Article thumbnail

Development of sorbent tube-thermal desorption based quantitation method for airborne phthalates and its application to environmental analysis

By ?????????

Abstract

In this thesis, the feasibility of sorbent tube (ST)-thermal desorption (TD)-gas chromatography (GC)-mass spectrometry (MS) analysis system was investigated for the quantitation of phthalates present in air. In an effort to improve the quantitation procedure for phthalates, I investigated the quantitation techniques for airborne phthalates by focusing on the effect of various sampling parameters on ST/TD-GC/MS applications. Then, the applicability of each ST-TD method was explored further by quantifying diverse phthalate compounds produced from actual environmental samples (five types of plastic/rubber products) under three different temperature conditions. In chapter 2, a novel quantitation method was developed to facilitate the simple and effective sampling and analysis of phthalates in air based on a sorbent tube (ST)-thermal desorption (TD)-gas chromatography (GC)-mass spectrometry (MS) system combination. Performance of the thermal desorption-based analysis was assessed using three different sorbent combinations: [1] quartz wool (QW), [2] glass wool (GW), and [3] quartz wool plus Tenax TA (QWTN) in terms of relative recovery in reference to a direct injection method. There was no significant difference in the average recovery for seven target phthalates between different sorbent tube types (QW, 70.2 ?? 4.28GW, 73.2 ?? 8.8and QWTN, 72.5 ?? 5.02%). However, recovery of phthalates in each sorbent tube type was different based on physicochemical properties of the compound (e.g., molecular weight and boiling point). The recovery of the QW tube was high for dimethyl phthalate and diethyl phthalate relative to other sorbent tubes, while that of the GW tube exhibited greater values for dibutyl phthalate, benzyl butyl phthalate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) phthalate, and di-n-octyl phthalate. The simple sorbent tube-thermal desorption approach was demonstrated to be feasible for the quantitation of seven phthalates present at 0.45 to 24.5 ng m-3 levels in actual air samples (20 L). In chapter 3, the adsorption properties of various sorbent materials were investigated to assess the factors causing analytical biases in the ST-based sampling of airborne phthalates. To this end, the recovery of phthalates was assessed in relation to four key sampling parameters: (1) three types of sorbent materials (QW, GW, and QWTN), (2) the concentration levels of phthalate standards, (3) purge flow rate, and (4) purge volume for analysis based on a ST-TD-GC-MS system. Among these parameters, the type of ST was the most influential in determining the recovery of phthalates. For a given ST type, the recovery of phthalates tended to improve with increases in the concentration level of standards. In case of QW and QWTN tubes, the breakthrough of phthalates was not observed up to the maximum purge volume (100 L) tested in this workhowever, in the case of GW, the recovery decreased drastically to 60% even at a purge volume of 1 L for low molecular weight compounds (dimethyl phthalalte). The results of this study demonstrated that accurate analysis of airborne phthalates should be achieved through proper control of key sampling parameters, particularly the choice of sorbent material. In chapter 4, emission concentrations and fluxes of airborne phthalates were measured from five types of polyvinyl chloride (PVC) consumer products (vinyl flooring, wallcovering, children???s toy, yoga mat, and edge protector) using a small chamber system made of impinger. To this end, airborne phthalates released from each of those PVC samples were collected using sorbent (QWTN) tubes at three different temperature control intervals (0, 3, and 6 hours) under varying temperature conditions (25, 40, and 90???) by the combination of TD and GC/MS system. Based on this study, a total of 11 phthalate compounds released from each of five PVC products were determined. The emission concentrations of most phthalate compounds were seen to