水道水中のハロアセトアルデヒド類およびハロアセトン類の PTV
>ࣀ࣮ࢺ@ Ỉ㐨Ỉ୰ࡢࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢ 379*&06 ἲࡼࡿ㧗ឤᗘศᯒἲࡢ㛤Ⓨ ᕝඖ 㐩ᙪ㸨 ▮㔝 ⨾✑ ᳃⏣ ᐶᏊ ୕ᶫ 㝯ኵ Development of a Highly Sensitive Method for Analysis of Haloacetaldehydes and Haloacetones in Tap Water by PTV-GC/MS Methods Tatsuhiko KAWAMOTO㸨㸪Miho YANO㸪Hiroko MORITA and Takao MITSUHASHI Life Science Division㸪Public Health Science Research Center㸪Hyogo Prefectural Institute of Public Health and Consumer Sciences㸪2-1-29㸪Arata-cho㸪Hyogo-ku㸪Kobe 652-0032㸪Japan During the water purification process, disinfection by-products, such as haloacetaldehydes and haloacetones are formed by ozone or chlorination. The sensitive analytical method for 4 haloacetaldehydes and 6 haloacetones in tap water was developed by programmable temperature vaporization (PTV)-GC/MS. haloacetaldehydes and haloacetones were extracted with MTBE after acidifying with H2SO4. Aqueous These extracts were analyzed by PTV-GC/MS. The quantitation limits of haloacetaldehydes and haloacetones by using these methods were 0.05-0.1Ǎg/L and 0.05Ǎg/L, respectively. Furthermore, we conducted a water-quality test using this method for 15 water samples collected from 15 monitoring points in the Hyogo Prefecture. Haloacetaldehydes and haloacetones were detected at the level of ND-11.0Ǎg/L and ND-1.7Ǎg/L, respectively. Ϩ ࡣࡌࡵ ࢹࣄࢻ௨እࡢࣁࣟࢭࢺࣝࢹࣄࢻ㢮㸪ࣁࣟࢭࢺࣥ㢮 ࡣ୰㛫యࡋ࡚⏕ᡂࡍࡿࡇࡀ▱ࡽࢀ࡚࠸ࡿࡀ 5)㸪Ỉ㐨 ᪥ᮏ࡛ࡣ㸪Ỉ㐨ἲỈ㉁ᇶ‽ᨵṇ㸦2004ᖺ4᭶1᪥㸧௨ Ỉ୰ࡢᏑᅾᐇែ㛵ࡍࡿ◊✲ࡣṤ࡞ࡉࢀ࡚࠸࡞࠸㸬Ỉ 㝆㸪ከࡃࡢᾘẘ⏕ᡂ≀ࡀ㏲ḟᨵṇ࡛つไᙉࡉࢀ࡚ࡁ 㐨ỈࡢᏳᛶࢆ☜ಖࡍࡿࡓࡵࡣ㸪ࡇࢀࡽࡢᾘẘ⏕ᡂ 㸯㸧 ࡓ 㸬ලయⓗ࡞ࡋ࡚㸪࣒࣍ࣝࣝࢹࣄࢻࡣ᪂ࡓᇶ ≀ࡢศᯒἲ㛤Ⓨ࠾ࡼࡧᐇែㄪᰝࡣ㔜せ⪃࠼ࡽࢀࡿ㸬 ‽㡯┠ࡋ࡚⨨࡙ࡅࡽࢀ㸪྾ධᭀ㟢⤒㊰ࡽⓎࡀࢇᛶ ࣝࢹࣄࢻ㢮ࡢศᯒἲࡘ࠸࡚ࡣ㸪ᚑ᮶㸪GC/ECD ࢆ⪃៖ࡋ࡚ᇶ‽್80Ǎg/Lࡀタᐃࡉࢀࡓ㸬ࡲࡓ㸪ᢪỈࢡࣟ ἲ 6)ࡀὶ࡛࠶ࡗࡓࡀ㸪ⴭ⪅ࡽࡣ㑅ᢥᛶࡢ㧗࠸ GC/MS ࣮ࣛࣝ㸦ࢺࣜࢡࣟࣟࢭࢺࣝࢹࣄࢻ㸧ࡣỈ㉁⟶⌮┠ᶆ ἲࡼࡿศᯒἲࢆ㛤Ⓨࡋ㸪ᐇែㄪᰝ㐺⏝ࡋ࡚ࡁࡓ 7)㸬 タᐃ㡯┠㸦┠ᶆ್20Ǎg/L㸧タᐃࡉࢀ㸪ࢭࢺࣝࢹࣄ ୍᪉㸪ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢ ࢻࡣせ᳨ウ㡯┠㸦┠ᶆ್ᮍタᐃ㸧ࡋ࡚タᐃࡉࢀࡓ2-4)㸬 ศᯒἲࡘ࠸࡚ࡣ㸪GC/ECD ἲࡀሗ࿌ ࡇࢀࡽࡢᾘẘ⏕ᡂ≀ࡣ㸪ࢺࣜࣁ࣓ࣟࢱࣥ࠾ࡼࡧࣁࣟ㓑 GC/MS ἲࡼࡿศᯒἲࡣṤ᳨ウࡉࢀ࡚࠸࡞࠸㸬ᚑࡗ 㓟ྠᵝ㸪ἙᕝỈ୰ࡢࣇ࣑ࣥ㉁ࡸ㢮ఝ≀㉁ίỈฎ⌮ ࡚㸪ࡼࡾ㑅ᢥᛶࡀඃࢀ㸪ࡘ㧗ឤᗘ࡞ GC/MS ࡼࡿศ ࡢ࢜ࢰࣥࡸሷ⣲ࡢᛂࡼࡾ⏕ᡂࡍࡿࡇࡀ▱ࡽࢀ࡚ ᯒἲ㛤Ⓨࡀᚲせ࡞ࡗ࡚࠸ࡿ㸬 ࠸ࡿ1)㸬ࡋࡋ࡞ࡀࡽ㸪࣒࣍ࣝࣝࢹࣄࢻࡸࢭࢺࣝ 8,9)ࡉࢀ࡚࠸ࡿࡀ㸪 ㏆ᖺ㸪ᙜ◊✲ᡤ࡛ࡣ␗⮯ⱞࡢỈ㐨Ỉࡘ࠸࡚⥭ᛴศ ᯒᑐᛂࡋ࡚㸪ࣁࣟࢭࢺࣥ㢮ࡢࡦࡘ࡛࠶ࡿⓎᛶ ᗣ⛉Ꮫ㒊 1,1,1-ࢺࣜࢡࣟࣟࢭࢺࣥࢆࣃ࣮ࢪ㸤ࢺࣛࢵࣉ (P&T) 㸨ูๅㄳồඛ㸸ࠛ652-0032 ⚄ᡞᕷරᗜ༊Ⲩ⏣⏫ 2-1-29 -GC/MSἲࡼࡾྠᐃ࣭ᐃ㔞ࡋ㸪Ỉ㐨Ỉࡢΰධ⤒㊰ࡢ රᗜ┴❧ᗣ⏕ά⛉Ꮫ◊✲ᡤ ᗣ⛉Ꮫ◊✲ࢭࣥࢱ࣮ ≉ᐃᐤࡋࡓ㸬ࡋࡋ㸪Ⓨᛶࡢࣁࣟࢭࢺࣥ㢮ࡸ ᗣ⛉Ꮫ㒊 ᕝඖ 㐩ᙪ ࣁࣟࣝࢹࣄࢻ㢮ࢆྵࡴ㣧ᩱỈᗣ༴ᶵ⟶⌮ࡢ㎿㏿ᑐ － 40 － රᗜ┴❧ᗣ⏕ά⛉Ꮫ◊✲ᡤᗣ⛉Ꮫ◊✲ࢭࣥࢱ࣮◊✲ሗ࿌ ➨ ྕ ᛂࡶ㔜せ࡛࠶ࡿࡇࡽ㸪ᐜ㔞ὀධᶵ⬟( PTV: 2. GC/MS ศᯒ᮲௳ Programmable temperature vaporization㸧⁐፹ᢳฟ 1) ᐃ᮲௳ࡢ᳨ウ -GC/MSἲࢆ⤌ࡳྜࢃࡏࡓ୍ᩧศᯒἲࡢ㛤Ⓨࢆ⾜ࡗࡓࡢ ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢ ࡛㸪ࡑࢀࡽࡢ⤖ᯝࡘ࠸࡚ሗ࿌ࡍࡿ㸬ࡲࡓ㸪රᗜ┴Ỉ㐨 GC/MS ศᯒ᮲௳㸦᪼ 㸪࣒࢝ࣛ᮲௳➼㸧ࢆ Table 1 Ỉ㉁⟶⌮ィ⏬10)ᇶ࡙ࡃ┘ど14ᆅⅬࡢỈ㐨Ỉ࠾ࡼࡧ␗ ♧ࡋࡓ㸬 ࡞࠾㸪㧗ឤᗘࢆ┠ⓗ PTV ᶵ⬟ᐜ㔞 5ǍL ࢆὀ ⮯ⱞࡢỈ㐨Ỉࡢྵ᭷㔞ㄪᰝࡶ⾜ࡗࡓࡢ࡛ేࡏ࡚ሗ࿌ࡍ ࡿ㸬 ධ᮲௳ࡋࡓ㸬 2) ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢࣔ ϩ ᮦᩱ᪉ἲ ࢽࢱ࣮࢜ࣥ ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢࣔࢽ 1. ヨᩱ➼ ࢱ࣮࢜ࣥࢆ Table 2 ♧ࡋࡓ㸬ࡇࢀࡽࡢ≉ᚩⓗ࡞࢜ 1. 1 ヨ⸆➼ ࣥࢆ⏝࠸࡚ᐃ㔞ࢆ⾜ࡗࡓ㸬 1) ศᯒᑐ㇟ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺ ࣥ㢮㸸 ձࢡࣟࣟࢭࢺࣝࢹࣄࢻ㸪ղࢪࢡࣟࣟࢭࢺ 3. Ỉ୰ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮 ࣝࢹࣄࢻ㸪ճࢺࣜࢡࣟࣟࢭࢺࣝࢹࣄࢻ㸪մࢺࣜࣈࣟ ࡢ⁐፹ᢳฟ-PTV-GC/MS ศᯒ ࣔࢭࢺࣝࢹࣄࢻ㸪յࢡࣟࣟࢭࢺࣥ㸪ն1,1-ࢪࢡࣟ Ỉ୰ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡣ㸪 ࣟࢭࢺࣥ㸪շࣈࣟࣔࢭࢺࣥ㸪ո1,1,1-ࢺࣜࢡࣟࣟ ⁐፹ᢳฟ-PTV-GC/MS ศᯒࢆ⾜ࡗࡓ㸬༶ࡕ㸪ヨᩱỈ୰ ࢭࢺࣥ㸪չ1,3-ࢪࢡࣟࣟࢭࢺࣥ㸪պ1,1,3-ࢺࣜࢡࣟࣟ 50mL㸦ࡲࡓࡣࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭ ࢭࢺࣥࡋࡓ㸬ࡇࡢ࠺ࡕ㸪␗⮯ཎᅉ≀㉁࡞ࡗࡓ 