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TWI859415B - Sampler for collecting personal exposure measurements of per- and polyfluoroalkyl compounds - Google Patents

Sampler for collecting personal exposure measurements of per- and polyfluoroalkyl compounds Download PDF

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TWI859415B
TWI859415B TW110105028A TW110105028A TWI859415B TW I859415 B TWI859415 B TW I859415B TW 110105028 A TW110105028 A TW 110105028A TW 110105028 A TW110105028 A TW 110105028A TW I859415 B TWI859415 B TW I859415B
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activated carbon
perfluoroalkyl
sampler
personal exposure
compounds
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TW202136736A (en
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山下信義
谷保佐知
高阪務
横井誠
堀千春
島村紘大
浅野拓也
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國立研究開發法人產業技術總合研究所
日商二村化學股份有限公司
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Abstract

本發明課題為提供一種個人暴露測量用全氟及多氟烷基化合物採樣器,其係可高效且可脫離地收集存在於工作環境等的大氣中的全氟及多氟烷基化合物,並且可攜帶、操作方便。 The subject of the invention is to provide a perfluoroalkyl compound sampler for personal exposure measurement, which can efficiently and removably collect perfluoroalkyl compounds in the atmosphere of the working environment, etc., and is portable and easy to operate.

解決手段為一種用來測量個人暴露量的可攜式全氟及多氟烷基化合物採樣器,其係具備可脫離地吸附全氟及多氟烷基化合物之以活性碳為主要吸附劑的活性碳過濾器部,其特徵為:活性碳的BET比表面積為900m2/g以上,並且活性碳過濾器部在風速0.5m/sec條件下的壓力損失未達6kPa。 The solution is a portable PFAS sampler for measuring personal exposure, which is equipped with an activated carbon filter section with activated carbon as the main adsorbent that can releasably adsorb PFAS. The characteristics are: the BET specific surface area of the activated carbon is above 900 m2 /g, and the pressure loss of the activated carbon filter section under the wind speed of 0.5m/sec is less than 6kPa.

Description

用於收集全氟及多氟烷基化合物之個人暴露測量用採樣器 Sampler for collecting personal exposure measurements of perfluorinated and polyfluorinated alkyl compounds

本發明關於一種用於收集全氟及多氟烷基化合物之採樣器,可收集大氣中的全氟及多氟烷基化合物,尤其是用來測定個人暴露量的可攜式個人用採樣器。The present invention relates to a sampler for collecting perfluorinated and polyfluorinated alkyl compounds, which can collect perfluorinated and polyfluorinated alkyl compounds in the atmosphere, and is particularly a portable personal sampler for measuring personal exposure.

全氟及多氟烷基化合物是具有高熱安定性、高化學安定性、高表面活性的氟化脂肪族化合物類。全氟及多氟烷基化合物發揮出前述特性,被廣泛使用在塗料或包裝材、液態滅火劑等的工業用途及化學用途等。Perfluoroalkyl and polyfluoroalkyl compounds are fluorinated aliphatic compounds with high thermal stability, high chemical stability, and high surface activity. Due to the above characteristics, perfluoroalkyl and polyfluoroalkyl compounds are widely used in industrial and chemical applications such as coatings, packaging materials, and liquid fire extinguishers.

一部分的全氟及多氟烷基化合物是安定性非常高的化學物質,因此在釋放到環境中之後,在自然條件下不易分解。因此近年來認識到全氟及多氟烷基化合物是殘留性有機污染物質(POPs),由2010年開始,在和殘留性有機物污染物質有關的斯德哥爾摩公約(POPs公約)之中,規範了全氟辛烷磺酸(PFOS)(IUPAC名:1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十七氟辛烷-1-磺酸)的製造或使用。Some PFAS are very stable chemicals, so they are not easily decomposed under natural conditions after being released into the environment. Therefore, in recent years, PFAS have been recognized as residual organic pollutants (POPs). Since 2010, the Stockholm Convention on Residual Organic Pollutants (POPs Convention) has regulated the production or use of perfluorooctane sulfonic acid (PFOS) (IUPAC name: 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonic acid).

此外,全氟烷基化合物具有完全氟化的直鏈烷基,是由化學式(ii)所表示的物質。已知有例如全氟辛烷磺酸(PFOS)或全氟辛酸(PFOA)(IUPAC名: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十五氟辛酸)等。In addition, the perfluoroalkyl compound has a completely fluorinated linear alkyl group and is represented by the chemical formula (ii). Examples of known perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) (IUPAC name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid) are shown.

表示多氟烷基化合物的烷基中一部分的氫被氟取代,是由化學式(iii)所表示的物質。已知有例如氟調聚醇等。The polyfluoroalkyl compound is a compound in which a part of hydrogen in the alkyl group is substituted with fluorine, and is represented by the chemical formula (iii). For example, fluorotelomer alcohols are known.

像這樣,全氟及多氟烷基化合物會持續殘存在自然界(水中,土壤中,大氣中),因此正在檢討如何來確立全氟及多氟烷基化合物的定量測試方法。定量測試方法的檢討課題為開發出具有全氟及多氟烷基化合物的高收集、吸附及脫離性能的採樣器。使含有微量全氟及多氟烷基化合物的試樣空氣通過,並將試樣空氣中所含的各種形態(粒子吸附性、半揮發性、揮發性)的全氟及多氟烷基化合物收集或吸附,藉由萃取步驟使該化合物由收集劑或吸附劑脫離至萃取液中,並且加以濃縮。濃縮後,以LC-MS/MS或GC-MS/MS等的測定裝置作定量測定,可進行試樣中所含的全氟及多氟烷基化合物的濃度測定。As such, PFASs continue to exist in nature (water, soil, and atmosphere), so the establishment of a quantitative test method for PFASs is under review. The topic of the review of the quantitative test method is to develop a sampler with high collection, adsorption, and desorption performance for PFASs. Sample air containing trace amounts of PFASs is passed through, and various forms of PFASs (particle adsorption, semi-volatile, volatile) contained in the sample air are collected or adsorbed, and the compounds are desorbed from the collector or adsorbent into the extract by an extraction step and concentrated. After concentration, the concentration of per- and polyfluoroalkyl compounds in the sample can be measured by quantitative analysis using a measuring device such as LC-MS/MS or GC-MS/MS.

為了測定大氣中的全氟及多氟烷基化合物,已知有使用高容量空氣採樣器的方法(參考例如非專利文獻1)。在此方法之中,在高容量空氣採樣器內部裝設由石英纖維濾紙等的微細纖維所形成的濾紙等,並對該採樣器通氣一定時間,採取大氣中懸浮粒子以測定大氣中懸浮粒子中所含的PFOS。In order to measure perfluorinated and polyfluorinated alkyl compounds in the atmosphere, a method using a high-capacity air sampler is known (see, for example, non-patent document 1). In this method, a filter paper formed of fine fibers such as quartz fiber filter paper is installed inside the high-capacity air sampler, and the sampler is ventilated for a certain period of time to sample suspended particles in the atmosphere to measure PFOS contained in the suspended particles in the atmosphere.

但是,對濾紙通氣所收集到的物質,會受限於吸附於大氣中的懸浮粒子的全氟烷基化合物的PFOS、PFOA等的非揮發性離子化合物。無法以該採樣器收集的全氟及多氟烷基化合物,可列舉具有揮發性的全氟及多氟烷基化合物。揮發性的全氟及多氟烷基化合物會通過濾紙,因此無法進行定量測定。However, the substances collected by ventilation of the filter paper are limited to non-volatile ionic compounds such as PFOS and PFOA of perfluoroalkyl compounds adsorbed on suspended particles in the atmosphere. Perfluoroalkyl compounds that cannot be collected by this sampler include volatile perfluoroalkyl compounds. Volatile perfluoroalkyl compounds pass through the filter paper and therefore cannot be quantitatively measured.

因此希望有一種採樣器,可收集無法藉由前述採樣器收集且大氣中懸浮粒子中所沒有的揮發性多氟烷基化合物等,以及以其他形態存在的全氟及多氟烷基化合物。Therefore, it is desired to have a sampler that can collect volatile polyfluoroalkyl compounds that cannot be collected by the above samplers and are not present in the suspended particles in the atmosphere, as well as perfluoro and polyfluoroalkyl compounds that exist in other forms.

另外,揮發性全氟及多氟烷基化合物的收集劑是使用二氧化矽膠體系收集劑等。例如有文獻提出由環糊精聚合物所形成的有機氟系化合物吸附劑(專利文獻1)。該吸附劑是特化為只吸附無法讓該化合物脫離,因此不適合作為定量測定所使用的收集材來使用。另外,環糊精聚合物為粉狀或微粒子狀,操作性差,液體或氣體通過時阻力高,會有微粉末往次級管路流出的風險等的問題。以這種方式,藉由現存的吸附劑無法充分收集揮發性全氟及多氟烷基化合物,會有無法正確地定量測定的問題。In addition, the collector of volatile perfluoroalkyl and polyfluoroalkyl compounds uses a silica colloid system collector and the like. For example, a document proposes an organic fluorine compound adsorbent formed by a cyclodextrin polymer (Patent Document 1). This adsorbent is specialized to only adsorb and cannot release the compound, so it is not suitable for use as a collector for quantitative measurement. In addition, cyclodextrin polymers are in powder or microparticle form, which has poor operability, high resistance when liquid or gas passes through, and there is a risk of fine powder flowing out to the secondary pipeline. In this way, volatile perfluoroalkyl and polyfluoroalkyl compounds cannot be fully collected by existing adsorbents, and there is a problem that quantitative measurement cannot be performed accurately.

此外,目前在日本國內,為了防止勞工的健康障礙,根據勞動安全衛生法的規定,需進行工作環境中的有害物質或粉塵的濃度測定及其結果的評估。工作環境測定是藉由所謂的A測定及B測定來進行,是在各單位工作場所以等間隔設置測定點進行測定。In addition, in order to prevent health problems among workers, the Labor Safety and Health Law currently requires the measurement of the concentration of harmful substances or dust in the workplace and the evaluation of the results. The workplace environment measurement is carried out through the so-called A measurement and B measurement, which are performed by setting up measurement points at equal intervals in each unit's workplace.

在實施風險評估時,希望採用將由該測定方法所測得的工作地點的等的空氣中的化學物質濃度等與工作者的暴露極限加以比較的方法,而正在檢討使用個人用採樣器來作個人暴露測量。When conducting risk assessment, it is desirable to compare the concentration of chemical substances in the air at the workplace, etc., measured by this method, with the worker's exposure limit, and the use of personal samplers for personal exposure measurement is being reviewed.

使用個人用採樣器的優點,可列舉在有害物質的產生源會移動的情況或在有害物質的產生源與工作者之間難以設置測定點的情況皆可正確地測定。其他優點還可列舉在操作有害性高的物質的情況等,可在工作者的呼吸區域附近設置採樣器,正確地進行測定。The advantages of using a personal sampler include accurate measurement when the source of harmful substances is moving or when it is difficult to set up a measurement point between the source of harmful substances and the worker. Other advantages include setting up the sampler near the worker's breathing zone to accurately measure when handling highly harmful substances.

個人暴露測量的方法可大致區別成被動式採樣法與主動式採樣法兩種。被動式採樣法是在工作者的呼吸區域裝設由收集材所形成的批次式之類的測定器具,利用分子擴散來收集對象物質,由該測定器具中的收集材萃取出對象物質並進行測定,以測定工作者的暴露量。主動式採樣法是工作者身上裝設包含對象物質收集過濾器及吸引幫浦的採樣器然後做工作,在工作後對藉由採樣器內的收集過濾器所收集到的對象物質量進行測定。 The methods of measuring personal exposure can be roughly divided into two types: passive sampling method and active sampling method. The passive sampling method is to install a batch type measuring instrument formed by a collecting material in the breathing area of the worker, use molecular diffusion to collect the target substance, extract the target substance from the collecting material in the measuring instrument and measure it to measure the worker's exposure. The active sampling method is to install a sampler containing a target substance collection filter and a suction pump on the worker and then do the work. After the work, the amount of the target substance collected by the collection filter in the sampler is measured.

在主動式採樣法之中,是在安裝個人用採樣器的狀態下做工作,因此從攜帶性或減輕工作員負擔的觀點看來,希望使用小型的吸引幫浦,然而收集過濾器所造成的壓力損失會成為問題。為了充分發揮收集性能,收集過濾器必須具備足量的收集用材料,因此無法避免吸引幫浦的大型化,導致攜帶性的降低,而且對工作者負擔增加的問題會發生。 In the active sampling method, the work is done with a personal sampler installed, so from the perspective of portability or reducing the burden on workers, it is desirable to use a small suction pump, but the pressure loss caused by the collection filter becomes a problem. In order to fully exert the collection performance, the collection filter must have a sufficient amount of collection material, so it is inevitable that the suction pump will be enlarged, resulting in reduced portability and increased burden on workers.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2012-101159號公報 [Patent Document 1] Japanese Patent Publication No. 2012-101159

[非專利文獻] [Non-patent literature]

[非專利文獻1]小谷野道子等人所著之「都市大氣中的全氟辛烷磺酸(PFOS)濃度的週間變化」大氣環境學會誌 第45卷 第6號 2010年11月10日,p.279-282 [Non-patent document 1] Michiko Otani et al., "Cyclic Variation of Perfluorooctane Sulfonate (PFOS) Concentrations in Urban Atmosphere", Journal of the Atmospheric Environment Society, Vol. 45, No. 6, November 10, 2010, p. 279-282

本發明是鑑於前述問題點而完成,提供一種可攜帶且操作方便的個人暴露測量用全氟及多氟烷基化合物採樣器,可高效且可脫離地收集存在於工作環境等的大氣中的全氟及多氟烷基化合物。 The present invention is made in view of the above-mentioned problems, and provides a portable and easy-to-operate perfluoroalkyl compound sampler for personal exposure measurement, which can efficiently and removably collect perfluoroalkyl compounds in the atmosphere of the working environment, etc.

