一、文獻回顧

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一、文獻回顧

近年醛酮之污染問題已逐漸廣受注意之有害空氣污染物，其中醛類常存於不完全燃燒之排放廢氣中及碳氫化合物受光化反應形成，並被視為空氣中之光化學反應之氧化物，而勞工於工作場所暴露於醛類之風險也為許多研究者所重視，

其中大部研究著重在對人體刺激性之影響，包括眼、呼吸過敏、頭疼、與口乾之症狀(Goldschmidt, 1984)，另該物質在文獻指出對人體是有毒且致癌的，並影響體內脂和酒精之新陳代謝反應(NRC, 1981)及可能與次氯酸作用形成致癌性物質 bis(chloromethyl) ether。醛和酮類化合物，而醛類之毒性隨分子量增加而減低。

因醛及酮在大氣光化反應形成光化學煙霧(smog)過程中為重要之前趨物質，同時在污染之大氣為主要之自由基及有機氣膠來源，故其同時為一次及二次污染物 (Tanner and Meng, 1984)，故如何敏銳地選擇在排放之廢氣及週界空氣測定該類物質已逐漸受到關心。從研究文獻得知醛類之分析，利用衍生方式再以高效率液相層析法 (high performance liquid chromatograph, HPLC)與氣相層析進行，並分述如下：

1-1 高效率液相層析法 1-1-1 DNPH法

醛類在HPLC之析常需以DNPH (2,4-dinitrophenyl hydrazine)先行衍生，反應產生相對應2,4-dinitrophenyl hydrazone 衍生物 (反應式如下)，此物質與UV 吸收值有較佳之相關性(Fung and Grosjean, 1981； Papa and Turner, 1972；Coutrim et al., 1993；de Andrade,1993)，而在相同之分子量之醛類及酮類大部份可藉配有逆相μ BondapakC18之管柱得以分離(Selim, 1977)。(Qlson K. et al., 1985 )亦以

LC-MS進行含羰基 (carbonyl)以DNPH進行衍生產生之物質。然而以該方法進

行醛酮分析時，試劑空白、實驗室空氣中之污染則需考量，而二氧化氮對DNPH 之反應對醛類之分析干擾應需注意(Karst. U. et al., 1993)。

在空氣對醛類之採樣方法-impinger 法，亦採用含DNPH之吸收液進行 (Fung ---(1)

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K. and Grosjean D., 1981 ; Grosjean D., 1982 ; Tanner R. L. and Meng Z., 1984)，另亦有以矽管柱附著DNPH及氫氯酸 (Bersley R. K. et al., 1980)，或以含玻璃珠之玻璃管柱並附磷酸及飽和之poly-(ethylene glycol)(Grosjean D., 1982)進行進行空氣中醛酮之採樣分析。(Bersley R. K. et al., 1980)之研究者則以填充Sep-Pak C18含 DNPH及磷酸之管柱決定空氣C1-C4之醛類物質，此方式其回收率可達95%以上，方法偵測極限則達 sub-ppb之水準，此方式為目前空氣採樣最常用之方法。

1-1-2 其它方法

Swarin and Lipari(1983)使用2-diphenylacetyl-1,3-indandione-1-hydrazone與醛類生成螢光性物質，並利用HPLC配合螢光偵檢器測定汔車中醛類物質，其反應式如圖2所示。另Groemping and Cammann (1993)亦利用該方法進行大氣中醛類物質之測定：

R CHO+

OH

N C

NH₂ O

CH

OH

N C

N O

CH

C R

+^H2O

Nondek et al.(1991 ； 1992) 多孔玻璃珠附著

ansylhydrazine[5-(dimethylamino)naphthalene-1-sulfohydrazide 利用 HPLC之螢光

及chemiluminescene檢知器進行醛類之線上偵測，對甲醛及乙醛之偵測極限值可

達0.1 ppb。

1-2 氣相層析法

1-2-1 Oxime 衍生法 (Oxime derivation)

早期醛類以DNPH進行衍生以GC進行分析，因此衍生物為低揮發性，故需將GC控制於高溫下進行方可，而Oxime之衍生物之揮發性則較DNPH衍生物為優，故Magin (1979；1980)曾以benzyloxime與香煙中含羰基之揮發性有機物，以 GC進行定性及半定量分析，此反應式如下：