increase systematically with the heating of PVC samples at each of three control intervals. However, concentrations of phthalates were generally maintained at constant levels as control duration was extended (up to 6 hrs) at lower temperatures (25 and 40???). In contrast, their concentrations decreased gradually through time when heated at the maximum temperature of analysis (90???). To facilitate the comparison of phthalate emissions between different PVC samples, their flux values were also examined as total phthalate by summing average fluxes of all 11 phthalates generated during the control period of 6 hrs. The information regarding the phthalate composition and their emission patterns varied dynamically with such variables as types of PVC samples, controlled temperatures, and duration of control.??? ??????????????? ??????????????? (sorbent tube: ST)/????????? (thermal desorption: TD)-??????????????????????????? (gas chromatography: GC)/??????????????? (mass spectrometry: MS) ???????????? ????????? ?????? ??? ??????????????? ???????????? ?????????????????? ???????????????. ???????????? ??????????????????????????? (semi-volatile organic compounds: SVOCs) ??? ????????? ?????????????????? ?????????????????? ??????????????? ?????????, ST/TD-GC/MS ????????? ????????? ?????? ??? ??????????????? ???????????? ??????????????? ????????????, ??????????????? ????????? ??? ??? ?????? ????????? ???????????? ???????????? ?????? ???????????????. ??? ???, ???????????? ??? 5?????? ???????????? (???????????? ??? ?????? ??????)????????? ???????????? ??????????????? ???????????? ?????? ??? ??????????????? ??????, ??? ???????????? ????????? ST/TD-GC/MS ????????? ?????? ???????????? ??????????????? ?????????. ??? 2???????????? ???????????? ???????????? ??????????????? ???????????? ?????? ??? ???????????? ???????????? ?????????, ST/TD-GC/MS ????????? ????????? ??????????????? ???????????? ???????????? ????????? ??????????????? ?????????. ?????? ?????????, 3?????? ?????? (Quartz wool: QW, Glass wool: GW, Quartz wool and Tenax TA: QWTN)??? ST??? ???????????? direct injection (DI) ????????? ????????? ST/TD ????????? ???????????? ???????????????. ??? ??????, 7?????? ??????????????? ???????????? ?????? ???????????? 70.2??4.28 (QW), 73.2?? 8.85 (GW), 72.5??5.02% (QWTN)?????? ????????? ????????? ?????? ??? ????????? ????????? ?????? ?????????. ????????? ?????? ???????????? ??????????????? ????????? ?????? ST??? ???????????? ?????? 10% ?????? ?????? ?????? ?????? ????????? ??? ?????????. dimethyl phthalate (DMP)??? diethyl phthalate (DEP) ???????????? ??????, QW tube?????? ???????????? ??????????????? ????????????. ?????????, ????????? dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), di(2-ethylhexyl) adipate (DEHA), di(2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DnOP) ???????????? ??????, GW tube?????? ?????? ???????????? ???????????????. ?????? ?????? ????????? ???????????? ???????????? (?????????, ?????????) ??? ???????????? ?????? (20 L)??? ???????????? ??? ??????, ?????? ??? ??????????????? ???????????? ?????? ?????? ?????? ???????????? ??????????????? ???????????? ??? ????????? ???????????? ????????? ?????? ???????????? ????????? ??? ?????????. ??????????????? ?????? ??????????????? ????????? ?????? ???????????? ????????? ???????????? ???????????? ????????? ??????????????? ???????????? ?????? ???????????? ???????????? ??? ?????? ????????? ????????????. ??? 3???????????? ??????????????? (ST)??? ???????????? ?????? ??? ??????????????? ???????????? ????????? ???, ????????? ???????????? ????????? ?????? ?????????????????? ??????????????? ?????? ??????????????? ?????????. ?????? ?????????, 3?????? ?????? (QW, GW, QWTN)??? ST??? ???????????? 3?????? ???????????? ?????? (???????????? ??????, ???????????? ??????, ???????????? ??????)??? ????????? ST??? ???????????? ???????????????. ?????? ?????? ???????????? ?????????????????? ????????? ??????????????? ???????????? TD ???????????? ????????? GC/MS??? ???????????????. ??? 