亦即,第1發明是關於一種個人暴露測量用全氟及多氟烷基化合物採樣器,其係具備可脫離地吸附全氟及多氟烷基化合物之以活性碳為主要吸附劑的活性碳過濾器部之用來測量個人暴露量的可攜式全氟及多氟烷基化合物採樣器,其特徵為:前述活性碳的BET比表面積為900m2/g以上,並且前述活性碳過濾器部在風速0.5m/sec條件下的壓力損失未達6kPa。 That is, the first invention is a perfluoroalkyl compound sampler for measuring personal exposure, which is a portable perfluoroalkyl compound sampler for measuring personal exposure, and has an activated carbon filter portion with activated carbon as a main adsorbent that can releasably adsorb perfluoroalkyl compounds. The characteristics of the perfluoroalkyl compound sampler are as follows: the BET specific surface area of the activated carbon is 900m2 /g or more, and the pressure loss of the activated carbon filter portion under a wind speed of 0.5m/sec does not reach 6kPa.

第2發明是關於如第1發明之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳之1nm以下的微孔容積之和(Vmic)為0.35cm3/g以上。 The second invention is a perfluoroalkyl compound sampler for personal exposure measurement according to the first invention, wherein the sum of the micropore volumes of the activated carbon with a diameter of less than 1 nm (V mic ) is 0.35 cm 3 /g or more.

第3發明是關於如第1或2發明之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳之2~60nm以下的中孔容積之和(Vmet)為0.03cm3/g以上。 The third invention is a perfluoroalkyl compound sampler for personal exposure measurement according to the first or second invention, wherein the sum of the mesopore volumes of the activated carbon below 2 to 60 nm (V met ) is 0.03 cm 3 /g or more.

第4發明是如第1至3發明中任一者之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳之下述(i)式規定的前述微孔容積之和(Vmic)與前述中孔容積之和(Vmet)的容積差(Vs)為0.35以上。 The fourth invention is a perfluoroalkyl compound sampler for personal exposure measurement according to any one of the first to third inventions, wherein the volume difference ( Vs ) between the sum of the micropore volumes ( Vmic ) and the sum of the mesopore volumes ( Vmet ) of the activated carbon as defined by the following formula (i) is 0.35 or more.

【數1】 V s =V mic -V met (i) [Number 1] V s = V mic - V met (i)

第5發明是關於如第1至4發明中任一者之個 人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳的表面氧化物量為0.10meq/g以上。 The fifth invention is a perfluoroalkyl compound sampler for personal exposure measurement as in any one of the first to fourth inventions, wherein the surface oxide content of the activated carbon is 0.10 meq/g or more.

第6發明是關於如第1至5發明中任一者之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳為纖維狀活性碳。 The sixth invention relates to a perfluoroalkyl compound sampler for personal exposure measurement as described in any one of the first to fifth inventions, wherein the activated carbon is fibrous activated carbon.

第7發明是關於如第1至5發明中任一者之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳為粒狀活性碳。 The seventh invention relates to a perfluoroalkyl compound sampler for personal exposure measurement as described in any one of the first to fifth inventions, wherein the activated carbon is granular activated carbon.

第8發明是關於如第1至7發明中任一者之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳過濾器部係被收載於碟型匣盒,前述匣盒係被備置成可著裝拆卸。 The eighth invention relates to a perfluoroalkyl compound sampler for personal exposure measurement as in any one of the first to seventh inventions, wherein the activated carbon filter portion is contained in a disc-shaped cartridge, and the cartridge is provided to be wearable and detachable.

第9發明是關於如第1至8發明中任一者之個人暴露測量用全氟及多氟烷基化合物採樣器,其中由胺基甲酸酯發泡體所形成的胺基甲酸酯發泡體過濾器部係被配置於前述活性碳過濾器部的前段而成。 The ninth invention relates to a perfluoroalkyl compound sampler for personal exposure measurement as in any one of the first to eighth inventions, wherein the urethane foam filter portion formed by the urethane foam is arranged in the front section of the activated carbon filter portion.

依據第1發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,由於是具備了可脫離地吸附全氟及多氟烷基化合物之以活性碳為主要吸附劑的活性碳過濾器部之用來測量個人暴露量的可攜式全氟及多氟烷基化合物採樣器,並且前述活性碳的BET比表面積900m2/g以上,前述活性碳過濾器部在風速0.5m/sec條件下的壓力損 失未達6kPa,因此可高效且可脫離地收集存在於工作環境等的大氣中的全氟及多氟烷基化合物,並且可攜帶、操作方便。 The perfluoroalkyl compound sampler for measuring personal exposure according to the first invention is a portable perfluoroalkyl compound sampler for measuring personal exposure, which is provided with an activated carbon filter section using activated carbon as a main adsorbent for detachably adsorbing perfluoroalkyl compounds, and the BET specific surface area of the activated carbon is 900 m2 /g or more, and the pressure loss of the activated carbon filter section under a wind speed of 0.5 m/sec is less than 6 kPa. Therefore, the perfluoroalkyl compound in the atmosphere of a working environment, etc. can be efficiently and detachably collected, and the sampler is portable and easy to operate.

依據第2發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,如第1發明,其中前述活性碳之1nm以下的微孔容積之和(Vmic)為0.35cm3/g以上,因此可高效且可脫離地收集全氟及多氟烷基化合物,可提高該化合物定量分析的精密度。 According to the perfluoroalkyl compound sampler for personal exposure measurement related to the second invention, as in the first invention, the sum of the micropore volumes of the activated carbon below 1 nm (V mic ) is 0.35 cm 3 /g or more, so that perfluoroalkyl compounds can be collected efficiently and releasably, thereby improving the precision of quantitative analysis of the compounds.

依據第3發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,如第1或2發明,其中前述活性碳之2~60nm以下的中孔容積之和(Vmet)為0.03cm3/g以上,因此可高效且可脫離地收集全氟及多氟烷基化合物,可提高該化合物定量分析的精密度。 According to the perfluoroalkyl compound sampler for personal exposure measurement related to the third invention, as in the first or second invention, the sum of the mesopore volumes of the activated carbon below 2 to 60 nm (V met ) is 0.03 cm 3 /g or more, so that perfluoroalkyl compounds can be collected efficiently and releasably, and the precision of quantitative analysis of the compounds can be improved.

依據第4發明所關連之個人暴露測量用全氟及多氟烷基化合物採樣器,如第1至3發明之任一者,其中前述活性碳之上述(i)式規定的前述微孔容積之和(Vmic)與前述中孔容積之和(Vmet)的容積差(Vs)為0.35以上,因此可高效且可脫離地收集全氟及多氟烷基化合物,可提高該化合物定量分析的精密度。 According to the perfluoroalkyl compound sampler for personal exposure measurement related to the fourth invention, such as any one of the first to third inventions, the volume difference (Vs) between the sum of the micropore volumes ( Vmic ) and the sum of the mesopore volumes ( Vmet ) of the activated carbon specified by the above formula ( i ) is 0.35 or more, so that perfluoroalkyl compounds can be collected efficiently and in a dissociable manner, thereby improving the precision of quantitative analysis of the compounds.

依據第5發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,如第1至4發明之任一者,其中前述活性碳的表面氧化物量為0.10meq/g以上,因此不僅具備了由活性碳的細孔所產生的吸附性能,還具備化學吸附能力,可更加提升中性全氟及多氟烷基化合物的吸附性能,並且可提高該化合物的定量分析精密度。According to the perfluoroalkyl compound sampler for personal exposure measurement related to the fifth invention, such as any one of the first to fourth inventions, the surface oxide content of the activated carbon is above 0.10 meq/g, so it not only has the adsorption performance generated by the fine pores of the activated carbon, but also has chemical adsorption capacity, which can further enhance the adsorption performance of neutral perfluoroalkyl compounds and improve the quantitative analysis precision of the compounds.

依據第6發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,如第1至5發明之任一者,其中前述活性碳為纖維狀活性碳,因此可確保過濾器部的通氣性,同時提高全氟及多氟烷基化合物的接觸效率,可提高吸附性能。According to the perfluoroalkyl compound sampler for personal exposure measurement related to the sixth invention, such as any one of the first to fifth inventions, the activated carbon is fibrous activated carbon, thereby ensuring the air permeability of the filter part and improving the contact efficiency of perfluoroalkyl compounds, thereby improving the adsorption performance.

依據第7發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,如第1至5發明之任一者,其中前述活性碳為粒狀活性碳,因此可適當地決定使用形態等,操作方便,甚至取得容易,經濟性高。According to the perfluoroalkyl compound sampler for personal exposure measurement related to the seventh invention, such as any one of the first to fifth inventions, the activated carbon is granular activated carbon, so the form of use can be appropriately determined, the operation is convenient, and it is easy to obtain and highly economical.

依據第8發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,如第1至7發明之任一者,其中前述活性碳過濾器部係被收載於碟型匣盒,前述匣盒係被備置成可著裝拆卸,因此可將該匣盒由採樣器拆下並立刻進行分析,而且容易更換,可連續使用,操作方便。According to the perfluoroalkyl compound sampler for personal exposure measurement related to the eighth invention, such as any one of the first to seventh inventions, the activated carbon filter portion is contained in a disc-shaped cartridge, and the cartridge is arranged to be detachable during wearing, so that the cartridge can be removed from the sampler and analyzed immediately, and is easy to replace, can be used continuously, and is convenient to operate.

依據第9發明所關連的個人暴露測量用全氟及多氟烷基化合物採樣器,如第1至8發明之任一者,其中由胺基甲酸酯發泡體所形成的胺基甲酸酯發泡體過濾器部係被配置於前述活性碳過濾器部的前段而成,因此可將以各種形態存在於大氣中的全氟及多氟烷基化合物依照形態選擇性地進行收集,可高效且總括地收集。According to the perfluoroalkyl compound sampler for personal exposure measurement related to the 9th invention, such as any one of the 1st to 8th inventions, the urethane foam filter part formed by the urethane foam is arranged in the front section of the above-mentioned activated carbon filter part, so that the perfluoroalkyl compounds existing in various forms in the atmosphere can be selectively collected according to the form, and can be collected efficiently and comprehensively.

本發明之個人暴露測量用全氟及多氟烷基化合物採樣器,是用來測定工作環境中的工作者等的個人的全氟及多氟烷基化合物暴露量。以攜帶的方式使用的個人用採樣器,通常是在本體部上具有過濾器部的一側連接了吸取空氣用的幫浦,透過過濾器部由另一側的吸氣開口部來吸取工作環境中的試樣大氣,以收集該試樣中的測定對象物。本發明之採樣器也是採用同樣的構造。The perfluoroalkyl and polyfluoroalkyl compound sampler for personal exposure measurement of the present invention is used to measure the perfluoroalkyl and polyfluoroalkyl compound exposure of the individual workers in the working environment. The personal sampler used in a portable manner is usually connected to a pump for sucking air on one side of the main body with a filter part, and the sample atmosphere in the working environment is sucked through the filter part from the suction opening on the other side to collect the measurement object in the sample. The sampler of the present invention also adopts the same structure.

從裝設了個人用採樣器的工作者經過一定時間之後回收過濾器部,並分析藉由該過濾器部所收集到的測定對象物量,可測定該工作環境中的個人暴露量。After a certain period of time, the filter part of the worker equipped with the personal sampler is collected, and the amount of the measurement object collected by the filter part is analyzed to measure the personal exposure amount in the working environment.

本發明之採樣器的收集對象為存在於大氣中的全氟及多氟烷基化合物。存在於大氣中的全氟及多氟烷基化合物大概可分類成三種。The sampler of the present invention collects perfluorinated and polyfluorinated alkyl compounds in the atmosphere. The perfluorinated and polyfluorinated alkyl compounds in the atmosphere can be roughly classified into three types.

第一種是附著於在大氣中懸浮的微小粒子(例如花粉或土壤粒子般的粉塵等)表面的粒子吸附性全氟及多氟烷基化合物,其大多數是離子性化合物。The first type is particle-adsorbing PFASs that adhere to the surface of tiny particles suspended in the atmosphere (e.g., dust such as pollen or soil particles), most of which are ionic compounds.