CH₂ O NH₂

+

R CHO CH₂ O N CH R+^H²^O

---(2)式

---(3)式

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Levin et al.(1981)則以含0.5M醋酸鈉緩衝溶液之甲醇與benzyloxime hydrochloride 進行衍生產生 O-benzyloxime ，並藉 GC 配 NPD 偵檢器 (nitrogen-selective diction)進行分離，此反應效率約有90%，此方法適用於移動車輛與固定污染源，但不適用於週界空氣之醛類分析。另O-pentafluorobenzyloximee 亦被用於含羰基之分析，其反應式如下

F F

F CH₂ O NH₂

F F

R CHO+ F _CH₂ O N CH R+^H2O

1-2-2 Bromination of unsaturated aldehyde oxime

丙烯醛(acrolein)屬不飽和之醛類，它對皮膚、眼晴與鼻黏膜有剌激性之影響，可利用4-hexylresorcinol衍生進行比色 (Cohen and Altshuller, 1961)，但此方法之選擇性不佳，雖然文獻利用GC進行丙烯醛之Bromination (Nishikawa et al., 1985)分析，但因該類衍生物不穩定及再現性不佳，故Nishikawa et al. ( 1986)修正丙烯醛之O-methyloxime反應，以測定環境中之丙烯醛，此修正反應式如下式，

該反應可於室溫下反應，反應產物為 2,3-dibromopropionaldehyde O-methyloxime，可藉由GC-MS分析。

CH₂ CH CHO

+

CH₃ O ^NH2 CH₃ O N CH CH CH₂

+

^H2O

CH₃ O N CH CH CH₂

+

^Br² ^CH³ ^CH

Br N CH CH

Br O

另不飽和醛與O-benzyloxime之衍生物再進行溴化作用，亦可用來檢測丙烯醛與crotonaldehyde，其反應式如下，其反應效率分別為98%與88% (Nishikawa et al., 1987)。

CH₂ CH CHO+ ^CH2 O NH₂ CH₂ O N CH CH CH₂+^H2O

CH₂ O N CH CH CH₂+ ^Br2 CH₂ O N CH CH CH Br Br

1-2-3其它方法

揮發性之醛類與 2-amino-ethanethiol(cysteamine)反應可形成 thiazolidine 化 ---(4)式

---(5)式

---(6)式

---(7)式

---(8)式

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合物 (Yasuhara and Shibamoto, 1991)，此反應稱為cysteamine法，反應方程式如下，此法配合 GC-NPD可測定移動車輛廢氣中 C1-C6之醛類物質 (Yasuhara and Shibamoto, 1994)：

+

R CHO

CH₂ CH₂ SH NH₂

NH S R

H

+

^H2O

APHA Method 122，Determination of C1-C5 aldehydes in Ambient Air and Source Emissions as 2,4-Dinitrophenylhydrazones by HPLC。

Beasley R.K., Hoffmann C.E., Rueppel M.L. and Worley J.W. 1980, “Sampling of Formaldehyde in Air with Coated Solid Sorbent and Determination by High Performance Liquid Chromatography “, Anal.Chem. 52:1110.

Cohen I. R. and Altshuller A. P. 1961, A new spectrophotometric method for the determination of acrolein combustion gases and in the atmosphere, Anal. Chem., 33:726-733.

Coutrim MX, Nakamura LA, Collins CH. 1993, Quantification of 2,4-dinitrophenyl-hydrazones of low molecular mass aldehydes and ketones using HPLC. Chromatographia.37:185–90.

de Andrade JB, Pinheiro HLC, Andrade MV. 1993, Determination of formaldehyde and acetaldehyde associated atmospheric aerosols by HPLC. Intern J Environ Anal Chem. 52:49–56.

Fung K, Grosjean D. 1981, Determination of nanogram amounts of carbonyls as 2,4-dinitrophenylhidrazones by high-performance liquid chromatography. Anal Chem. 53:166–71.