4????????? ????????? (ST ??????, ???????????? ??????, ???????????? ??????, ???????????? ??????) ????????? ST??? ???????????? ?????? ??? ????????? ????????? ????????? ST ????????? ????????? ????????????. ????????? ????????? ST ???????????? ???????????? ????????? ??????????????? ????????? ???????????? ???????????? ?????? ??? ?????????. QW, QWTN tube????????? ?????? ??????????????? ???????????? ????????? ???????????? ????????? ???????????? ?????? ?????? ????????? ???????????? ?????????. ?????????, GW tube????????? 1 L??? ??????????????? ???????????? ????????? (DMP, DEP)??? ?????? ????????? ??????????????? ????????????, ???????????? 24.6~84.4% ???????????? ???????????????. ??????????????? ???????????? ????????? ST??? ???????????? ??? ????????? ????????? ?????? ???????????? ???????????????. ????????? QWTN tube????????? ???????????? ????????? ????????? ????????? ??????????????? ????????? ????????? ????????????, ???????????? ????????? 0.2 L min-1??? ???, 1 L min-1?????? ???????????? ?????? ?????? ?????? ??? ??? ?????????. ????????? ST??? ???????????? ?????? ??? ?????????????????? ????????? ???, ???????????? ????????? ??? ??? ?????? ?????? ?????? ????????? ???????????? ?????? ????????? ????????? ????????? ????????????. ??? 4???????????? ???????????? ???????????? ?????? ????????? ????????????, 5?????? PVC ?????? (?????? ?????????, ??????, ?????????, ?????? ??????, ????????? ?????????)?????? ???????????? ??????????????? ???????????? ?????? ????????? ???????????? ???????????????. ?????? ?????????, ????????? PVC ????????? ???????????? ????????? ???, 3?????? ???????????? (25, 40, 90???) ??? ???????????? ?????? (0, 3, 6??????)??? ?????? ???????????? ??????????????? ???????????? QWTN tube??? ???????????? TD-GC/MS ??????????????? ?????????????????????. ??? ???????????? ????????? 5?????? PVC ???????????? ??? 11?????? ????????? ??????????????? ???????????? ????????? ??? ?????????. ???????????? ????????? ????????? ??????????????? PVC ????????? ????????? ??????????????? ????????? ?????????????????? ?????? ????????? ???????????? ????????? ?????????. ?????????, PVC ????????? ????????? ?????? ?????? (25, 40???)??? ????????? ???????????? 6????????? ???????????? ?????? ?????????????????? ????????? ????????? ????????? ????????? ???????????????. ?????????, PVC ????????? ????????? 90????????? ????????????, PVC ???????????? ????????? ?????????????????? ????????? ????????? ?????? ????????? ???????????? ????????? ????????????. PVC ????????? ????????? ?????? ?????????????????? ???????????? ?????????????????? ?????????, 6?????? ?????? ????????? 11?????? ??????????????? ???????????? ?????? ????????? (?????? ?????? ??? ?????? ?????? ??? ????????? ?????????????????? ??????) ?????? ????????? ???????????? ??? ????????? ?????? ???????????????. ??? ??????, PVC ????????? ??????, ????????????, ???????????? ????????? ?????? ??????????????? ???????????? ?????? ????????? ???????????? ???????????? ?????? ????????? ??? ?????????. ??? ????????????????????? ST/TD-GC/MS ????????? ????????? ?????? ??? ??????????????? ???????????? ?????????????????? ????????????, ????????? ???????????? (????????????, ????????????, ????????? ???????????? ??????)??? ????????? ?????? ???????????? ???????????????. ST/TD ????????? ????????? ????????? ????????? ???????????????????????? ???????????? ????????? ????????? ???????????? ??? ?????????. ?????? ???~?????? L??? ???????????????????????? ??????????????? ???????????? ???????????? ??? ????????? ????????? ?????? ??? ?????? ???????????? ?????????????????? ????????????. ?????? ?????? ST/TD ????????? ?????????????????? ????????? ????????? ?????? ??????????????????????????? (polycyclic aromatic hydrocarbons: PAHs), ???????????? ???????????? (polychlorinated biphenyls: PCBs), ??????????????????????????? (persistent organic pollutants: POPs) ??? SVOCs??? ???????????? ??? ???????????? ?????? ????????? ????????? ????????????.Docto

Publisher: ???????????????
Year: 2017
OAI identifier: oai:repository.hanyang.ac.kr:20.500.11754/33104
Provided by: HANYANG Repository
Download PDF:
Sorry, we are unable to provide the full text but you may find it at the following location(s):
  • http://hdl.handle.net/20.500.1... (external link)
  • http://dcollection.hanyang.ac.... (external link)
  • Suggested articles


    To submit an update or takedown request for this paper, please submit an Update/Correction/Removal Request.