第二種是N-乙基全氟辛烷磺酸醯胺乙醇(之後表記為「N-EtFOSE」)或N-甲基全氟辛烷磺酸醯胺乙醇(之後表記為「N-MeFOSE」)等的半揮發性全氟烷基化合物。半揮發性有機化合物根據世界衛生組織(WHO)的定義,是指沸點260~380℃的化合物。已知因為半揮發性全氟烷基化合物分解,會產生PFOS或PFOA。N-EtFOSE是由以下的化學式(iv)所表示的物質,N-MeFOSE是由化學式(v)所表示的物質。 The second type is semi-volatile perfluoroalkyl compounds such as N-ethyl perfluorooctanesulfonamide ethanol (hereinafter referred to as "N-EtFOSE") or N-methyl perfluorooctanesulfonamide ethanol (hereinafter referred to as "N-MeFOSE"). According to the definition of the World Health Organization (WHO), semi-volatile organic compounds refer to compounds with a boiling point of 260~380℃. It is known that PFOS or PFOA will be produced due to the decomposition of semi-volatile perfluoroalkyl compounds. N-EtFOSE is a substance represented by the following chemical formula (iv), and N-MeFOSE is a substance represented by chemical formula (v).

【數4】 C 8 F 17 -SO 2 -N(C 2 H 5 )-C 2 H 4 -OH …(iv) 【Number 4】 C 8 F 17 - SO 2 - N ( C 2 H 5 )- C 2 H 4 - OH …(iv)

【數5】 C 8 F 17 -SO 2 -N(CH 3 )-C 2 H 4 -OH …(v) 【Number 5】 C 8 F 17 - SO 2 - N ( CH 3 )- C 2 H 4 - OH …(v)

然後,第三種是由前述化學式(iii)所表示,以氟調聚醇(之後表記為「FTOHS」)為代表,在大氣中以氣體的形式存在的揮發性全氟及多氟烷基化合物。揮發性有機化合物,根據世界衛生組織(WHO)的定義,是指沸點50~160℃的化合物。 Then, the third type is represented by the above chemical formula (iii), represented by fluorotelomer alcohol (hereinafter referred to as "FTOHS"), which is a volatile perfluoroalkyl compound that exists in the form of gas in the atmosphere. According to the definition of the World Health Organization (WHO), volatile organic compounds refer to compounds with a boiling point of 50~160℃.

本發明的測定對象物全氟及多氟烷基化合物,如前述般,是以三種形態存在於大氣中。本發明之採樣器,是以在活性碳過濾器部收集揮發性全氟及多氟烷基化合物為主要目的,進一步在活性碳過濾器部的前段配置胺基甲酸酯發泡體過濾器部,還可收集半揮發性全氟烷基化合物。 The perfluoroalkyl and polyfluoroalkyl compounds to be measured in the present invention exist in three forms in the atmosphere as mentioned above. The sampler of the present invention is mainly used to collect volatile perfluoroalkyl and polyfluoroalkyl compounds in the activated carbon filter section. A urethane foam filter section is further arranged in the front section of the activated carbon filter section to collect semi-volatile perfluoroalkyl compounds.

本發明之採樣器包含了具備以吸引的方式導入試樣大氣的吸氣開口部與以活性碳作為吸附劑的活性碳過濾器部的針筒型或碟型匣盒,以及透過該匣盒吸引試樣大氣的幫浦。此外,作為測定對象物的全氟及多氟烷基化合物之中,依照該化合物的形態,還可在匣盒的吸氣部側裝設具備由胺基甲酸酯發泡體所形成的胺基甲酸酯發泡體過濾器部的匣盒。 The sampler of the present invention includes a syringe-type or disc-type cartridge having an air intake opening for introducing sample atmosphere by suction and an activated carbon filter using activated carbon as an adsorbent, and a pump for sucking the sample atmosphere through the cartridge. In addition, among the perfluoro and polyfluoroalkyl compounds as the measurement object, a cartridge having a urethane foam filter formed of urethane foam can be installed on the side of the air intake portion of the cartridge according to the form of the compound.

首先,配置於上游側的胺基甲酸酯發泡體過濾器部的胺基甲酸酯發泡體(PUF)可收集半揮發性全氟烷基化合物。此外,亦可在胺基甲酸酯發泡體過濾器部的上游側裝設周知的微粒子收集用的採樣器。微粒子收集用的採樣器,可適當地選擇慣性衝擊器或利用濾紙的過濾裝置等。 First, the urethane foam (PUF) of the urethane foam filter disposed on the upstream side can collect semi-volatile perfluoroalkyl compounds. In addition, a well-known sampler for collecting microparticles can be installed on the upstream side of the urethane foam filter. The sampler for collecting microparticles can be appropriately selected from an inertial impactor or a filter device using filter paper.

然後,活性碳過濾器部主要是以收集揮發性全氟及多氟烷基化合物為目標。活性碳過濾器部中的活性碳的吸附性能,如由後述實施例所推導般,可藉由將比表面積定在900m2/g以上發揮出來。藉由形成一定以上活性碳的細孔,可確保該化合物的吸附性能。 Then, the activated carbon filter section is mainly aimed at collecting volatile perfluoroalkyl and polyfluoroalkyl compounds. The adsorption performance of the activated carbon in the activated carbon filter section can be brought into play by setting the specific surface area to 900m2 /g or more, as deduced from the examples described below. By forming the pores of the activated carbon above a certain size, the adsorption performance of the compound can be ensured.

活性碳也可藉由細孔的孔徑來規定。像活性碳這樣的吸附材的情況,微孔、中孔、大孔之任一種細孔皆存在。藉由使其中任一範圍的細孔更發達,活性碳的吸附對象、性能會發生變化。在本發明中,會希望活性碳所具有的性能是可高效且可脫離地吸附全氟及多氟烷基化合物的分子。 Activated carbon can also be specified by the pore size. In the case of an adsorbent such as activated carbon, any of micropores, mesopores, and macropores exist. By making the pores in any range more developed, the adsorption object and performance of the activated carbon will change. In the present invention, it is hoped that the activated carbon has the performance of being able to efficiently and releasably adsorb molecules of perfluoroalkyl and polyfluoroalkyl compounds.

藉由在配置於比活性碳過濾器部還前段的胺基甲酸酯發泡體過濾器部收集半揮發性全氟烷基化合物,可防止活性碳的微孔被塞住,可期待減少吸附性能的劣化。另外,藉由在胺基甲酸酯發泡體過濾器部或在胺基甲酸酯發泡體過濾器部的前段進一步裝設微粒子收集用的過濾器,可在活性碳過濾器部的前段將微粒子除去,因此可期待活性碳的性能劣化進一步受到抑制。此外,個人暴露測量用的採樣器是假設不太會長時間使用,因此即使不裝設胺基甲酸酯發泡體過濾器部等,也能充分取樣測定對象物。By collecting semivolatile perfluoroalkyl compounds in the urethane foam filter section disposed in front of the activated carbon filter section, clogging of the micropores of the activated carbon can be prevented, and the deterioration of the adsorption performance can be expected to be reduced. In addition, by further installing a filter for collecting microparticles in the urethane foam filter section or in front of the urethane foam filter section, microparticles can be removed in the front of the activated carbon filter section, so the performance degradation of the activated carbon can be expected to be further suppressed. In addition, the sampler for personal exposure measurement is assumed not to be used for a long time, so even if the urethane foam filter section is not installed, the measurement object can be fully sampled.

以這種方式,可總括地收集粒子(所吸附的全氟及多氟烷基化合物)、半揮發性全氟烷基化合物、揮發性全氟及多氟烷基化合物,因此可總括且高精密度地測定工作環境的大氣中的全氟及多氟烷基化合物的個人暴露量。尤其是可測定以往難以測定的揮發性全氟及多氟烷基化合物的個人暴露量。In this way, particles (adsorbed PFAS), semivolatile PFAS, and volatile PFAS can be collected in a comprehensive manner, so that personal exposure to PFAS in the atmosphere of the working environment can be measured comprehensively and with high precision. In particular, personal exposure to volatile PFAS, which was difficult to measure in the past, can be measured.

此外,本發明之採樣器是使用作為個人暴露測量用,因此是以可攜帶的方式構成,因此所可採用的吸氣動力源,從採樣器使用者(工作者)的操作方便性佳的觀點看來,希望是小型的幫浦。由於小型幫浦的吸引力不大,因此必須降低對幫浦的負荷。由此看來,希望過濾器部的壓力損失小,在風速0.5m/sec條件下的壓力損失設定在未達6kPa即可。In addition, the sampler of the present invention is used for personal exposure measurement and is therefore portable. Therefore, the suction power source that can be used is preferably a small pump from the perspective of good operation convenience for the sampler user (worker). Since the attraction of a small pump is not large, the load on the pump must be reduced. Therefore, it is desirable that the pressure loss of the filter part is small, and the pressure loss under the wind speed of 0.5m/sec is set to less than 6kPa.

而且,吸附全氟及多氟烷基化合物的活性碳,是由纖維狀活性碳或粒狀活性碳所形成。纖維狀活性碳是適當地使纖維碳化並且活化所得到的活性碳,已知有例如酚樹脂系、丙烯酸樹脂系、纖維素系、煤炭瀝青系等。纖維長或截面直徑等是適當的。在纖維截面直徑過大的情況,表面積會變少,接觸效率降低,因此從提升吸附能力的觀點看來,纖維截面直徑以定在30μm以下為佳。Furthermore, the activated carbon that adsorbs perfluoro and polyfluoroalkyl compounds is formed by fibrous activated carbon or granular activated carbon. Fibrous activated carbon is activated carbon obtained by properly carbonizing and activating fibers, and known examples include phenolic resins, acrylic resins, cellulose, coal asphalt, etc. The fiber length or cross-sectional diameter is appropriate. When the fiber cross-sectional diameter is too large, the surface area will decrease and the contact efficiency will decrease. Therefore, from the perspective of improving the adsorption capacity, the fiber cross-sectional diameter is preferably set to be less than 30 μm.

纖維狀活性碳可成形為氈狀作為活性碳過濾器部。藉由成形為氈狀,可提升通氣性。使用纖維狀活性碳的活性碳過濾器部的表面積大,因此會有吸附速度高的傾向。由此看來,可提升通氣性同時提高吸附性能。The fibrous activated carbon can be formed into a felt shape as an activated carbon filter. By forming it into a felt shape, the air permeability can be improved. The activated carbon filter using fibrous activated carbon has a large surface area, so it tends to have a high adsorption rate. In this way, the air permeability can be improved while the adsorption performance can be improved.

粒狀活性碳的原料,已知有木材(廢木材、疏伐材、鋸屑)、咖啡豆的濾渣、粗糠、椰子殼、樹皮、水果的果仁等的原料。這些來自天然的原料,容易藉由碳化、活化來讓細孔發達。另外,由於是廢棄物的二次利用,因此可廉價地採購。其他還有輪胎、石油瀝青、胺基甲酸酯樹脂、酚樹脂等的合成樹脂的燒結物,甚至煤炭等也可作為原料來使用。若活性碳的粒徑小,則製成過濾器體時密度會變高,全氟及多氟烷基化合物的吸附量會提升。另一方面,若粒徑變大,則製成過濾器體時的密度變小,通氣性會提升。由此看來,粒狀活性碳的平均粒徑若定在200μm以上的範圍,則可確保通氣性。The raw materials of granular activated carbon are known to include wood (waste wood, thinning materials, sawdust), coffee bean filter residue, bran, coconut shell, bark, fruit kernels, etc. These natural raw materials can easily develop fine pores through carbonization and activation. In addition, since it is a secondary utilization of waste, it can be purchased at a low price. Other raw materials include tires, petroleum asphalt, urethane resins, phenol resins, etc., sintered products of synthetic resins, and even coal, which can be used as raw materials. If the particle size of the activated carbon is small, the density will increase when the filter body is made, and the adsorption of perfluoroalkyl and polyfluoroalkyl compounds will increase. On the other hand, if the particle size becomes larger, the density of the filter body will decrease when it is made, and the air permeability will increase. From this, it can be seen that if the average particle size of granular activated carbon is set in the range of 200μm or more, air permeability can be ensured.

此外,本發明是個人暴露量的採樣器,因此所搭載的活性碳不太可能會吸附全氟及多氟烷基化合物到吸附性能的極限。因此,平均粒徑的上限沒有被特別規定。然而,若過度提高通氣性,則會有發生對象物質洩漏的顧慮,因此以物性來擔保吸附性能,並且藉由任意調整過濾器部的厚度,可降低洩漏發生的可能性。 In addition, the present invention is a personal exposure sampler, so the activated carbon carried is unlikely to adsorb perfluoroalkyl compounds to the limit of adsorption performance. Therefore, the upper limit of the average particle size is not specifically specified. However, if the air permeability is increased excessively, there will be concerns about the leakage of the target substance, so the adsorption performance is guaranteed by physical properties, and the possibility of leakage can be reduced by arbitrarily adjusting the thickness of the filter part.