1,1,1,- ࢺࣥ㢮ࡢᶆ‽ᾮࡋ࡚㸪0㸪0.05, 0.1㸪0.5㸪1.0㸪2.0㸪 ࢺࣜࢡࣟࣟࢭࢺࣥࡢᵓ㐀ᘧࢆ Fig. 1 ♧ࡋࡓ㸬 5.0㸪10.0㸪20.0Ǎg/L ࢆྵࡴᵝ⢭〇Ỉࢆຍ࠼࡚ 50mL ࡇࢀࡽࡢΰྜᶆ‽ᾮࡣ㸪ྛ✀ᶆ‽ရ㸦ᮾிᡂᕤᴗ♫ ࡋࡓࡶࡢ㸧ࢆ㸪ඹᰦヨ㦂⟶ 50mL ᥇ࡾ㸪◲㓟㸦1 〇㸧ࢆ࠸ࡎࢀࡶ㹲㸫ࣈࢳ࣓ࣝࢳ࢚࣮ࣝࢸࣝ㸦MTBE㸧࡛ 㸩1㸧ࢆ 3.2mL ຍ࠼࡚ᙉ㓟ᛶ㸦pH㸺0.5㸧ࡋ㸪ሷࢼ 1,000mg/L ⃰ᗘࡢࡶࡢࢆㄪ〇ࡋ㸪୍ᐃ㔞ࢆΰࡋ࡚ ࢺ࣒ࣜ࢘ 20g MTBE㸦3mL㸪2mL㸧ࢆຍ࠼࡚⃭ࡋࡃ 100mg/L ࡢᶆ‽ཎᾮࢆㄪ〇ࡋࡓ㸬ࡇࡢΰྜᶆ‽ཎᾮࢆ ࠺ࡍࡿᢳฟ᧯సࢆ 2 ᅇ⧞ࡾ㏉ࡋ࡚⾜࠸㸪ࣁࣟࢭࢺ MTBE ࡛㐺ᐅᕼ㔘ࡋ㸪ྛ✀ᐇ㦂ᚲせ࡞ᶆ‽⁐ᾮࢆㄪ〇 ࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࢆᢳฟࡋࡓ㸬 ࡋࡓ㸬 2) ⢭〇Ỉ㸸Milli Q SP. TOC㸦࣑࣏ࣜ♫〇㸧࡛ㄪ〇ࡋ Table 1 GC/MS operation conditions ࡓࡶࡢࢆ⢭〇Ỉࡋࡓ㸬 GC/MS㸸 TSQ Quantum GC (Termo Fisher Scientific co., ltd.) 3) ࣑ࢿ࢛࣮ࣛࣝ࢘ࢱ࣮㸸 ῧຍᅇᐇ㦂⏝࠸ࡓ࣑ࢿࣛ Column㸸Vocol 㸦I.D. 0.25mm, Length 30m, Phase thickness 1.5Ǎm㸧 ࢛࣮ࣝ࢘ࢱ࣮ࡣ࢚ࣦࣥ㸦࢚ࣦࣥ♫〇㸪ࣇࣛࣥࢫ㸧 Carrier Gas 㸸 He (1mL/min) PTV: 40䉝 (2min) 䊻 10䉝/min 䊻 280䉝 (10min) ࢆ⏝࠸ࡓ㸬pH㸪SS㸦ᾋ㐟≀㉁㸧ࡢ ᐃࡘ࠸࡚ࡣ㸪ୖ Oven temp.㸸40Υ㸦5min㸧Ѝ 5Υ/min Ѝ 220Υ Ỉヨ㦂ἲ 11)‽ᣐࡋ࡚⾜ࡗࡓ㸬 Injection volume㸸5ǍL 4) ሷࢼࢺ࣒ࣜ࢘㸸 ሷࢼࢺ࣒ࣜ࢘㸦ග⣧⸆ᕤᴗ♫ 〇㸧ࡣ≉⣭ࢆ⏝ࡋ㸪㟁Ẽ⅔࡛ 500Υ㸪5 㛫⇱ࡋࡓ Mode 㸸Full scan, SIM Ionization energy 㸸 70 eV Ionization current㸸 150 ǍA Source temp.㸸 185 Υ Interface temp.㸸 280 Υ ᚋ㸪⏝ࡲ࡛ࢹࢩࢣ࣮ࢱ࣮୰ಖᏑࡋࡓ㸬 5) ᭷ᶵ⁐፹㸸 MTBE ࡣ㛵ᮾᏛ♫〇ࡢỈ㉁ヨ㦂⏝ࢆ㸪 ࣓ࢱࣀ࣮ࣝ㸪n-࣊࢟ࢧࣥࡣṧ␃㎰⸆ヨ㦂⏝ 5,000㸦ග Table 2 Monitor ion of haloaldehydes and haloacetones ⣧⸆ᕤᴗ♫〇㸧ࢆ⏝࠸ࡓ㸬 O Cl Cl Cl Fig. 1 Chemical structure of 1,1,1-trichloroacetone － 41 － No. 1 2 3 4 5 6 7 8 9 10 Compounds chloroacetaldehyde dichloroacetaldehyde chloroacetone trichloroacetaldehyde 1,1-dichloroacetone bromoacetone 1,1,1-trichloroacetone 1,3-dichloroacetone 1,1,3-trichloroacetone tribromoacetaldehyde Monitor ion (m/z) 50 78 80 83 84 112 77 78 92 82 111 119 63 83 91 93 136 138 97 119 125 77 126 128 77 79 83 173 175 254 ࡓ㸬࠸ࡎࢀࡢ ᐃ≀㉁ࡶ㧗ᴟᛶࡢ Vocol ࣒࢝ࣛ㸦ࢫ࣌ࣝ Sample (50mL) ࢥ♫〇㸧࡛ࡢศ㞳ࡣⰋዲ࡛࠶ࡗࡓ㸬ᅗࡣ♧ࡋ࡚࠸࡞࠸ 䊹residual chlorine removal (0.3% sodium thiosulfate) 䊹dilute sulfulic acid (3.2mL) 䊹sodium chloride (20g) ࡀ㸪ᚤᴟᛶ㹼୰ᴟᛶ࣒࡛࢝ࣛࡣࢡࣟࣟࢭࢺࣝࢹࣄࢻ ࡣಖᣢࡉࢀࡎ㸪ࡲࡓ MTBE ࡛࠶ࡿᢳฟ⁐፹ࣆ࣮ࢡࡢ ศ㞳ࡀᅔ㞴࡛࠶ࡗࡓ㸬㧗ᶫࡽ 8)ࡣ㸪ⴭ⪅ࡽྠࡌ Vocol Solvent phase extraction (MTBE䠖3, 2mL) ࣒࢝ࣛࢆ⏝࠸ࡓ GC/MS ศᯒ࠾࠸࡚ࢡࣟࣟࢭࢺࣝ ࢹࣄࢻࡢ☜ㄆࡣ MTBE 㔜࡞ࡿࡓࡵᅔ㞴࡛࠶ࡾ㸪 Organic layer (MTBE) GC-ECD ࡛ᐃ㔞ࢆ⾜ࡗࡓࡢሗ࿌ࡀ࡞ࡉࢀ࡚࠸ࡿࡀ㸪ⴭ ⪅ࡽࡢ࣒࢝ࣛ᪼ ᮲௳࡛ࡣಖᣢ㛫 6.97 ศࢡࣟࣟ Dehydration ࢭࢺࣝࢹࣄࢻࡢࣆ࣮ࢡࢆㄆࡵ㸪ࣛࣈ᳨࣮ࣛࣜ⣴࡛ࡶ 䚷anhydrous sodium sulfate ୍⮴ࡋࡓ㸬ࡇࡢ⌮⏤ࢆ᳨ウࡋࡓ⤖ᯝ㸪ⴭ⪅ࡽࡢ᪼ ᮲௳ GC/MS(SIM) ࡛ࡣึᮇ ᗘ 40Υ࡛࠶ࡿࡢᑐࡋ࡚㸪㧗ᶫࡽ 8)ࡣึᮇ ᗘ 45Υ࡛࠶ࡾ㸪ࡲࡓ᪼ ᮲௳ࡢ㐪࠸ࡀ⌮⏤ࡢ୍ࡘ࡞ࡗ Fig. 2 Analytical procedures for haloaldehydes and haloacetones ࡚࠸ࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡓ㸬 ࡑࡋ࡚㸪 ↓Ỉ◲㓟ࢼࢺ࣒࡛ࣜ࢘⬺Ỉࡋࡓࡶࡢࢆ᳨ᾮࡋ㸪 PTV-GC/MS ศᯒ౪ࡋࡓ㸦Fig. 2㸧 㸬ࣁࣟࢭࢺࣝࢹ ࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢศᯒࡢࡓࡵࡢ᳨㔞⥺సᡂ 㸦⃰ᗘ⠊ᅖ㸸0㸪0.05㹼20.0Ǎg/L㸧࠾ࡼࡧᐃ㔞࠶ࡓࡗ ࡚ࡣ㸪㑅ᢥⓗ᳨࢜ࣥฟ㸦SIM㸧ἲࡼࡾ ᐃࢆ⾜ࡗࡓ㸬 ᮏἲ࠾ࡅࡿࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭ ࢺࣥ㢮ࡢῧຍᅇᐇ㦂ࡢᖹᆒᅇ⋡ኚືಀᩘࡣ㸪5 ᅇ ࡢ⧞ࡾ㏉ࡋᐇ㦂ࡼࡾồࡵࡓ㸬 4. Ỉ㐨Ỉ୰ࡢࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭ Fig. 3 Total ion chromatogram of haloacetaldehydes and haloacetones ࢺࣥ㢮ࡢᐇែㄪᰝ රᗜ┴Ỉ㐨Ỉ㉁⟶⌮ィ⏬ Haloacetaldehydes and haloacetones: 1mg/L 10)ᇶ࡙࠸ࡓỈ㉁┘どᆅⅬ ࡢ࠺ࡕ㸪┘ど 14 ᆅⅬ㸦Ỉ※✀ู㸸†Ỉ 1 ᆅⅬ㸪Ἑᕝ Ỉ 5 ᆅⅬ㸪అὶỈ 2 ᆅⅬ㸪ὸᡞ 4 ᆅⅬ㸪῝ᡞ 2 ᆅⅬ㸧 ࡘ࠸࡚㸪 2013 ᖺ 6 ᭶ 25 ᪥᥇ỈࡋࡓỈ㐨Ỉࢆ⏝࠸ࡓ㸬 մ trichloroacetaldehyde յ 1,1-dichloroacetone ն bromoacetone Table 3 Retetion time, regression equation, correlation coefficient(r), limit of quantitation(LOQ) of 50mL ࢆϩࡢ 3.