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用于天然淡水中 99TcO4-定量的稳定且选择性的闪烁阴离子交换传感器。

Stable and selective scintillating anion-exchange sensors for quantification of 99TcO4- in natural freshwaters.

机构信息

Department of Analytical Chemistry and Environmental Control, Atomic Energy Authority, Egypt.

出版信息

J Environ Radioact. 2013 Dec;126:156-64. doi: 10.1016/j.jenvrad.2013.07.025. Epub 2013 Sep 4.

DOI:10.1016/j.jenvrad.2013.07.025
PMID:24012764
Abstract

New dual functionality scintillating anion-exchange resins were developed for selective determination of (99)TcO4(-) in various natural freshwater samples. Stable scintillating particles were formed by preparing the vinyl monomer 2-[4-(4'-vinylbiphenylyl)]-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (vPBD), starting with the commercial organic flour TBut-PBD and its subsequent copolymerization with styrene, divinylbenzene, and p-chloromethylstyrene mixture. To integrate the radiochemical separation and radiometric detection steps within the same bead, the chloromethyl groups of the scintillating resins were subjected to amination reactions with dioctylamine (DOA) and trioctylamine (TOA). On-line quantification of (99)TcO4(-) was achieved by packing the scintillating anion-exchange resin into Teflon tubing for quantification by a flow scintillation analyzer (FSA). The two functionalized resins were selective for pertechnetate over the common anions in natural freshwaters, especially Cl(-) and SO4(2-) with up to 1000 ppm and with up to 10 ppm I(-) and Cr2O7(2-). The uptake efficiency of the TOA sensor decreased from 97.88% to 85.08% in well water and river water, respectively, while the counting efficiency was almost constant (69.50%). The DOA performance showed lower efficiency in the two water types relative to TOA. On the other hand, the DOA sensor could be regenerated by 5 M HNO3 for reuse at least four times without losing its chemical or optical performance. The detection limit was 1.45 Bq which could be achieved by loading 45 mL from well and tap water containing the maximum contaminant level (MCL) of (99)Tc (33 Bq/L).

摘要

新型双重功能闪烁阴离子交换树脂被开发用于选择性测定各种天然淡水样品中的 (99)TcO4(-)。通过制备乙烯基单体 2-[4-(4'-联苯基) ]-5-(4-叔丁基苯基)-1,3,4-恶二唑 (vPBD),从商业有机粉末 TBut-PBD 开始,并随后与苯乙烯、二乙烯基苯和对氯甲基苯乙烯混合物共聚,形成稳定的闪烁颗粒。为了将放射化学分离和放射性检测步骤集成在同一珠粒内,将闪烁树脂的氯甲基基团与二辛胺 (DOA) 和三辛胺 (TOA) 进行胺化反应。通过将闪烁阴离子交换树脂填充到特氟龙管中,并用流动闪烁分析仪 (FSA) 进行定量,实现了 (99)TcO4(-) 的在线定量。两种功能化树脂对天然淡水中的高氯酸盐具有选择性,相对于常见阴离子(尤其是 Cl(-) 和 SO4(2-)),其选择性高达 1000 ppm,对 I(-) 和 Cr2O7(2-) 的选择性高达 10 ppm。在井水和河水两种水中,TOA 传感器的摄取效率分别从 97.88%降至 85.08%,而计数效率几乎保持不变(69.50%)。DOA 性能在这两种水类型中的效率相对较低。另一方面,DOA 传感器可以通过 5 M HNO3 再生,至少可重复使用四次而不会失去其化学或光学性能。检测限为 1.45 Bq,通过从井水和自来水中加载 45 mL 即可达到,井水和自来水中 (99)Tc 的最大污染物水平 (MCL) 为 33 Bq/L。

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