Gioacchini AM, Roda A, Galletti GC, Bocchini P, Manetta AC, Baraldini M. 1996, High-performance liquid chromatography-electrospray mass spectrometric analysis of phenolic acids and aldehydes. J chromatogr. A 1996:730:31–37.

Goldschmidt BM. 1984, Role of aldehydes in carcinogenesis. J Environ Sci Health;

2:231–49.

Groemping A. H. J. and Cammann K. 1993, Development and comparison of different fluorimetric HPLC-methods with standard methods for the determination of formaldehyde in the atmosphere, Chromatographia, 35:142-148.

Grosjean D. 1982, Environ.Sci. Technol., 16:254.

Grosjean D. and Fung K. 1982, Anal. Chem., 54:1221.

---(9)式

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Karst. U. et al. 1993, Fresenius J. Anal. Chem., 345:48.

Magin J. Chromatogr D. F. 1979, Preparation and gas chromatographic

characterization of benzyloximes and p-nitrobenzyloximes of short-chain(C1-C7) carbonyls, Journal of Chromatography, 178:219-227.

Magin J. D. F. 1980, Gas chromatography of simple monocarbonyls in cigarette whole smoke as the benzyloxime derivatives, Journal of Chromatography, 202:255-261.

Nishikawa H. et al. 1986,Determination of micro amount of acrolein in air by gas chromatography, Journal of Chromatography, 370:327-333.

Nishikawa, H. and Sakai, T. 1995, “Derivatization and Chromatographic Determination of Aldehydes in Gaseous And Air Samples”, Journal of Chromatography . A 710:159-165.

Nondek L. et al. 1991, Determination of carbonyl compounds in air by HPLC using on-line analyzed microcartridges, fluorescence and chemilumines detection, Chromatographia, 32:33-39.

Papa LJ, Turner LP. 1972, Chromatographic determination of carbonyl compounds as their chromatography I. Gas chromatography. J Chromatogr Sci. 10:744–7.

Peters R, Hellenbrand J, Mengerink Y, Van der Wal SJ. 2004, On-line determination of carboxylic acids, aldehydes and ketones by High-performance liquid chromatography-diode array detection-atmospheric chemical ionization mass spectrometry after derivatization with 2-nitrophenylhydrazine. J chromatogr.

A2004: 1031:30–50.

Qlson K.and Swarin S. J. 1985, J. Chromatogr., 333:337.

Sakuragawa A, Yoneno T, Inoue K, Okutani T. 1999, Trace analysis of carbonyl compounds by liquid chromatography-mass spectrometry after collection as 2,4-dinitrophenylhydrazine derivatives. J chromatogr. A 1999:844:403–408.

Sakuragawa, A. ,Yoneno, T. ,Inoue, K. and Okutani T. 1999, “Trace Analysis of Carbonyl Compounds by after Collection As 2,4-Dinitrophenylthyhydrazine derivatives”, Journal of Chromatography. A1999:844: 403-408.

Selim S. 1977, Separation and quantitative determination of traces of carbonyl compounds as their 2,4-dinitrophenylhdrazones by high-pressure liquid chromatography, Journal of Chromatography, Journal of Chromatography, 136:271-277.

Swarin S. J. and Lipari F. 1983, Deternation of formaldehyde and other aldehydes by

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high performance liquid chromatography with fluorescence detection, Journal of Liquid Chromatography, 6:425-444.

Tanner R.L. and Meng Z. 1984, “Seasonal Variations in Ambient Atmospheric Levels of Formaldehyde and Acetaldehyde “, Environ. Sci. Technol. 18:723-726.

US EPA Method TO-11A: Determination of Formaldehyde in Ambient Air Using Adsorbent Cartridge Followed by High Performance Liquid Chromatography (HPLC).

US EPA Method TO-5: Determination of Aldehydes and Ketones in Ambient Air Using High Performance Liquid Chromatography (HPLC).

行政院環境保護署，（81年），大氣中有機汙染物質檢驗方法之建立-第二年，

EPA-81-E3S3-09-01。

行政院環境保護署，（86年），煙道排氣中醛類檢測方法之驗證與研究，

EPA-86-1304-01-01。

一、 文獻回顧