ࡢ᪉ἲᚑࡗ࡚㸪ࣁࣟࢭࢺࣝࢹࣄࢻ haloaldehydes and haloacetones 㢮ཬࡧࣁࣟࢭࢺࣥ㢮ࢆ MTBE ࡛ᢳฟࢆ⾜࠸㸪ࡇࢀࢆ ศᯒ⏝᳨ᾮࡋࡓ㸬 ճ chloroacetone չ 1,1,3-trichloroacetone պ tribromoacetaldehyde Ỉ㸦Ỉ※✀ู: ἙᕝỈ㸧ࡘ࠸࡚ࡶ ᐃࢆ⾜ࡗࡓ㸬 㓟ࢼࢺ࣒ࣜ࢘ࡼࡾ⬺ሷ⣲ࢆ⾜ࡗࡓᚋ㸪ࡇࡢ࠺ࡕヨᩱỈ ղ dichloroacetaldehyde շ 1,1,1-trichloroacetone ո 1,3-dichloroacetone ࡲࡓ㸪2013 ᖺ 8 ᭶ 28 ᪥␗⮯ⱞࡢ┦ㄯࡀ࠶ࡗࡓỈ㐨 ྛᆅⅬࡽ᥇ྲྀࡋࡓỈ㐨Ỉࢆ㸪0.3㸣㸦W/V㸧ࡢࢳ࢜◲ ձ chloroacetaldehyde No. Compounds R.T. (min) Regression equation* r LOQ (Ǎg/L) 1 2 3 4 5 6 7 8 9 10 6.97 9.46 12.12 12.76 14.03 16.28 19.08 21.89 25.07 27.38 y=359996x y=139299x y=100722x y=259992x y=100031x y=193999x y=122997x y=599962x y=544999x y=109023x 0.994 0.994 0.998 0.993 0.999 0.999 1.000 1.000 1.000 0.999 0.1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Ϫ ⤖ᯝ࠾ࡼࡧ⪃ᐹ 1. PTV-GC/MS ࡼࡿࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧ ࣁࣟࢭࢺࣥ㢮ࡢศᯒἲ 1) PTV-GC/MS ศᯒ᮲௳ 4 ✀㢮ࡢࣁࣟࢭࢺࣝࢹࣄࢻ㢮 6 ✀㢮ࡢࣁࣟࢭ ࢺࣥ㢮ࡢィ 10 ✀㢮ࡢࢺ࣮ࢱࣝ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛࢆ Fig. 3 㸪ࡲࡓྛ ᐃ≀㉁ࡢಖᣢ㛫ࢆ Table 3 ♧ࡋ － 42 － chloroacetaldehyde dichloroacetaldehyde chloroacetone trichloroacetaldehyde 1,1-dichloroacetone bromoacetone 1,1,1-trichloroacetone 1,3-dichloroacetone 1,1,3-trichloroacetone tribromoacetaldehyde 䚷*: Conc. 0.05䠉20.0Ǎg/L (9points: 0, 0.05, 0.1, 0.5, 1.0, 2.0, 5.0, 10.0, 20.0Ǎg/L) රᗜ┴❧ᗣ⏕ά⛉Ꮫ◊✲ᡤᗣ⛉Ꮫ◊✲ࢭࣥࢱ࣮◊✲ሗ࿌ ➨ ྕ ࡲࡓ㸪ᮏ◊✲࡛ࡣ PTV ᶵ⬟ࡼࡿヨᩱὀධἲࢆ᥇⏝ࡋ 3) ᳨㔞⥺ᐃ㔞ୗ㝈್ ࡚࠸ࡿࡇࡶศ㞳ᗘࢆ㧗ࡵ࡚࠸ࡿ⌮⏤⪃࠼ࡽࢀࡓ㸬 ᳨㔞⥺ࡢ୍ḟᘧ㸪 ┦㛵ಀᩘ࠾ࡼࡧᐃ㔞ୗ㝈್ࢆTable 3 2) ࣐ࢫࢫ࣌ࢡࢺࣝゎᯒ ♧ࡋࡓ㸬ྛࣁࣟࢭࢺࣝࢹࣄࢻ࠾ࡼࡧࣁࣟࢭࢺࣥ 4 ✀㢮ࡢࣁࣟࢭࢺࣝࢹࣄࢻ㢮 6 ✀㢮ࡢࣁࣟࢭ ⃰ᗘࣆ࣮ࢡ㠃✚್ࡢ┦㛵ಀᩘࡣ r=0.993 ௨ୖ㧗࠸ ࢺࣥ㢮ࡢィ 10 ✀㢮ࡢ࠺ࡕ㸪ࢡࣟࣟࢭࢺࣝࢹࣄࢻ࠾ ್ࢆ♧ࡋ㸪⃰ᗘᛂ⟅ᛶࡢ┤⥺ᛶࡀᴟࡵ࡚Ⰻዲ࡛࠶ࡗࡓ㸬 ࡼࡧࢪࢡࣟࣟࢭࢺࣝࢹࣄࢻࢆࡋ࡚ Fig. 4 ࣐ࢫ ᐃ㔞ୗ㝈್ࢆ Signal/Noise㸦S/N㸧ẚ=10 ࡋ࡚ồࡵ ࣃࢱ࣮ࣥࢆ♧ࡋࡓ㸬 ࡿ㸪ࢡࣟࣟࢭࢺࣝࢹࣄࢻࡣ 0.1Ǎg/L ࡛࠶ࡾ㸪ࡑࢀ ࢡࣟࣟࢭࢺࣝࢹࣄࢻࡣሷ⣲ࡢྠయࡽศᏊࣉࣟ ௨እࡣࡍ࡚ 0.05Ǎg/L ࡛࠶ࡗࡓ㸬ࡇࢀࡽࡢ⤖ᯝࡣ㸪 m/z78 m/z80 ࡀ᳨ฟࡉࢀ㸪ᙉᗘ Gonzalez ࡽ 9)㸪㧗ᶫࡽ 8)ࡽࡢ⤖ᯝẚ㍑ࡋ࡚㧗ឤᗘ࡛࠶ ࢺࣥ࢜ࣥ[M]+ࡢ ࡋ࡚ࡣᙉ࠸ࣆ࣮ࢡࡋ᳨࡚ฟࡉࢀࡓ㸬ࡲࡓ㸪 ࡗࡓ㸬 [ClCH2-CHO]+ ࡀ 㛤 ࡋ ࡓ [ClCH 㸫 ࣭ ]+ ࡢ m/z50 㸪 ୖグࡢ୧⪅ࡢ⤖ᯝࡣ㸪࠸ࡎࢀࡶ GC/ECD ἲࡼࡿࡶ 