活性碳過濾器部被收納在如圖1及圖2所示般的碟型匣盒10中,可著裝拆卸地裝設於採樣器即可。藉由將活性碳過濾器部20收納於該匣盒,可將該匣盒由採樣器拆下並立刻進行分析。碟型匣盒10中,試樣大氣會由吸氣開口部11擴散至本體部12並通過,因此認為吸附效率會提升。活性碳過濾器部20,如圖2所示般,若形成為例如氈狀過濾器部21,則操作方便性佳。另外,由於著裝拆卸容易,因此容易更換,可連續使用且操作方便性佳。 The activated carbon filter section is housed in a disc-shaped cartridge 10 as shown in FIG. 1 and FIG. 2, and can be installed in a detachable manner on the sampler. By housing the activated carbon filter section 20 in the cartridge, the cartridge can be removed from the sampler and analyzed immediately. In the disc-shaped cartridge 10, the sample atmosphere diffuses from the air intake opening 11 to the main body 12 and passes through, so it is believed that the adsorption efficiency will be improved. The activated carbon filter section 20, as shown in FIG. 2, is easy to operate if it is formed into, for example, a felt filter section 21. In addition, since it is easy to wear and disassemble, it is easy to replace, can be used continuously, and is easy to operate.

活性碳原料可因應必要在200℃~600℃的溫度區域加熱碳化來形成微細孔。接下來,讓活性碳原料在600℃~1200℃的溫度區域暴露於水蒸氣、二氧化碳而作活化處理。結果可製成各種細孔發達的活性碳。此外在活化時,其他方法還有氯化鋅活化等。另外還進行逐次洗淨。 The activated carbon raw material can be heated and carbonized in the temperature range of 200℃~600℃ to form fine pores as needed. Next, the activated carbon raw material is exposed to water vapor and carbon dioxide in the temperature range of 600℃~1200℃ for activation. As a result, various activated carbons with developed fine pores can be produced. In addition, other methods include zinc chloride activation. In addition, sequential washing is also performed.

此處,如前述般,還加上了規定活性碳本身的物性的指標。此規定可藉由前述活化條件來控制。該活性碳的比表面積定在900m2/g以上。在本說明書中,各試作例的比表面積是利用BET法(Brunauer、Emmett及Teller法)來測定。在比表面積低於900m2/g的情況,細孔容積會變小,單一的活性碳所能夠吸附的物質種類會受到限定。由此可推導出,在本發明所關連的全氟及多氟烷基化合物 吸附用活性碳之中,前述比表面積的範圍值是適當的。 Here, as mentioned above, an index for defining the physical properties of the activated carbon itself is also added. This definition can be controlled by the aforementioned activation conditions. The specific surface area of the activated carbon is above 900m2 /g. In this specification, the specific surface area of each trial example is measured using the BET method (Brunauer, Emmett and Teller method). When the specific surface area is lower than 900m2 /g, the pore volume becomes smaller, and the types of substances that can be adsorbed by a single activated carbon are limited. It can be deduced that the aforementioned range of specific surface area is appropriate in the activated carbon for adsorbing perfluoro and polyfluoroalkyl compounds related to the present invention.

而且可知,形成於活性碳的細孔分佈對於全氟及多氟烷基化合物的吸附也有貢獻。在本說明書中,微孔是指細孔直徑在1nm以下的細孔,如藉由後述實施例所推導般,微孔的細孔容積(Vmic)的合計若定在0.35cm3/g以上,則全氟及多氟烷基化合物的吸附性能會提升。此外,在本說明書中,各試作例之1nm以下的微孔容積,是利用MP法(Micropore法)來測定。認為藉由形成一定以上的微孔,該化合物會容易被收集在細孔中。 It is also known that the distribution of pores formed in activated carbon also contributes to the adsorption of perfluoroalkyl and polyfluoroalkyl compounds. In this specification, micropores refer to pores with a pore diameter of less than 1 nm. As deduced from the examples described below, if the total pore volume (V mic ) of the micropores is set to more than 0.35 cm 3 /g, the adsorption performance of perfluoroalkyl and polyfluoroalkyl compounds will be improved. In addition, in this specification, the volume of micropores less than 1 nm in each trial example is measured using the MP method (Micropore method). It is believed that by forming micropores of a certain size or more, the compound will be easily collected in the pores.

另外,在本說明書中,中孔是指細孔直徑在2~60nm的範圍的細孔,如藉由後述實施例所推導般,中孔的細孔容積(Vmet)的合計若定在0.03cm3/g以上,則全氟及多氟烷基化合物的吸附性能會提升。此外,在本說明書中,各試作例之2~60nm的範圍的中孔容積,是利用DH法(Dollimore-Heal法)來測定。由於利用DH法來進行測定,因此測定對象是定為2.43~59.72nm的細孔。認為藉由形成一定以上的中孔,該化合物會變得容易進入微孔。 In addition, in this specification, mesopores refer to pores with a pore diameter in the range of 2 to 60 nm. As deduced from the examples described below, if the total pore volume (V met ) of the mesopores is set to 0.03 cm 3 /g or more, the adsorption performance of perfluoroalkyl and polyfluoroalkyl compounds will be improved. In addition, in this specification, the mesopore volume in the range of 2 to 60 nm in each trial example is measured using the DH method (Dollimore-Heal method). Since the DH method is used for measurement, the measurement object is pores set to 2.43 to 59.72 nm. It is believed that by forming a certain amount of mesopores, the compound will become easier to enter the micropores.

而且還認為,微孔的細孔容積與中孔的細孔容積之差對於有效率地吸附全氟及多氟烷基化合物也有貢獻。如藉由後述實施例所推導般,藉由將微孔容積之和(Vmic)與中孔容積之和(Vmet)的容積差(Vs)定為0.35以上,可高效率且可脫離地吸附全氟及多氟烷基化合物。認為藉由採用使中孔不過度發達且使微孔良好發達的活性碳,可提升全氟及多氟烷基化合物的吸附性能,而且在後來的萃取操作時,該化合物可順利地脫離,而能夠良好地進行定量測定。It is also believed that the difference between the pore volume of micropores and the pore volume of mesopores also contributes to the efficient adsorption of perfluoroalkyl and polyfluoroalkyl compounds. As deduced by the examples described below, by setting the volume difference ( Vs) between the sum of the micropore volume (Vmic) and the sum of the mesopore volume (Vmet ) to 0.35 or more, perfluoroalkyl and polyfluoroalkyl compounds can be adsorbed efficiently and releasably. It is believed that by using activated carbon in which the mesopores are not overdeveloped and the micropores are well developed, the adsorption performance of perfluoroalkyl and polyfluoroalkyl compounds can be improved, and in the subsequent extraction operation, the compounds can be smoothly removed, and quantitative determination can be performed well.

另外,以這樣的方式製成的活性碳之中,也有酸性官能基存在於活性碳的表面。藉由活性碳的表面氧化而增加的酸性官能基,主要是羧基、酚性羥基等的親水性基。活性碳表面的酸性官能基會對收集能力造成影響。關於這些酸性官能基的量,可由表面氧化物量來掌握。認為若活性碳表面氧化物量增加,則活性碳表面的親水性會提高,全氟及多氟烷基化合物之中尤其親水性的氟短鏈聚合物化合物類的收集性能會提升。In addition, in the activated carbon made in this way, there are also acidic functional groups on the surface of the activated carbon. The acidic functional groups that increase by oxidation of the surface of the activated carbon are mainly hydrophilic groups such as carboxyl groups and phenolic hydroxyl groups. The acidic functional groups on the surface of the activated carbon will affect the collection ability. The amount of these acidic functional groups can be determined by the amount of surface oxides. It is believed that if the amount of oxides on the surface of the activated carbon increases, the hydrophilicity of the surface of the activated carbon will increase, and the collection performance of hydrophilic short-chain polymer compounds, especially perfluoro and polyfluoroalkyl compounds, will be improved.

增加活性碳表面氧化物的手段可列舉以下的手段。其中一個是再度經過加熱步驟來促進表面殘基的氧化以增加酸性官能基的手段。亦即在空氣或氧氣環境中的氧化。或者,同時在空氣環境下還導入溫度25~40℃、濕度60~90%的空氣。於是,在150~900℃下經過1~10小時的加熱,而完成了本發明的吸附活性碳。認為藉由伴隨濕潤的空氣來進行加熱,存在於活性碳表面的烷基等的烴基會被氧化,或水的羥基會被導入表面,酸性官能基會增加。The following means can be cited as means for increasing the surface oxides of activated carbon. One of them is to promote the oxidation of surface residues to increase acidic functional groups by a heating step again. That is, oxidation in air or oxygen environment. Alternatively, air with a temperature of 25 to 40°C and a humidity of 60 to 90% is introduced into the air environment at the same time. Thus, after heating at 150 to 900°C for 1 to 10 hours, the adsorbed activated carbon of the present invention is completed. It is believed that by heating with humid air, the alkyl groups such as alkyl groups existing on the surface of the activated carbon will be oxidized, or the hydroxyl groups of water will be introduced into the surface, and the acidic functional groups will increase.

其他還有藉由氧化劑使活性碳表面氧化來增加表面氧化物的手段。氧化劑可列舉次氯酸、過氧化氫等。將活性碳浸漬於含有這些氧化劑的液體,然後乾燥,可得到表面氧化物量增加的活性碳。There are other methods to increase the surface oxide by oxidizing the surface of activated carbon with an oxidant. Examples of oxidants include hypochlorous acid and hydrogen peroxide. By soaking activated carbon in a liquid containing these oxidants and then drying, activated carbon with increased surface oxide content can be obtained.

該活性碳表面的酸性官能基量,如後述各試作例般,能夠以表面氧化物量來測定。具體而言,可將表面氧化物量定在0.10meq/g以上。在低於0.10meq/g的情況下,活性碳的疏水性會變高,收集對象的全氟及多氟烷基化合物之中,尤其氟短鏈聚合物化合物類的收集性能會有降低的傾向。藉由將表面氧化物量定在0.10meq/g以上,可提高活性碳表面的親水性,可高效率地吸附全氟及多氟烷基化合物。 [實施例]The amount of acidic functional groups on the surface of the activated carbon can be measured as the amount of surface oxides, as described in the various test examples below. Specifically, the amount of surface oxides can be set at 0.10 meq/g or more. When it is lower than 0.10 meq/g, the hydrophobicity of the activated carbon will increase, and the collection performance of perfluoro and polyfluoroalkyl compounds, especially fluorinated short-chain polymer compounds, will tend to decrease. By setting the amount of surface oxides at 0.10 meq/g or more, the hydrophilicity of the activated carbon surface can be increased, and perfluoro and polyfluoroalkyl compounds can be efficiently adsorbed. [Example]

[吸附性能及通氣性能的檢討] 本發明人等為了製作個人暴露測量用採樣器,而製作出設置於採樣器的試作例1~19的過濾器部,並且進行吸附測試及通氣測試。[Review of adsorption performance and ventilation performance] In order to produce a sampler for personal exposure measurement, the inventors of the present invention produced filter parts of trial examples 1 to 19 installed in the sampler, and conducted adsorption tests and ventilation tests.

[使用活性碳] 本發明人等在製作試作例的過濾器部時,使用了下述原料。 ・纖維狀活性碳 FUTAMURA化學股份有限公司製:纖維狀活性碳「FE3010」(平均纖維徑:15μm) FUTAMURA化學股份有限公司製:纖維狀活性碳「FE3012」(平均纖維徑:15μm) FUTAMURA化學股份有限公司製:纖維狀活性碳「FE3015」(平均纖維徑:15μm) FUTAMURA化學股份有限公司製:纖維狀活性碳「FE3018」(平均纖維徑:15μm) ・粒狀活性碳 FUTAMURA化學股份有限公司製:粒狀活性碳「CW240SZ」(平均粒徑:620μm) FUTAMURA化學股份有限公司製:粒狀活性碳「CW480SZ」(平均粒徑:260μm) FUTAMURA化學股份有限公司製:粒狀活性碳「CW8150SZ」(平均粒徑:200μm) FUTAMURA化學股份有限公司製:粒狀活性碳「SZ100M」(平均粒徑:100μm)[Use of activated carbon] The inventors used the following raw materials to prepare the filter section of the trial example. ・Fiber-like activated carbon Futamura Chemical Co., Ltd.: Fiber-like activated carbon "FE3010" (average fiber diameter: 15μm) Futamura Chemical Co., Ltd.: Fiber-like activated carbon "FE3012" (average fiber diameter: 15μm) Futamura Chemical Co., Ltd.: Fiber-like activated carbon "FE3015" (average fiber diameter: 15μm) Futamura Chemical Co., Ltd.: Fiber-like activated carbon "FE3018" (average fiber diameter: 15μm) ・Granular activated carbon Futamura Chemical Co., Ltd.: Granular activated carbon "CW240SZ" (average particle size: 620μm) Futamura Chemical Co., Ltd.: Granular activated carbon "CW480SZ" (average particle size: 260μm) Futamura Chemical Co., Ltd.: Granular activated carbon "CW8150SZ" (average particle size: 200μm) Futamura Chemical Co., Ltd.: Granular activated carbon "SZ100M" (average particle size: 100μm)

[活性碳的調製] <活性碳C1> 將與FUTAMURA化學製纖維狀活性碳「FE3010」相同原料的酚樹脂纖維在600℃下碳化而成的纖維狀碳化物10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置70小時後取出,將乾燥後的纖維狀碳化物定為活性碳C1。[Preparation of activated carbon] <Activated carbon C1> 10 g of fibrous carbonized by carbonizing phenol resin fibers, which are the same raw materials as fibrous activated carbon "FE3010" manufactured by Futamura Chemical Co., Ltd. at 600°C, was immersed in 500 ml of a 4.0% hydrogen peroxide solution, left to stand for 70 hours, and then taken out. The dried fibrous carbonized product was designated as activated carbon C1.

