.1-131%，SPM55.6-116%；基质加标回收率为水相41.1-126%，沉积物56.9-128%，SPM44.8-124%，可以用于环境样品中OPEs的定性定量分析。. 2）海河流域水、沉积物和SPM中ΣOPEs为80.1-777ng/L，18.9-86.5ng/g dw，6.40-234ng/g dw。水相中，氯代OPEs占绝对主导地位，但在沉积物和SPM中，氯代OPEs占比下降，烷基类OPEs的比例有所升高。太湖水和沉积物中ΣOPEs分别为166-1530ng/L和2.82-47.5ng/g dw，污染程度呈现从西北向东南逐渐降低的趋势。OPEs制造业和周边机场可能是两个研究区域OPEs的重要来源。. 3）计算出水-沉积物间OPEs的LogKoc为3.51-5.21(海河流域)，3.09-6.92(太湖)；水-SPM间LogKoc为3.31-4.44（海河），LogKd为2.02-5.94（太湖）。疏水性在OPEs的水-沉积物界面分配行为中起重要作用。此外，OPEs的logKoc还与OPEs的化学结构有关。天然水体中pH和电导率等不是影响OPEs分配的主要因素。. 4）对TPHP的吸附行为展开研究，获得了相关的吸附动力学和热力学参数，发现TPHP吸附属于放热过程，随着温度的增加，TPHP吸附呈现下降趋势。