㸦m/z48㸧ࡀ≉ᚩⓗ࡞࢜ࣥࡋ᳨࡚ฟࡉࢀࡓࡇࡽ㸪 ࡢ࡛࠶ࡗࡓࡀ㸪ⴭ⪅ࡽࡢ PTV-GC/MS ࡼࡿ᪉ἲࡣ㸪ࡼ m/z78㸪m/z80㸪m/z50 ࡢ࢜ࣥࢆᐃ㔞࢜ࣥࡋࡓ ࡾ㑅ᢥᛶࡀ㧗ࡃ㸪ࡘ㧗ឤᗘ࡛࠶ࡗࡓࡇࡽ㸪᭷⏝࡞ 㸦Table 2㸧 㸬 ศᯒἲ⪃࠼ࡽࢀࡓ㸬 ࢪࢡࣟࣟࢭࢺࣝࢹࣄࢻࡶሷ⣲ࡢྠయࡽศᏊࣉ 4) ῧຍᅇᐇ㦂 ࣟࢺࣥ࢜ࣥ[M]+ࡢ m/z112 m/z114 ࡀ᳨ฟࡉࢀࡓ㸬 Ỉ㐨Ỉࡣࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺ ࡲࡓ㸪 m/z84m/z86ࡀᙉ࠸ࣆ࣮ࢡࡋ᳨࡚ฟࡉࢀࡓࡀ㸪 ࣥ㢮ࡀྵࡲࢀ࡚࠸ࡿࡓࡵ㸪 ᐃ≀㉁ࢆࡃྵࡲ࡞࠸࣑ࢿ ࡇࢀࡣ[Cl2CH-CHO]+ࡀ㛤ࡋࡓ[Cl2CH2]+᥎ᐃࡉࢀ ࢛࣮ࣛࣝ࢘ࢱ࣮ࢆ⏝࠸࡚Ỉ୰⃰ᗘ 0.1Ǎg/L ࡢῧຍᅇᐇ ࡓ㸬ࡇࢀࡽࡢ࢜ࣥࡢ࠺ࡕ㸪m/z112㸪m/z86 ཬࡧ m/z84 㦂ࢆ⾜ࡗࡓ㸬ᢳฟ᧯స㸦๓ฎ⌮㸧ࢆ⾜ࡗ࡚࠸࡞࠸↓ฎ⨨ ࢆᐃ㔞࢜ࣥࡋࡓ㸬 ⩌࠾ࡅࡿྛྜ≀ࡢ᳨㔞⥺ᘧࡽồࡵࡓᅇ⋡ኚື ࡢࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮 ಀᩘࢆ Table 4 ♧ࡋࡓ㸬ࢡࣟࣟࢭࢺࣝࢹࣄࢻࡢ ࡘ࠸࡚ࡶྠᵝࡢゎᯒࢆ⾜࠸㸪Table 2 ♧ࡍ≉ᚩⓗ࡞ࣇ 50.2㸣ࢆ㝖࠸࡚㸪࠸ࡎࢀࡢྜ≀࠾࠸࡚ࡶ 80.1㸣㹼 ࣛࢢ࣓ࣥࢺ࢜ࣥࢆᐃ㔞࢜ࣥࡋࡓ㸬 103.0㸣‶㊊࡛ࡁࡿᅇ⋡ࡀᚓࡽࢀࡓ㸬ࢡࣟࣟࢭࢺ ࣝࢹࣄࢻࡢᅇ⋡ࡘ࠸࡚㸪㧗ᶫࡽ 8)ࡣ 0.4Ǎg/L ࡢῧ ຍ⃰ᗘ࡛㸪୰ᛶỈ⁐ᾮ࠾࠸࡚ࡣ 41.5㸣㸪㓟ᛶỈ⁐ᾮ ࠾࠸࡚ࡣ 23.7㸣࡛࠶ࡗࡓሗ࿌ࡋ࡚࠸ࡿ㸬ࡲࡓ㸪ࡑࡢཎ ᅉࡣࢡࣟࣟࢭࢺࣝࢹࣄࢻࡢỈࡢ⁐ゎᛶࡀ㧗࠸ࡓࡵ ࡛࠶ࡗࡓࡋ࡚࠸ࡿ㸬ⴭ⪅ࡽࡢ⤖ᯝࡶྠᵝప࠸ᅇ⋡ ࡛࠶ࡗࡓࡀ㸪ࡑࡢኚືಀᩘࡣ 4.4㸣⌧ᛶࡀⰋዲ࡛࠶ ࡗࡓࡓࡵ㸪ᐃ㔞ྍ⬟ุ᩿ࡋࡓ㸬 ୍᪉㸪ࢡࣟࣟࢭࢺࣝࢹࣄࢻ௨እࡢྜ≀ࡢኚືಀ ᩘࡣ 2.8㹼4.0㸣⌧ᛶࡢ㧗࠸⤖ᯝ࡛࠶ࡗࡓ㸬 Table 4 Recoveries of haloaldehydes and haloacetones in tap water No. 1 2 3 4 5 6 7 8 9 10 Fig. 4 Mass spectrum of haloacetaldehydes Upper panel: chloroacetaldehyde, 1mg/L Lower panel: dichloroacetaldehyde, 1mg/L Compounds Spiked(Ǎg/L) chloroacetaldehyde 0.1 dichloroacetaldehyde 0.1 chloroacetone 0.1 trichloroacetaldehyde 0.1 1,1-dichloroacetone 0.1 bromoacetone 0.1 1,1,1-trichloroacetone 0.1 1,3-dichloroacetone 0.1 1,1,3-trichloroacetone 0.1 tribromoacetaldehyde 0.1 R(%) 50.2 80.1 97.3 103.0 98.5 84.0 99.2 100.0 100.0 99.2 CV(%) 4.4 3.9 2.9 3.0 4.0 3.9 3.0 3.6 3.8 2.8 (n = 5) － 43 － 2. Ỉ㐨Ỉ୰ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺ ࣜࢡࣟࣟࢭࢺࣝࢹࣄࢻࡢ᭱㧗⃰ᗘ್ࡣ㸪つไ್ࡢᴫ ࡡ 1/2 ࡢ⃰ᗘࣞ࣋ࣝ࠶ࡾ㸪ࡇࡢࡢᾘẘ⏕ᡂ≀ࡘ ࣥ㢮ࡢ⃰ᗘㄪᰝ රᗜ┴Ỉ㐨Ỉ㉁┘ど 14 ᆅⅬ࠾ࡅࡿࣁࣟࢭࢺࣝ ࠸࡚ࡣప⃰ᗘࣞ࣋ࣝ㸦1.4Ǎg/L ௨ୗ㸧࡛࠶ࡿࡇࡀศ ࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢ⃰ᗘㄪᰝࢆ ࡗࡓ㸬୍᪉㸪␗⮯ⱞࡢ࠶ࡗࡓỈ㐨Ỉࡽ㸪1,1,1-ࢺࣜ PTV-GC/MS ἲࢆ⏝࠸࡚⾜ࡗࡓ㸬 ࢡࣟࣟࢭࢺࣥࡢࡳࡀ᭱㧗⃰ᗘ್ 5.0Ǎg/L ୍࡛㐣ᛶ᳨ ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡢㄪᰝ ฟࡉࢀࡓ㸦Fig.5㸧 㸬ࡇࡢỈ㐨Ỉࡽ᳨ฟࡉࢀࡓᏛ≀㉁ ⤖ᯝࢆ Table 5 ♧ࡋࡓ㸬ࢺࣜࢡࣟࣟࢭࢺࣝࢹࣄࢻ ࡢ࣐ࢫࢫ࣌ࢡࢺࣝࡣ㸪1,1,1-ࢺࣜࢡࣟࣟࢭࢺࣥᶆ‽⁐ ࡀẚ㍑ⓗ㧗࠸⃰ᗘ᳨࡛ฟࡉࢀࡓࡀ㸪᭱㧗⃰ᗘࡣ 11.0Ǎg/L ᾮྠࡌ࣐ࢫࢫ࣌ࢡࢺ࡛ࣝ࠶ࡾ㸪ྠᵝࡢ⮯࠸ᡂศ࡛࠶ࡗ ࠶ࡾ㸪┠ᶆ್ 20Ǎg/L ẚࡿప⃰ᗘࣞ࣋ࣝ㸦ᴫࡡ 1/2 ࡓࡇࡽ㸪␗⮯ཎᅉ≀㉁᩿ᐃࡉࢀࡓ㸬 ⃰ᗘ㸧࠶ࡗࡓ㸬ࡇࡢ㸪1,3-ࢪࢡࣟࣟࢭࢺࣥ㸪1,1,3- ϫ せ ᪨ ࢺࣜࢡࣟࣟࢭࢺࣥࢆ㝖࠸࡚㸪ከࡃࡢࣁࣟࢭࢺࣝࢹ ࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡀ᳨ฟࡉࢀࡓࡀ㸪ప⃰ᗘࣞ ࣋ࣝ࠶ࡗࡓ㸬ࡇࢀࡽࡢ⤖ᯝࡣ㸪㧗ᶫࡽ 12)ࡢᮾி㒔ෆࡢ Ỉ㐨Ỉ୰ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ Ỉ㐨Ỉࡢㄪᰝ⤖ᯝᴫࡡ୍⮴ࡋ࡚࠸ࡓ㸬 㢮ࡘ࠸࡚㸪PTV-GC/MS ἲࡼࡿศᯒἲࡢ㛤Ⓨᐇែ ௨ୖ㸪ࡇࢀࡽࡢ⤖ᯝࡽ㸪Ỉ㉁ᇶ‽࡛つไࡉࢀࡓࢺ ㄪᰝࢆ⾜ࡗࡓ⤖ᯝ㸪௨ୗࡢ▱ぢࡀᚓࡽࢀࡓ㸬 1. ᮏ◊✲࡛㛤Ⓨࡋࡓࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁ Table 5 Concentration of haloaldehydes and ࣟࢭࢺࣥ㢮ࡣ㸪ᚑ᮶㸪GC/ECD ἲ࡛ศᯒࡉࢀ࡚࠸ࡓࡀ㸪 haloacetones in tap water PTV ᶵ⬟ MTBE ࢆ⏝࠸ࡓ⁐፹ᢳฟ-GC/MS ἲࡢ⤌ࡳ No. Compounds 1 2 3 4 5 6 7 8 9 10 chloroacetaldehyde dichloroacetaldehyde chloroacetone trichloroacetaldehyde 1,1-dichloroacetone bromoacetone 1,1,1-trichloroacetone 1,3-dichloroacetone 1,1,3-trichloroacetone tribromoacetaldehyde Concentration (Ǎg/L) Min. Max. N.D. 1.4 N.D. 0.8 N.D. 1.7 N.D. 11.0 N.D. 0.4 N.D. 0.2 N.D. 0.4 N.D. N.D. N.D. N.D. N.D. 0.1 ྜࢃࡏࡼࡾ㸪㑅ᢥᛶࡀ㧗ࡃ㧗ឤᗘ࡞୍ᩧศᯒࡀྍ⬟ ࡞ࡗࡓ㸬ࡇࢀࡽࡢᐃ㔞ୗ㝈್ࡣ㸪0.05㹼0.1Ǎg/L ࡛࠶ࡗ ࡓ㸬 2. ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮ࡘ ࠸࡚㸪࣑ࢿ࢛࣮ࣛࣝ࢘ࢱ࣮ࢆ⏝࠸࡚ῧຍᅇᐇ㦂ࢆ⾜ࡗ ࡓ⤖ᯝ㸪ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭࢺࣥ㢮 ࡢᅇ⋡ࡣ㸪ࢡࣟࣟࢭࢺࣝࢹࣄࢻࡢ 50.2㸣ࢆ㝖࠸࡚㸪 80.1㸣㹼103.0㸣‶㊊࡛ࡁࡿᅇ⋡ࡀᚓࡽࢀࡓ㸬ኚືಀ ᩘࡣ 4.4㸣௨ୗ⌧ᛶࡢ㧗࠸⤖ᯝ࡛࠶ࡿࡇࢆㄆࡵࡓ㸬 ࡇࢀࡽࡢ⤖ᯝࡽ㸪 ᮏศᯒἲࡢ᭷⏝ᛶࡀ᫂ࡽ࡞ࡗࡓ㸬 3. ᮏἲࢆරᗜ┴Ỉ㐨Ỉ㉁⟶⌮ィ⏬ᇶ࡙࠸ࡓ┘ど 14 