<活性碳C2> 將FUTAMURA化學製纖維狀活性碳「FE3010」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置150小時後取出,將乾燥後的纖維狀活性碳定為活性碳C2。<Activated carbon C2> 10 g of FUTAMURA Chemical fibrous activated carbon "FE3010" was immersed in 500 ml of 4.0% hydrogen peroxide solution, left to stand for 150 hours, and then taken out. The dried fibrous activated carbon was designated as activated carbon C2.

<活性碳C3> 將FUTAMURA化學製纖維狀活性碳「FE3012」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置150小時後取出,將乾燥後的纖維狀活性碳定為活性碳C3。<Activated carbon C3> 10 g of FUTAMURA Chemical fibrous activated carbon "FE3012" was immersed in 500 ml of 4.0% hydrogen peroxide solution, left to stand for 150 hours, and then taken out. The dried fibrous activated carbon was designated as activated carbon C3.

<活性碳C4> 將FUTAMURA化學製纖維狀活性碳「FE3015」定為活性碳C4。<Activated carbon C4> Futamura Chemical's fibrous activated carbon "FE3015" is designated as activated carbon C4.

<活性碳C5> 將FUTAMURA化學製纖維狀活性碳「FE3015」10g浸漬於過氧化氫濃度1.5%溶液500ml,靜置70小時後取出,將乾燥後的纖維狀活性碳定為活性碳C5。<Activated carbon C5> 10g of FUTAMURA Chemical fibrous activated carbon "FE3015" was immersed in 500ml of 1.5% hydrogen peroxide solution, left to stand for 70 hours, and then taken out. The dried fibrous activated carbon was designated as activated carbon C5.

<活性碳C6> 將FUTAMURA化學製纖維狀活性碳「FE3015」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置70小時後取出,將乾燥後的纖維狀活性碳定為活性碳C6。<Activated carbon C6> 10 g of FUTAMURA Chemical fibrous activated carbon "FE3015" was immersed in 500 ml of 4.0% hydrogen peroxide solution, left to stand for 70 hours, and then taken out. The dried fibrous activated carbon was designated as activated carbon C6.

<活性碳C7> 將FUTAMURA化學製纖維狀活性碳「FE3015」10g浸漬於過氧化氫濃度14.0%溶液500ml,靜置350小時後取出,將乾燥後的纖維狀活性碳定為活性碳C7。<Activated carbon C7> 10g of FUTAMURA Chemical fibrous activated carbon "FE3015" was immersed in 500ml of 14.0% hydrogen peroxide solution, left to stand for 350 hours, and then taken out. The dried fibrous activated carbon was designated as activated carbon C7.

<活性碳C8> 將FUTAMURA化學製纖維狀活性碳「FE3015」10g浸漬於濃度18.9%的過氧化氫溶液500ml,靜置480小時後取出,將乾燥後的纖維狀活性碳定為活性碳C8。<Activated carbon C8> 10g of FUTAMURA Chemical fibrous activated carbon "FE3015" was immersed in 500ml of 18.9% hydrogen peroxide solution, left to stand for 480 hours, and then taken out. The dried fibrous activated carbon was designated as activated carbon C8.

<活性碳C9> 將FUTAMURA化學製纖維狀活性碳「FE3018」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置50小時後取出,將乾燥後的纖維狀活性碳定為活性碳C9。<Activated carbon C9> 10 g of FUTAMURA Chemical fibrous activated carbon "FE3018" was immersed in 500 ml of a 4.0% hydrogen peroxide solution, left to stand for 50 hours, and then taken out. The dried fibrous activated carbon was designated as activated carbon C9.

<活性碳C10> 將FUTAMURA化學粒狀活性碳「CW240SZ」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置70小時後取出,將乾燥後的粒狀活性碳定為活性碳C10。<Activated carbon C10> 10 g of FUTAMURA chemical granular activated carbon "CW240SZ" was immersed in 500 ml of 4.0% hydrogen peroxide solution, left to stand for 70 hours, and then taken out. The dried granular activated carbon was designated as activated carbon C10.

<活性碳C11> 將FUTAMURA化學粒狀活性碳「CW480SZ」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置70小時後取出,將乾燥後的粒狀活性碳定為活性碳C11。<Activated carbon C11> 10 g of FUTAMURA chemical granular activated carbon "CW480SZ" was immersed in 500 ml of a 4.0% hydrogen peroxide solution, left to stand for 70 hours, and then taken out. The dried granular activated carbon was designated as activated carbon C11.

<活性碳C12> 將FUTAMURA化學粒狀活性碳「CW8150SZ」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置70小時後取出,將乾燥後的粒狀活性碳定為活性碳C12。<Activated carbon C12> 10 g of FUTAMURA chemical granular activated carbon "CW8150SZ" was immersed in 500 ml of 4.0% hydrogen peroxide solution, left to stand for 70 hours, and then taken out. The dried granular activated carbon was designated as activated carbon C12.

<活性碳C13> 將FUTAMURA化學粒狀活性碳「SZ100M」10g浸漬於濃度4.0%的過氧化氫溶液500ml,靜置70小時後取出,將乾燥後的粒狀活性碳定為活性碳C13。<Activated carbon C13> 10g of FUTAMURA chemical granular activated carbon "SZ100M" was immersed in 500ml of 4.0% hydrogen peroxide solution, left to stand for 70 hours, and then taken out. The dried granular activated carbon was designated as activated carbon C13.

[活性碳的物性的測定] 比表面積(m2 /g)是使用MicrotracBEL股份有限公司製的自動比表面積/細孔分佈測定裝置「BELSORP-miniII」,測定77K的氮氣吸附等溫線,藉由BET法求得(BET比表面積)。[Measurement of Physical Properties of Activated Carbon] The specific surface area (m 2 /g) was determined by the BET method (BET specific surface area) by measuring the nitrogen adsorption isotherm at 77K using an automatic specific surface area/pore distribution measuring device "BELSORP-miniII" manufactured by Microtrac BEL Co., Ltd.

表面氧化物量(meq/g),是適用Boehm的方法,讓各例的吸附活性碳在0.05N氫氧化鈉水溶液中振盪,然後過濾,將該濾液以0.05N鹽酸中和滴定時的氫氧化鈉量。The surface oxide content (meq/g) was determined by applying the Boehm method, wherein the adsorbent activated carbon of each example was oscillated in a 0.05N sodium hydroxide aqueous solution, then filtered, and the filtrate was neutralized with 0.05N hydrochloric acid to determine the amount of sodium hydroxide during titration.

平均細孔直徑(nm)是將細孔的形狀假設為圓筒形,使用由前述測定所得到的細孔容積(ml/g)及比表面積(m2 /g)之值,由數學式(vi)求得。The average pore diameter (nm) is calculated from the mathematical formula (vi) using the values of the pore volume (ml/g) and specific surface area (m 2 /g) obtained from the above measurements, assuming that the pores are cylindrical.

[微孔容積] 細孔容積是使用自動比表面積/細孔分佈測定裝置(「BELSORP-miniII」,MicrotracBEL股份有限公司製),藉由氮氣吸附法來作測定。活性碳C1~C13之微孔容積之和(Vmic )(cm3 /g),亦即細孔直徑在1nm以下的範圍的細孔容積,是由氮氣吸附等溫線的t-plot,藉由MP法來解析細孔直徑在1nm以下的範圍的dV/dD之值而求得。[Micropore volume] The pore volume is measured by nitrogen adsorption using an automatic specific surface area/pore distribution measuring device ("BELSORP-miniII", manufactured by MicrotracBEL Co., Ltd.). The sum of the micropore volumes (V mic ) (cm 3 /g) of activated carbons C1 to C13, i.e., the pore volume in the range of pore diameters below 1 nm, is obtained by analyzing the dV/dD value in the range of pore diameters below 1 nm using the MP method from the t-plot of the nitrogen adsorption isotherm.

[中孔容積] 細孔直徑在2~60nm的範圍的dV/dD之值,是由氮氣吸附等溫線藉由DH法來解析。此外,解析軟體中的細孔直徑2~60nm的直徑範圍為2.43~59.72nm。由此解析結果可求得活性碳C1~C13之中孔容積之和(Vmic )(cm3 /g),亦即細孔直徑在2~60nm的範圍的細孔容積。[Mesopore volume] The dV/dD value of the pore diameter range of 2-60nm is analyzed by the DH method from the nitrogen adsorption isotherm. In addition, the diameter range of the pore diameter of 2-60nm in the analysis software is 2.43-59.72nm. From this analysis result, the sum of the mesopore volumes (V mic ) (cm 3 /g) of activated carbon C1-C13 can be obtained, that is, the pore volume of the pore diameter range of 2-60nm.

[容積差] 活性碳C1~C13的容積差(Vs )是由微孔容積之和(Vmic )(cm3 /g)扣掉中孔容積之和(Vmet )(cm3 /g)之值,由上述(i)式來計算。[Volume Difference] The volume difference (V s ) of activated carbons C1 to C13 is calculated by subtracting the sum of mesopore volumes (V met ) (cm 3 /g) from the sum of micropore volumes (V mic ) (cm 3 /g) using the above formula (i).

活性碳C1~C13的物性如表1~3。表1~3由上開始依序為BET比表面積(m2 /g)、表面氧化物量(meq/g)、平均細孔直徑(nm)、微孔容積(Vmic )(cm3 /g)、中孔容積(Vmet )(cm3 /g)、容積差(Vs )(cm3 /g)。The physical properties of activated carbons C1 to C13 are shown in Tables 1 to 3. Tables 1 to 3 are, from the top, BET specific surface area (m 2 /g), surface oxide content (meq/g), average pore diameter (nm), micropore volume (V mic ) (cm 3 /g), mesopore volume (V met ) (cm 3 /g), and volume difference (V s ) (cm 3 /g).

[過濾器部的製作] 為了評估吸附性能,使用試作例1~10來進行吸附測試。另外,為了評估通氣性能,使用試作例11~19進行通氣測試。[Production of filter unit] In order to evaluate the adsorption performance, adsorption tests were conducted using Prototypes 1 to 10. In addition, in order to evaluate the ventilation performance, ventilation tests were conducted using Prototypes 11 to 19.

<試作例1> 製作出以活性碳C1為主原料的纖維狀碳化物氈(厚度2.0mm、直徑25mm、重量110mg),定為試作例1的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒內。<Trial Example 1> Fiber-like carbide felt (thickness 2.0 mm, diameter 25 mm, weight 110 mg) with activated carbon C1 as the main raw material was produced and defined as the filter part of Trial Example 1. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例2> 製作出以活性碳C2為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量110mg),定為試作例2的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒內。<Trial Example 2> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 110 mg) with activated carbon C2 as the main raw material was produced and defined as the filter part of Trial Example 2. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例3> 製作出以活性碳C3為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量100mg),定為試作例3的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒內。<Trial Example 3> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 100 mg) with activated carbon C3 as the main raw material was produced and defined as the filter part of Trial Example 3. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例4> 製作出以活性碳C4為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量90mg),定為試作例4的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒內。<Trial Example 4> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 90 mg) with activated carbon C4 as the main raw material was produced and defined as the filter part of Trial Example 4. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例5> 製作出以活性碳C5為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量90mg),定為試作例5的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒。<Trial Example 5> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 90 mg) with activated carbon C5 as the main raw material was produced and defined as the filter part of Trial Example 5. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例6> 製作出以活性碳C6為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量90mg),定為試作例6的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒。<Trial Example 6> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 90 mg) with activated carbon C6 as the main raw material was produced and defined as the filter part of Trial Example 6. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例7> 製作出以活性碳C7為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量90mg),定為試作例7的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒。<Trial Example 7> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 90 mg) with activated carbon C7 as the main raw material was produced and defined as the filter part of Trial Example 7. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例8> 製作出以活性碳C8為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量90mg),定為試作例8的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒。<Trial Example 8> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 90 mg) with activated carbon C8 as the main raw material was produced and defined as the filter part of Trial Example 8. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例9> 製作出以活性碳C9為主原料的纖維狀活性碳氈(厚度2.0mm、直徑25mm、重量70mg),定為試作例9的過濾器部。該過濾器部設置於內直徑25mm的聚丙烯製碟型匣盒。<Trial Example 9> Fiber-shaped activated carbon felt (thickness 2.0 mm, diameter 25 mm, weight 70 mg) with activated carbon C9 as the main raw material was produced and defined as the filter part of Trial Example 9. The filter part was set in a polypropylene disc-shaped box with an inner diameter of 25 mm.

<試作例10> 將150mg活性碳C11填充至12ml針筒,成為2mm厚的填充層的過濾器部,定為試作例10的過濾器部。在該填充層的前後配置10μm以上的粒子無法通過的燒結聚乙烯薄片(Dikma公司製,以下相同),將活性碳固定。<Trial Example 10> 150 mg of activated carbon C11 was filled into a 12 ml syringe to form a filter portion with a 2 mm thick filling layer, which was defined as the filter portion of Trial Example 10. Sintered polyethylene sheets (manufactured by Dikma, the same below) that prevent particles larger than 10 μm from passing were placed before and after the filling layer to fix the activated carbon.

<試作例11> 將32mg活性碳C1填充至6ml針筒,成為2mm厚的填充層的過濾器部,定為試作例11的過濾器部。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 11> 32 mg of activated carbon C1 was filled into a 6 ml syringe to form a filter portion with a 2 mm thick filling layer, which was defined as the filter portion of Trial Example 11. Sintered polyethylene sheets with an average pore size of 10 μm were placed before and after the filter portion (filling layer) to fix the activated carbon.

<試作例12> 將30mg活性碳C2填充至6ml針筒,成為2mm厚的填充層的過濾器部,定為試作例12的過濾器部。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 12> 30 mg of activated carbon C2 was filled into a 6 ml syringe to form a filter portion with a 2 mm thick filling layer, which was defined as the filter portion of Trial Example 12. Sintered polyethylene sheets with an average pore size of 10 μm were placed before and after the filter portion (filling layer) to fix the activated carbon.

<試作例13> 將28mg活性碳C3填充至6ml針筒,成為2mm厚的填充層的過濾器部,定為試作例13的過濾器部。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 13> 28 mg of activated carbon C3 was filled into a 6 ml syringe to form a filter section with a 2 mm thick filling layer, which was defined as the filter section of Trial Example 13. Sintered polyethylene sheets with an average pore size of 10 μm were placed before and after the filter section (filling layer) to fix the activated carbon.

<試作例14> 將24mg活性碳C6填充至6ml針筒,成為2mm厚的填充層的過濾器部,定為試作例14的過濾器部。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 14> 24 mg of activated carbon C6 was filled into a 6 ml syringe to form a filter section with a 2 mm thick filling layer, which was defined as the filter section of Trial Example 14. Sintered polyethylene sheets with an average pore size of 10 μm were placed before and after the filter section (filling layer) to fix the activated carbon.

<試作例15> 將20mg活性碳C9填充至6ml針筒,成為2mm厚的填充層的過濾器部,定為試作例15的過濾器部。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 15> 20 mg of activated carbon C9 was filled into a 6 ml syringe to form a filter section with a 2 mm thick filling layer, which was defined as the filter section of Trial Example 15. Sintered polyethylene sheets with an average pore size of 10 μm were placed before and after the filter section (filling layer) to fix the activated carbon.

<試作例16> 將150mg活性碳C10填充至6ml針筒,成為2mm厚的填充層的過濾器部,定為試作例16的過濾器部。此外,在填充時,是以活性碳面呈水平的方式進行疏填充。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 16> 150 mg of activated carbon C10 was filled into a 6 ml syringe to form a filter portion with a 2 mm thick filling layer, which was defined as the filter portion of Trial Example 16. In addition, during filling, the activated carbon surface was filled sparsely in a horizontal manner. Sintered polyethylene sheets with an average pore size of 10 μm were placed in front and behind the filter portion (filling layer) to fix the activated carbon.

<試作例17> 將180mg活性碳C11填充至6ml針筒型匣盒,成為2mm厚的填充層的過濾器部,定為試作例17的過濾器部。此外,在填充時,是以活性碳面呈水平的方式進行疏填充。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 17> 180 mg of activated carbon C11 was filled into a 6 ml syringe-type cartridge to form a filter section with a 2 mm thick filling layer, which was defined as the filter section of Trial Example 17. In addition, during filling, the activated carbon surface was filled sparsely in a horizontal manner. Sintered polyethylene sheets with an average pore size of 10 μm were arranged in front and behind the filter section (filling layer) to fix the activated carbon.

<試作例18> 將200mg活性碳C12填充至6ml針筒型匣盒,成為2mm厚的填充層的過濾器部,定為試作例18的過濾器部。此外,在填充時,是以活性碳面呈水平的方式進行疏填充。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 18> 200 mg of activated carbon C12 was filled into a 6 ml syringe-type cartridge to form a filter section with a 2 mm thick filling layer, which was defined as the filter section of Trial Example 18. In addition, during filling, the activated carbon surface was filled sparsely in a horizontal manner. Sintered polyethylene sheets with an average pore size of 10 μm were placed in front and behind the filter section (filling layer) to fix the activated carbon.

<試作例19> 將230mg活性碳C13填充至6ml針筒型匣盒,成為2mm厚的填充層的過濾器部,定為試作例19的過濾器部。此外,在填充時,是以活性碳面呈水平的方式進行疏填充。在該過濾器部(填充層)的前後配置平均氣孔徑10μm的燒結聚乙烯薄片,將活性碳固定。<Trial Example 19> 230 mg of activated carbon C13 was filled into a 6 ml syringe-type cartridge to form a filter section with a 2 mm thick filling layer, which was defined as the filter section of Trial Example 19. In addition, during filling, the activated carbon surface was filled sparsely in a horizontal manner. Sintered polyethylene sheets with an average pore size of 10 μm were placed in front and behind the filter section (filling layer) to fix the activated carbon.

[吸附性能的測定] 使用試作例1~試作例10來進行全氟及多氟烷基化合物的收集效率的測定。全氟及多氟烷基化合物這次是使用氟調聚醇(之後表記為「FTOHs」)、氟碘化合物及氟溴化合物來進行評估。FTOHs是由上述化學式(iii)所表示的物質,物質名稱會依照碳數而不同。例如在C8 F17 CH2 CH2 OH的情況,命名為8:2 FTOH (IUPAC名:3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟-1-癸醇)。N-EtFOSA是由以下的化學式(vii)所表示的物質。[Determination of adsorption performance] The collection efficiency of perfluoro and polyfluoroalkyl compounds was determined using Prototypes 1 to 10. Perfluoro and polyfluoroalkyl compounds were evaluated using fluorotelomer alcohols (hereinafter referred to as "FTOHs"), fluoroiodine compounds, and fluorobromide compounds. FTOHs are substances represented by the above chemical formula (iii), and the names of the substances vary depending on the number of carbon atoms. For example, in the case of C 8 F 17 CH 2 CH 2 OH, it is named 8:2 FTOH (IUPAC name: 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol). N-EtFOSA is a substance represented by the following chemical formula (vii).

在設置有試作例1~試作例10的過濾器部的匣盒的前段直接連結填充了聚胺基甲酸酯發泡體(PUF)(柴田科學股份有限公司製,直徑20mm、長度50mm)的20ml的針筒(AS ONE股份有限公司製,直徑20mm)。另外,在各個匣盒的後段透過聚丙烯管來連接取樣幫浦(柴田科學股份有限公司製,「MP-Σ500N II」),並使用聚氯乙烯膠帶以使其不會洩漏。A 20 ml syringe (manufactured by AS ONE Co., Ltd., diameter 20 mm) filled with polyurethane foam (PUF) (manufactured by Shibata Scientific Co., Ltd., diameter 20 mm, length 50 mm) was directly connected to the front section of the cassettes provided with the filter parts of Trial Examples 1 to 10. In addition, a sampling pump (manufactured by Shibata Scientific Co., Ltd., "MP-Σ500N II") was connected to the rear section of each cassette through a polypropylene tube, and polyvinyl chloride tape was used to prevent leakage.

將各標準物質以甲醇稀釋成100ppb的溶液100μl添加至聚胺基甲酸酯發泡體(PUF),以2.0L/min的速度將25℃的空氣通氣8小時。通氣後,使用以二氯甲烷與醋酸乙酯為主成分的混合溶劑15ml,以1滴/秒的速度通過各個匣盒,並採取萃取液。Each standard substance was diluted with methanol to a 100 ppb solution, 100 μl was added to the polyurethane foam (PUF), and 25°C air was ventilated at a rate of 2.0 L/min for 8 hours. After ventilation, 15 ml of a mixed solvent with dichloromethane and ethyl acetate as the main components was passed through each cartridge at a rate of 1 drop/second, and the extract was collected.

對該萃取液,使用GC-MS/MS(「GCMS-TQ8050」,島津製作所股份有限公司製),以MRM模式進行定量測定,確認收集性能。The extract was quantitatively analyzed using GC-MS/MS ("GCMS-TQ8050", manufactured by Shimadzu Corporation) in the MRM mode to confirm the collection performance.

表4~8揭示了試作例1~試作例10對各個標準物質的回收率(%),包括氟調聚醇(FTOH),還有氟碘化合物及氟溴化合物。對象物質為4:2 FTOH (IUPAC名:3,3,4,4,5,5,6,6,6-九氟-1-己醇)、 6:2 FTOH (IUPAC名:3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟-1-辛醇)、 8:2 FTOH、10:2 FTOH (IUPAC名:3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-二十一氟-1-十二烷醇)、6:2 FTI (IUPAC名:1,1,1,2,2,3,3,4,4,5,5,6,6-十三氟-8-碘辛烷)、8:2 FTI (IUPAC名:1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-十七氟-12-碘十二烷)、10:2 FTI (IUPAC名:1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-二十一氟-12-碘十二烷)、PFDeI (IUPAC名:1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-二十一氟-10-碘十二烷)、PFDoI (IUPAC名:1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-二十五氟-12-碘十二烷)、PFBuDiI (IUPAC名:1,1,2,2,3,3,4,4-八氟-1,4-二碘丁烷)、PFHxDiI (IUPAC名:IUPAC名:1,1,2,2,3,3,4,4,5,5,6,6-十二氟-1,6-二碘己烷)、PFoDiI (IUPAC名:1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-十六氟-1,8-二碘辛烷)、C8 H3 BrF6 (IUPAC名:1-溴-3,5-雙(三氟甲基)苯)。Tables 4 to 8 reveal the recovery rates (%) of various standard substances in Trial Examples 1 to 10, including fluorotelomer alcohol (FTOH), fluoroiodine compounds, and fluorobromide compounds. The target substances are 4:2 FTOH (IUPAC name: 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol), 6:2 FTOH (IUPAC name: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol), 8:2 FTOH, 10:2 FTOH (IUPAC name: 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicofluoro-1-dodecanol), 6:2 FTI (IUPAC name: 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane), 8:2 FTI (IUPAC name: 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-12-iodododecane), 10:2 FTI (IUPAC name: 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-heneicofluoro-12-iodododecane), PFDeI (IUPAC name: 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-heneicofluoro-10-iodododecane), PFDoI (IUPAC name: 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-pentafluoro-12-iodododecane), PFBuDiI (IUPAC name: 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane), PFHxDiI (IUPAC name: 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane), PFoDiI (IUPAC name: 1,1,2,2,3,3,4,4,5,5,6,6-hexafluoro-1,8-diiodooctane), C 8 H 3 BrF 6 (IUPAC name: 1-bromo-3,5-bis(trifluoromethyl)benzene).

碘氟化合物(FTI)是由以下的化學式(viii)所表示的物質,PFDeI及PFDoI是由化學式(ix)所表示的物質,PFBuDiI、PFHxDiI及PFoDiI是由化學式(x)所表示的物質、溴氟化合物(C8 H3 BrF6 )是由化學式(xi)所表示的物質。The iodine fluoride compound (FTI) is a substance represented by the following chemical formula (viii), PFDeI and PFDoI are substances represented by chemical formula (ix), PFBuDiI, PFHxDiI and PFoDiI are substances represented by chemical formula (x), and the bromine fluoride compound (C 8 H 3 BrF 6 ) is a substance represented by chemical formula (xi).

關於各標準物質的回收率的評估,是將回收率在70%以上的情況定為「◎」,未達70%且在50%以上的情況定為「○」,未達50%且在40%以上的情況定為「△」,未達40%的情況定為「×」。總合評估是在各標準物質的回收率的評估之中,將「○」為7個(半數)以下,「△」或「×」一個都沒有的情況定為「A」,「×」一個都沒有的情況定為「B」,只要有一個「×」即定為「C」。The recovery rate of each standard substance was evaluated as "◎" when the recovery rate was 70% or more, "○" when it was less than 70% but more than 50%, "△" when it was less than 50% but more than 40%, and "×" when it was less than 40%. The overall evaluation was evaluated in the recovery rate of each standard substance, and the case where there were less than 7 "○"s (half of the cases), no "△"s or "×"s was evaluated as "A", no "×"s were evaluated as "B", and even one "×" was evaluated as "C".

此外,表中「ND」代表在偵測極限以下。In addition, "ND" in the table means below the detection limit.

另外,為了確認添加至PUF中的各標準物質是否並未揮發而殘留,也針對在PUF中的殘存率(%)進行了測量。PUF中的殘存率如果在10%以下,則可確認揮發的標準物質充分接觸到各試作例。In addition, in order to confirm whether each standard substance added to PUF does not volatilize and remain, the residual rate (%) in PUF is also measured. If the residual rate in PUF is less than 10%, it can be confirmed that the volatile standard substance has fully contacted each test sample.