ᆅⅬࡢỈ㐨Ỉ୰ࣁࣟࢭࢺࣝࢹࣄࢻ㢮࠾ࡼࡧࣁࣟࢭ ࢺࣥ㢮⃰ᗘㄪᰝ㐺⏝ࡋࡓ⤖ᯝ㸪ࡑࢀࡒࢀ㸪ND㹼 11.0Ǎg/L㸪ND㹼1.7Ǎg/L ࡢ⃰ᗘ⠊ᅖ᳨࡛ฟࡉࢀࡿࡇࡀ ศࡗࡓ㸬 4. ␗⮯ⱞࡢ┦ㄯࡀ࠶ࡗࡓỈ㐨Ỉࡽࡣ㸪1,1,1-ࢺࣜࢡ ࣟࣟࢭࢺࣥࡢࡳࡀ᭱㧗⃰ᗘ್ࡣ 5.0Ǎg/L ᳨࡛ฟࡉࢀ㸪 ᶆ‽⁐ᾮྠࡌ࣐ࢫࢫ࣌ࢡࢺࣝ࠾ࡼࡧྠࡌ⮯࠸ᡂศ࡛࠶ ࡗࡓࡇࡽ㸪ཎᅉ≀㉁᩿ᐃࡉࢀࡓ㸬 ㅰ ㎡ ᮏ✏ࢆ⤊࠼ࡿ࠶ࡓࡾ㸪ヨᩱࡢ᥇ྲྀ➼ࡈ༠ຊ㡬ࡁࡲ Fig. 5 Mass spectrum of 1,1,1-trichloroacetone ࡋࡓරᗜ┴ᗣ⚟♴㒊⏕ά⾨⏕ㄢ㸪⟶㎄ᗣ⚟♴ົᡤ ୪ࡧྛᕷ⏫Ỉ㐨ᴗయࡢ㛵ಀ⪅ࡢⓙᵝ῝ࡃឤㅰ࠸ࡓ Upper panel: mass spectrum of order-causing sample Lower panel: mass spectrum of 1,1,1-trichloroacetone standard solution (50Ǎg/L) ࡋࡲࡍ㸬 ᩥ ⊩ － 44 － රᗜ┴❧ᗣ⏕ά⛉Ꮫ◊✲ᡤᗣ⛉Ꮫ◊✲ࢭࣥࢱ࣮◊✲ሗ࿌ ➨ ྕ 1) ཌ⏕ປാ┬㸸 ࠕỈ㉁ᇶ‽㛵ࡍࡿ┬௧ࠖ, ᖹᡂ 15 ࣄࢻࡢGC/MS ࢆ⏝࠸ࡓ㎿㏿, ṇ☜ࡘ㧗ឤᗘ࡞ศᯒ ᖺ 5 ᭶ 30 ᪥, ཌ⏕ປാ┬௧➨ 101 ྕ (2003) ἲࡢ᳨ウ. රᗜ⾨◊ሗ, 36, 114-118 (2001) 2) ཌ⏕ປാ┬ᗣᒁỈ㐨ㄢ㛗㏻▱㸸㺀Ỉ㉁ᇶ‽㛵ࡍࡿ 8) 㧗ᶫಖ㞝, ᳃⏣ᫀᩄ㸸 Ỉ㐨Ỉ୰ࡢࣁࣟࢤࣥᾘẘ ┬௧ࡢไᐃཬࡧỈ㐨ἲ⾜つ๎ࡢ୍㒊ᨵṇ୪ࡧỈ ⏕ᡂ≀ࡢከᡂศ⣔⤫ศᯒἲ, ⎔ቃᏛ, 7(3), 495-506 㐨Ỉ㉁⟶⌮࠾ࡅࡿ␃ព㡯ࡘ࠸࡚㺁, ᖹᡂ 15 ᖺ (1997) 10 ᭶ 10 ᪥, ỈⓎ➨ 1010001 ྕ (2003) 9) Gonzalez, A.C., Krasner, S.W., Weinberg, H.S., 3) ཌ⏕ປാ┬ᗣᒁ㛗㏻▱㸸㺀Ỉ㉁ᇶ‽㛵ࡍࡿ┬௧ࡢ Richardson, S.D.: Determination of newly ไᐃཬࡧỈ㐨ἲ⾜つ๎ࡢ୍㒊ᨵṇࡘ࠸࡚㺁, ᖹᡂ identified disinfection by-products in drinking 15 ᖺ 10 ᭶ 10 ᪥, ỈⓎ➨ 1010004 ྕ (2003) water. Proc AWWA Water Qual. Technol. Conf., 4) ཌ⏕ປാ┬ᗣᒁỈ㐨ㄢ㛗㏻▱㸸 㺀Ỉ㐨Ỉ㉁⟶⌮ィ⏬ 2000(3-2), 1146-1164 (2000) ࡢ⟇ᐃ࠶ࡓࡗ࡚ࡢ␃ព㡯ࡘ࠸࡚㺁ࡢ୍㒊ᨵṇ 10) රᗜ┴ᗣ⏕ά㒊⏕ά⾨⏕ㄢ: ࠕරᗜ┴Ỉ㐨Ỉ㉁⟶ ࡘ࠸࡚, ᖹᡂ 16 ᖺ 1 ᭶ 22 ᪥, ỈⓎ➨ 0122002 ྕ ⌮ィ⏬ࠖ, ᖹᡂ 6 ᖺ 3 ᭶⟇ᐃ(➨ 1 ḟ) (1994)㸪ᖹᡂ (2004) 17 ᖺ 9 ᭶⟇ᐃ(➨ 2 ḟ) (2005) 5) 㧗ᶫಖ㞝, ᳃⏣ᫀᩄ㸸 Ỉ㐨ỈཬࡧỈ㐨ཎỈ୰ࡢᚤ㔞 11㸧᪥ᮏỈ㐨༠⦅㸸ୖỈヨ㦂ἲ 2011 ᖺ∧㸪ϩ㸬⌮ ᭷ᶵྜ≀ࡢ୍ぴ⾲, ⎔ቃᏛ, 6(3), 375-400 (1996) 6) ᪥ᮏỈ㐨༠⦅: ୖỈヨ㦂᪉ἲ 2001 ᖺ∧, P107-114, Ꮫ⦅㸪P76㸪P92㸪ᮾி㸦2011㸧 12) 㧗ᶫಖ㞝㸪 ᳃⏣ᫀᩄ㸸 Ỉ㐨Ỉ୰ࡢࣁࣟࢤࣥᾘẘ P119-120, P247-257 㸪 ᪥ᮏỈ㐨༠ฟ∧, ᮾி (2001) 7) ᕝඖ㐩ᙪ, ᕳᖭᕼᏊ, ᑎすΎ㸸 Ỉ㐨Ỉ୰࣒࣍ࣝࣝࢹ － 45 － ⏕ᡂ≀, ⎔ቃᏛ, 8(3), 455-464 (1998) [ᖹᡂ26ᖺ3᭶28᪥ཷ⌮]
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