此外,在表9~11中,半揮發性的對象物質是使用乙基全氟辛烷磺醯胺(IUPAC名:N-乙基-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十七氟辛烷-1-磺醯胺)(之後表記為「N-EtFOSA」)、N-甲基全氟辛烷磺醯胺(IUPAC名:1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十七氟-N-甲基-1-辛烷磺醯胺)(之後表記為「N-MeFOSA」)、N-甲基全氟辛烷磺醯胺乙醇(IUPAC名:1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十七氟-N-(2-羥乙基)-N-甲基-1-辛烷磺醯胺)(之後表記為「N-MeFOSE」)及N-乙基全氟辛烷磺醯胺乙醇(IUPAC名:N-乙基-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十七氟-N-(2-羥乙基)-1-辛烷磺醯胺)(之後表記為「N-EtFOSE」),並測量了裝設在試作例1~10的前段的胺基甲酸酯發泡體過濾器部的回收率(%)。In Tables 9 to 11, the semivolatile target substances are ethyl perfluorooctanesulfonamide (IUPAC name: N-ethyl-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonamide) (hereinafter referred to as "N-EtFOSA"), N-methyl perfluorooctanesulfonamide (IUPAC name: 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-N-methyl-1-octanesulfonamide) (hereinafter referred to as "N-MeFOSA"), N-methyl perfluorooctanesulfonamide ethanol (IUPAC name: :1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-N-(2-hydroxyethyl)-N-methyl-1-octanesulfonamide) (hereinafter referred to as "N-MeFOSE") and N-ethylperfluorooctanesulfonamideethanol (IUPAC name: N-ethyl-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-N-(2-hydroxyethyl)-1-octanesulfonamide) (hereinafter referred to as "N-EtFOSE"), and the recovery rate (%) of the urethane foam filter installed in the front stage of Trial Examples 1 to 10 was measured.

N-EtFOSA是由前述化學式(vii)所表示的物質,N-MeFOSA是由以下的化學式(xii)所表示的物質。N-EtFOSA is a substance represented by the above-mentioned chemical formula (vii), and N-MeFOSA is a substance represented by the following chemical formula (xii).

[結果與考察] 關於試作例3~10,任一標準物質的回收率皆有良好的結果。在試作例1及試作例2的情況,結果是在偵測極限以下或非常低的回收率,可知無法吸附,並不具備足夠的收集性能。推測試作例1及試作例2並不具有收集所必要的比表面積,因此並未充分發揮收集性能。[Results and Discussion] For Trial Examples 3 to 10, the recovery rates of all standard substances were good. In the case of Trial Examples 1 and 2, the results were below the detection limit or very low recovery rates, indicating that adsorption was not possible and the collection performance was not sufficient. It is inferred that Trial Examples 1 and 2 did not have the specific surface area required for collection, and therefore the collection performance was not fully utilized.

關於試作例3~10,所有標準物質的回收率皆顯示良好的收集結果,而具有優異的收集性能。結果顯示若比表面積定在900m2 /g以上,則可達成對象物質的吸附。For Trial Examples 3 to 10, the recovery rates of all standard substances showed good collection results, and the collection performance was excellent. The results showed that if the specific surface area is set at 900m2 /g or more, the adsorption of the target substance can be achieved.

另外結果還顯示,若將活性碳原料相同的試作例4與增加表面氧化物量的試作例5~8加以比較,則試作例5~8的情況,對象物質的吸附性能較為良好。可理解藉由提升活性碳的表面氧化物量,具有親水性基的FTOH的親和性會提升,FTOH的吸附性能會提升。The results also show that when comparing Trial Example 4 with the same activated carbon raw material and Trial Examples 5 to 8 with increased surface oxide content, the adsorption performance of the target substance is better in Trial Examples 5 to 8. It can be understood that by increasing the surface oxide content of activated carbon, the affinity of FTOH with a hydrophilic group is increased, and the adsorption performance of FTOH is improved.

結果顯示,胺基甲酸酯發泡體過濾器部對於半揮發性的對象物質有安定而良好的回收率。而且,若從所有的氟調聚醇類都在偵測極限以下看來,結果顯示可選擇性地收集半揮發性全氟烷基化合物。The results showed that the urethane foam filter has a stable and good recovery rate for semi-volatile target substances. In addition, since all fluorotelomer alcohols are below the detection limit, the results show that semi-volatile perfluoroalkyl compounds can be selectively collected.

[通氣性能的測定] 接下來,本發明人等使用試作例11~19的過濾器部來進行通氣測試。此外,將填充層設定為2mm厚,是因為若填充層在2mm以下,則難以均勻填充至匣盒內,可能會出現無法充分與對象物質接觸之處,會有氣體從近路通過的顧慮。[Measurement of ventilation performance] Next, the inventors of the present invention used the filter parts of trial examples 11 to 19 to conduct ventilation tests. In addition, the filling layer was set to 2 mm thick because if the filling layer is less than 2 mm, it would be difficult to fill the box evenly, and there might be places where it could not fully contact the target material, and there would be concerns that gas would pass through through a shortcut.

藉由測量試作例11~試作例19的匣盒前後的壓力差,測定壓力損失,以進行通氣性能的評估。在各試作例的匣盒前後連接壓差計的測定用聚丙烯管,並使用聚氯乙烯膠帶以使其不洩漏。藉由取樣幫浦(柴田科學股份有限公司製,「SIP-32L型」)使25℃的空氣通過,並將風量定為1.0、2.0、3.0、4.0及5.0L/min五階段的風量,測量各試作例的匣盒前後的壓力差。The pressure loss was measured by measuring the pressure difference before and after the cassettes of Prototypes 11 to 19 to evaluate the ventilation performance. A polypropylene tube for measuring the differential pressure gauge was connected before and after the cassettes of each Prototype, and polyvinyl chloride tape was used to prevent leakage. Air at 25°C was passed through a sampling pump ("SIP-32L" manufactured by Shibata Scientific Co., Ltd.), and the air volume was set to five stages of 1.0, 2.0, 3.0, 4.0, and 5.0 L/min, and the pressure difference before and after the cassettes of each Prototype was measured.

表12及表13揭示了試作例11~試作例19的匣盒,以及僅填充兩枚燒結聚乙烯薄片且不具備活性碳過濾器部而被定為「BLANK」的匣盒,匣盒前後的壓差(kPa)。此外,在表中,各試作例是被填充至6ml針筒,因此五階段的風量分別被換算成了表中右方欄位的風速。壓力損失大致與風速成比例,因此以各試作例的匣盒在0.5m/sec風速下的壓力損失為基準來進行評估。然後,表14及表15揭示了各試作例的壓力損失與「BLANK」的壓力損失之差,並計算出各試作例的活性碳過濾器部的壓力損失。將活性碳過濾器部的壓力損失未達5kPa的情況評為「○」,5kPa以上未達6kPa的情況評為「△」,6kPa以上的情況評為「×」。Tables 12 and 13 reveal the pressure difference (kPa) before and after the cassettes of Prototype Examples 11 to 19, and the cassette designated as "BLANK" because it is filled with only two sintered polyethylene sheets and does not have an activated carbon filter. In addition, in the table, each prototype was filled into a 6ml syringe, so the air volume in the five stages was converted into the wind speed in the right column of the table. The pressure loss is roughly proportional to the wind speed, so the pressure loss of the cassette of each prototype at a wind speed of 0.5m/sec was used as the basis for evaluation. Then, Tables 14 and 15 reveal the difference between the pressure loss of each prototype and the pressure loss of "BLANK", and the pressure loss of the activated carbon filter part of each prototype is calculated. The case where the pressure loss in the activated carbon filter part was less than 5 kPa was evaluated as "○", the case where it was 5 kPa or more but less than 6 kPa was evaluated as "△", and the case where it was 6 kPa or more was evaluated as "×".

[結果與考察] 在試作例19之中,作為吸附劑的活性碳的粒徑過小,壓力損失變大,若將吸引幫浦的風量定在4.0L/min(風速0.5m/sec)以上,則負荷變得過大,而無法安全運作,因此為「-(無法測量)」。試作例18的匣盒,壓力損失會到達一般小型幫浦性能上無法順利運作的程度,因此在吸附劑採用粒狀活性碳的情況,會希望將平均粒徑定在200μm以上。[Results and considerations] In Trial Example 19, the particle size of the activated carbon used as the adsorbent was too small, resulting in a large pressure loss. If the air volume of the suction pump was set at 4.0L/min (wind speed 0.5m/sec) or more, the load would be too large to operate safely, so it was rated as "- (unmeasurable)". The pressure loss of the cartridge in Trial Example 18 was such that the general small pump could not operate smoothly, so when using granular activated carbon as the adsorbent, it is desirable to set the average particle size to 200μm or more.

在使用了纖維狀活性碳或平均粒徑大於200μm的粒子狀活性碳的試作例11~16之中,即使考慮到流路縮短等的問題而使用充足厚度的過濾器層,也幾乎沒有壓力損失,可說是在以小型幫浦作為吸引動力源的情況,也能充分測定對象物質。In Experimental Examples 11 to 16 using fibrous activated carbon or granular activated carbon with an average particle size greater than 200 μm, there was almost no pressure loss even when a filter layer of sufficient thickness was used to take into account problems such as shortened flow paths, and it can be said that the target substance can be fully measured even when a small pump is used as the suction power source.

[實際環境下全氟及多氟烷基化合物的收集實驗] 使用上述試作例5的活性碳過濾器部,進行實際環境下的全氟及多氟烷基化合物的收集實驗。在設置有試作例5的過濾器部的匣盒的前段直接連結填充有聚胺基甲酸酯發泡體(PUF)(柴田科學股份有限公司製,直徑20mm、長度50mm)的20ml針筒(AS ONE股份有限公司製,直徑20mm)。另外,在各個匣盒的後段透過聚丙烯管連接取樣幫浦(柴田科學股份有限公司製,「MP-Σ500N II」),並使用聚氯乙烯膠帶以使其不洩漏。[Collection experiment of perfluorinated and polyfluoroalkyl compounds in actual environment] Using the activated carbon filter part of the above-mentioned trial example 5, the collection experiment of perfluorinated and polyfluoroalkyl compounds in actual environment was carried out. A 20ml syringe (manufactured by AS ONE Co., Ltd., diameter 20mm) filled with polyurethane foam (PUF) (manufactured by Shibata Scientific Co., Ltd., diameter 20mm, length 50mm) was directly connected to the front section of the cassette where the filter part of trial example 5 was set. In addition, a sampling pump (manufactured by Shibata Scientific Co., Ltd., "MP-Σ500N II") was connected to the rear section of each cassette through a polypropylene tube, and polyvinyl chloride tape was used to prevent it from leaking.

將上述構造的採樣器設置於本發明人住家(2020年1月)的客廳及寢室。有鑑於實際的使用狀況,應該接近人呼吸區域的高度,分別設置在離地板約140cm的高度。此外,在本實驗中,為了提升測定靈敏度,以通氣量10.0ml/min通氣11小時。此外,本發明人住家客廳的氣溫是在12.9~23.0℃(平均22℃)、寢室的氣溫是在12.9~23.0℃(平均22℃)的條件下。The sampler of the above structure was set in the living room and bedroom of the inventor's home (January 2020). In view of the actual usage, it should be close to the height of the human breathing zone and set at a height of about 140 cm from the floor. In addition, in this experiment, in order to improve the measurement sensitivity, ventilation was performed for 11 hours at a ventilation volume of 10.0 ml/min. In addition, the temperature of the living room of the inventor's home was 12.9-23.0°C (average 22°C), and the temperature of the bedroom was 12.9-23.0°C (average 22°C).

在試作例5的活性碳過濾器部,是以氟調聚醇類(FTOHs)的4:2 FTOH、6:2 FTOH、8:2 FTOH、10:2 FTOH,氟碘化合物的6:2 FTI、8:2 FTI、10:2 FTI、PFDeI、PFDoI、PFBuDi、PFHxDiI、PFoDiI,氟溴化合物的C8 H3 BrF6 作為全氟及多氟烷基化合物來進行測量。FTI是由前述化學式(viii)所表示的物質。此外還使用了4:2 FTOH、6:2 FTOH、8:2 FTOH、10:2 FTOH作為替代試驗品,也進行了回收率(%)的測定。In the activated carbon filter section of Experiment 5, fluorotelomer alcohols (FTOHs) such as 4:2 FTOH, 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH, fluoroiodine compounds such as 6:2 FTI, 8:2 FTI, 10:2 FTI, PFDeI, PFDoI, PFBuDi, PFHxDiI, and PFoDiI, and fluorobromine compounds such as C 8 H 3 BrF 6 were used for measurement as perfluoro and polyfluoroalkyl compounds. FTI is a substance represented by the above chemical formula (viii). In addition, 4:2 FTOH, 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH were used as alternative test products, and the recovery rate (%) was also measured.

在由聚胺基甲酸酯發泡體(PUF)形成的胺基甲酸酯發泡體過濾器部,使用全氟辛酸類的N-MeFOSA、N-EtFOSA、全氟辛烷磺酸類的N-MeFOSE、N-EtFOSE來進行回收率(%)的測定。此外還使用了N-MeFOSA、N-EtFOSA、N-MeFOSE、N-EtFOSE作為替代試驗品,也進行了回收率(%)的測定。In the urethane foam filter part formed of polyurethane foam (PUF), the recovery rate (%) was measured using N-MeFOSA and N-EtFOSA of perfluorooctanoic acid, and N-MeFOSE and N-EtFOSE of perfluorooctane sulfonic acid. In addition, the recovery rate (%) was also measured using N-MeFOSA, N-EtFOSA, N-MeFOSE, and N-EtFOSE as alternative test products.

對於通氣後的過濾器部,使用以二氯甲烷與醋酸乙酯為主成分的混合溶劑15ml,以1滴/秒的速度通過各個匣盒及胺基甲酸酯發泡體過濾器部,並採取萃取液。對該萃取液,使用GC-MS/MS(「GCMS-TQ8050」,島津製作所股份有限公司製),以MRM模式進行定量測定。For the filter section after ventilation, 15 ml of a mixed solvent with dichloromethane and ethyl acetate as the main components was passed through each cartridge and the urethane foam filter section at a rate of 1 drop/second to collect an extract. The extract was quantitatively measured using GC-MS/MS ("GCMS-TQ8050", manufactured by Shimadzu Corporation) in MRM mode.

表16揭示了活性碳過濾器部、表17揭示了胺基甲酸酯發泡體過濾器部中的全氟及多氟烷基化合物相對於試樣大氣的濃度(pg/m3 )。全氟及多氟烷基化合物的濃度,是將所收集到的全氟及多氟烷基化合物(對象物質)的收集量(pg)除以對採樣器通氣的累計流量(m3 )所求得之值,由下述數學式(xiii)求得。此外,表中的「BLANK」,是在進行實驗之前,對活性碳過濾器部、胺基甲酸酯發泡體過濾器部進行同樣的測定所偵測到的數值,「LOQ」代表測定裝置對各物質可定量測定的下限值。「-」代表在定量下限值以下,「ND」代表在偵測極限以下。Table 16 shows the concentration of perfluoroalkyl compounds in the activated carbon filter section and Table 17 shows the concentration of perfluoroalkyl compounds in the urethane foam filter section relative to the sample atmosphere (pg/m 3 ). The concentration of perfluoroalkyl compounds is obtained by dividing the collected amount of perfluoroalkyl compounds (target substances) (pg) by the cumulative flow rate (m 3 ) of ventilation to the sampler, and is obtained by the following mathematical formula (xiii). In addition, "BLANK" in the table is the value detected by the same measurement of the activated carbon filter section and the urethane foam filter section before the experiment, and "LOQ" represents the lower limit of the quantitative measurement of each substance by the measuring device. "-" represents below the quantitative lower limit, and "ND" represents below the detection limit.

[實際環境下全氟及多氟烷基化合物收集實驗的結果與考察] 在表16所示的活性碳過濾器部的實驗結果之中,在開發者住家的客廳及寢室這兩個場所偵測到氟調聚醇(FTOHs)之中的6:2 FTOH、8:2 FTOH、10:2 FTOH這三種。已知該FTOHs被使用於地毯或衣物、室內裝飾品,在設置了各種家具的客廳或寢室之中偵測到該FTOHs可認為是合理的結果。另外,在客廳與寢室中偵測到的對象物質雖然是同種類,然而觀察到濃度有明確的差異,而且替代試驗品的回收率也很良好,因此可說是顯示出作為全氟及多氟烷基化合物的測定所使用的採樣器的顯著性。此外還顯示,即使在以10.0ml/min通氣11小時的條件下也能達成高水準的分析。 [Results and investigation of the collection experiment of perfluorinated and polyfluoroalkyl compounds in the actual environment] In the experimental results of the activated carbon filter section shown in Table 16, three types of fluorotelomer alcohols (FTOHs) including 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH were detected in the living room and bedroom of the developer's home. These FTOHs are known to be used in carpets, clothing, and interior decorations, and it is reasonable to detect these FTOHs in the living room or bedroom where various furniture are installed. In addition, although the target substances detected in the living room and the bedroom were of the same type, a clear difference in concentration was observed, and the recovery rate of the surrogate test product was also good, which can be said to show the significance of the sampler used for the determination of perfluoroalkyl and polyfluoroalkyl compounds. In addition, it was shown that a high level of analysis could be achieved even under the condition of ventilation at 10.0ml/min for 11 hours.

在表17所示的胺基甲酸酯發泡體過濾器部的實驗結果之中,客廳及寢室皆得到並未偵測到對象物質的結果,然而替代試驗品的回收率良好,因此作為半揮發性全氟及多氟烷基化合物的採樣器的精密度良好,認為在測定對象的客廳及寢室中,半揮發性全氟及多氟烷基化合物幾乎不存在。 In the experimental results of the urethane foam filter shown in Table 17, the target substance was not detected in both the living room and the bedroom. However, the recovery rate of the alternative test product was good, so the precision of the sampler for semi-volatile perfluoroalkyl compounds was good. It is believed that semi-volatile perfluoroalkyl compounds are almost non-existent in the living room and bedroom.

如以上所述般,藉由使用具有可脫離地吸附全氟及多氟烷基化合物的物性的活性碳,可得到可效率良好地收集大氣中的該化合物的過濾器的活性碳過濾器部。另外,藉由將該活性碳製成吸附劑,形成具有一定通氣性的過濾器,可製成可攜帶且可進行高精密度的測定的個人暴露測量用的全氟及多氟烷基化合物採樣器。 As described above, by using activated carbon having the property of releasably adsorbing perfluoroalkyl compounds, an activated carbon filter portion of a filter that can efficiently collect the compounds in the atmosphere can be obtained. In addition, by making the activated carbon into an adsorbent to form a filter with a certain degree of air permeability, a portable perfluoroalkyl compound sampler for personal exposure measurement that can perform high-precision measurements can be produced.

另外,藉由在活性碳過濾器部的前段配置胺基甲酸酯發泡體過濾器部,可在胺基甲酸酯發泡體過濾器部收集半揮發性全氟烷基化合物,在活性碳過濾器部收集揮發性全氟及多氟烷基化合物,進行所謂的分別收集。而且還可謀求減少當作吸附劑的活性碳的吸附性能劣化。此外,藉由在胺基甲酸酯發泡體過濾器部的前段配置收集粒子的慣性衝擊器等,還可對各種形態的全氟及多氟烷基化合物取樣,可總括地進行全氟及多氟烷基化合物的收集、測定。 In addition, by configuring a urethane foam filter section in the front section of the activated carbon filter section, semi-volatile perfluoroalkyl compounds can be collected in the urethane foam filter section, and volatile perfluoro and polyfluoroalkyl compounds can be collected in the activated carbon filter section, so-called separate collection can be performed. It is also possible to reduce the deterioration of the adsorption performance of the activated carbon used as an adsorbent. In addition, by configuring an inertial impactor for collecting particles in the front section of the urethane foam filter section, various forms of perfluoro and polyfluoroalkyl compounds can be sampled, and perfluoro and polyfluoroalkyl compounds can be collected and measured in a comprehensive manner.

[產業上的可利用性] [Industrial availability]

本發明之個人暴露測量用全氟及多氟烷基化合物採樣器,由攜帶性高,可對個人裝設,可高效且可脫離地收集工作環境中的全氟及多氟烷基化合物,因此可使以現今採樣器無法測定的該化合物個人暴露量成為可測定。由此可知,能夠有效果、有效率地定量評估工作者等對規範對象的環境殘留性有機污染物質的暴露量,可顯著防止工作者的健康障礙。 The perfluoroalkyl and polyfluoroalkyl compound sampler for personal exposure measurement of the present invention is highly portable and can be installed on individuals. It can efficiently and detachably collect perfluoroalkyl and polyfluoroalkyl compounds in the working environment, so that the personal exposure to the compounds that cannot be measured by current samplers can be measured. It can be seen that the exposure of workers to environmental residual organic pollutants of regulated objects can be quantitatively evaluated effectively and efficiently, which can significantly prevent health problems of workers.

10:碟型匣盒 10: Disc-shaped box

11:吸氣開口部 11: Inhalation opening

12:本體部 12: Main body

20:活性碳過濾器部 20: Activated carbon filter section

21:氈狀過濾器部 21: Felt filter part

[圖1]為表示被設置於本發明之個人暴露測量用全氟及多氟烷基化合物採樣器中的碟型匣盒的概要圖。 [圖2]為圖1的碟型匣盒的一部分截面圖。[Figure 1] is a schematic diagram showing a disk-shaped cartridge installed in the perfluoroalkyl compound sampler for personal exposure measurement of the present invention. [Figure 2] is a partial cross-sectional view of the disk-shaped cartridge of Figure 1.

Claims (9)

一種個人暴露測量用全氟及多氟烷基化合物採樣器,其係具備以可脫離地吸附全氟及多氟烷基化合物之以活性碳為主要吸附劑的活性碳過濾器部之用來測量個人暴露量的可攜式全氟及多氟烷基化合物採樣器,其特徵為:前述活性碳的BET比表面積為900m2/g以上,前述活性碳過濾器部在風速0.5m/sec條件下的壓力損失未達6kPa。 A perfluoroalkyl compound sampler for measuring personal exposure is a portable perfluoroalkyl compound sampler for measuring personal exposure, which is equipped with an activated carbon filter section with activated carbon as the main adsorbent for releasably adsorbing perfluoroalkyl compounds. The activated carbon has a BET specific surface area of 900 m2 /g or more, and the pressure loss of the activated carbon filter section under a wind speed of 0.5 m/sec does not reach 6 kPa. 如請求項1之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳之1nm以下的微孔容積之和(Vmic)為0.35cm3/g以上。 For the per- and polyfluoroalkyl compound sampler for personal exposure measurement as claimed in claim 1, the sum of the micropore volumes of the activated carbon having a size of less than 1 nm (V mic ) is greater than 0.35 cm 3 /g. 如請求項1或2之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳之2~60nm以下的中孔容積之和(Vmet)為0.03cm3/g以上。 For the per- and polyfluoroalkyl compound sampler for personal exposure measurement as claimed in claim 1 or 2, the sum of the mesopore volumes of the activated carbon having a diameter of 2 to 60 nm (V met ) is 0.03 cm 3 /g or more. 一種個人暴露測量用全氟及多氟烷基化合物採樣器,其係具備以可拆卸地吸附全氟及多氟烷基化合物之以活性碳為主要吸附劑的活性碳過濾器部之用來測量個人暴露量的可攜式全氟及多氟烷基化合物採樣器,其特徵為:前述活性碳的BET比表面積為900m2/g以上,前述活性碳過濾器部在風速0.5m/sec條件下的壓力損失未達6kPa,前述活性碳之下述(i)式規定的前述活性碳之1nm以下 的微孔容積之和(Vmic)與前述活性碳之2~60nm以下的中孔容積之和(Vmet)的容積差(Vs)為0.35以上, V s =V mic -V met (i)。 A perfluoroalkyl compound sampler for measuring personal exposure is a portable perfluoroalkyl compound sampler for measuring personal exposure, which is equipped with an activated carbon filter section with activated carbon as a main adsorbent for detachably adsorbing perfluoroalkyl compounds. The activated carbon has a BET specific surface area of 900 m2 /g or more, the pressure loss of the activated carbon filter section under a wind speed of 0.5 m/sec is less than 6 kPa, and the volume difference (Vs) between the sum of the micropore volume of the activated carbon below 1 nm ( Vmic ) and the sum of the mesopore volume of the activated carbon below 2 to 60 nm ( Vmet ) as specified by the following formula ( i ) of the activated carbon is 0.35 or more, Vs = Vmic - Vmet ... ( i). 如請求項1或4之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳的表面氧化物量為0.10meq/g以上。 For perfluoroalkyl and polyfluoroalkyl compound samplers for personal exposure measurement as in claim 1 or 4, the surface oxide content of the activated carbon is 0.10 meq/g or more. 如請求項1或4之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳為纖維狀活性碳。 For perfluoroalkyl compound samplers for personal exposure measurement as in claim 1 or 4, the activated carbon is fibrous activated carbon. 如請求項1或4之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳為粒狀活性碳。 For perfluoroalkyl compound samplers for personal exposure measurement as in item 1 or 4, the activated carbon is granular activated carbon. 如請求項1或4之個人暴露測量用全氟及多氟烷基化合物採樣器,其中前述活性碳過濾器部係被收載於碟型匣盒,前述匣盒係被備置成可著裝拆卸。 For example, in the perfluorinated and polyfluorinated alkyl compound sampler for personal exposure measurement as claimed in claim 1 or 4, the activated carbon filter portion is contained in a disc-shaped cartridge, and the cartridge is provided to be wearable and detachable. 如請求項1或4之個人暴露測量用全氟及多氟烷基化合物採樣器,其中由胺基甲酸酯發泡體所形成的胺基甲酸酯發泡體過濾器部係被配置於前述活性碳過濾器部的前段而成。 For example, in the perfluoroalkyl compound sampler for personal exposure measurement of claim 1 or 4, the urethane foam filter part formed by the urethane foam is arranged in the front section of the activated carbon filter part.
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