我が国における塩素系難燃剤
Dechlorane Plusの汚染について
先山孝則（大阪市立環境科学研究所）☆ 分析化学, 61 (9), 745-754 (2012)☆ Organohalogen Compounds, 74, 146-149 (2012)☆ 第20-22環境化学討論会(2011-2013)☆ 19th International Mass Spectrometry Conference (Kyoto, 2012)

発表概要★分析方法について• 前処理と測定方法• 操作上の注意点★Dechlorane Plusの汚染実態• これまでの国内の概要調査結果• 諸外国での調査事例との比較★今後の研究課題

Dechlorane Plus® とは？
๏塩素系難燃剤：Mirex(Dechlorane:1970年代禁止) の代わりに開発
๏ 開発・製造

๏ OxyChem(USA)で開発 → Anpon社 (中国)でも2003年から製造：>2,000t/年？
๏ Hexachlorocyclopentadieneと1,5- cyclooctadiene のDiels-Alder反応により生成๏ 特性๏ 耐候性(UV安定性：電線用PE、TVケース用ABSやHIPS）
๏ 耐熱性（290℃まで安定）
๏ 耐トラッキング性（400〜600Vにも適合）
๏ 低煙性（BFRより低煙）
๏ 着色性（白色粉末）
๏ 難燃助剤の削減（三酸化アンチモンの削減が可能）
๏ ダイオキシンフリー（燃焼時にDXNの発生問題が無い)

๏ 用途

๏ 電気電子部品、特殊電線、自動車、接着剤の分野で、熱可塑性や熱硬化性の樹脂や合成ゴムなどに添加

syn-Dechlorane Plusanti-Dechlorane Plus

CAS No.135821-03-3

CAS No.135821-74-8
ClClClClCl

Cl

Dechlorane (Mirex)

Hexachlorocyclopentadiene

CAS No. 2385-85-5

CAS No. 77-47-4

POPs条約対象物質(条約発効当初)✴付属書A記載物質：製造・使用禁止(廃絶)• アルドリン• ディルドリン• エンドリン• クロルデン• ヘプタクロル• トキサフェン• マイレックス• ヘキサクロロベンゼン(HxCBz)• ポリ塩化ビフェニル（PCB）

ClClClClClClClClClClClCl

ClClClCl

ClClClO

Dechlorane Plusに関する調査研究• Hoh ら が2006年に五大湖周辺で残留を確認• →2010年頃から欧米や中国で研究報告が急増• 日本での研究→2010年時点では報告なかった• 2011年より調査開始• 環境中でng/gレベル• の残留を確認• 国内報告例増える• 底質・土壌・ダスト• 生物(魚、母乳)• 大気・植物• 食品

Measurement method;

Sample treatment
Samples

0.1,:,5g:wet

Shoxlet,Extrac0on

10%,Acetone/Toluene,300mL,,16hr,over

Clean:up,Spike,Desulfuriza0on,

Tetrabutyl,ammonium,sulﬁte,,Florisil,CartridgeColumn,Clean:up,Sep:Pak,Plus,Florisil,(Waters)

DP#

Fraction

1st,Fr.

,,,,,5%,Dichloromethan/n:Hexane,10mL

,2nd,Fr.,

25%,Dichloromethan/n:Hexane,20mL

Ac0ve,Carbon,Cartridge,Column,Clean:up,

Supelclean,ENVI:Carb,500mg,(Supelco),
n:Hexane,20mL

Syringe,Spike,
HRGC/HRMS,Measurement,

HCH,#
othersFraction

Measurement method;

Instruments

Accuracy of quantitative measurement

What happened in this studyAccuracy of quantitative measurement

Our suggestion about DP solution• DP in n-nonane product (100ug/mL)• Decreasing anti-DP concentration of DP product during low
temperature storage.

• This mechanism has not yet been fully clarified.

• Dilution of product• anti-DP might be decreased by concentration dependence.

• Torre et al. reported• anti-DP decreased in nonane solution but nothing mentioned
about concentration.

Accuracy of quantitative measurement

Most appropriate standard solution
The product (100ug/mL)
should be stored at room temperature.
Freezer storage
should be taken diluted solution.
Our investigation:
Nonane product (100ug/mL),
anti-DP concentration decreased during Freezer storage (-25℃).

Diluted solution (10ug/mL),
No decrease during one month storage in Freezer.

Environmental overview
Dechlorane Plus in Japanese various matrices.
Sample matrix

Sampling location

Ambient air (pg/m )Numberof sample

Dechlorane Plus Conc.

fanti

Mean

Range

Mean

Range

Samplingyear

3

Urban sites, Kanagawa

47.3

2.0 - 180.75

0.71 - 0.83

2012

Urban rivers, Osaka30

330.24 - 230

0.76

0.69 - 0.84

2008-2011

Urban area, Home garden, Osaka

11.7-0.810.81

2011

Deposits of window, Urban area, Osaka

2250240 - 270

0.83

0.81 - 0.85

2011

Road sediments, Urban area, Osaka

211074 - 150

0.80

0.78 - 0.82

2011

Indoor dust (ng/g-dry)

Residential homes, Urban area
, Osaka and Hyogo513

2.9 - 420.65

0.41 - 0.77

2011

Plant leaf (pg/g-wet)(ng/g-dry)

Urban area, Osaka7180( 0.5224 - 460
0.082 - 1.2

0.64

0.56 - 0.76

2013

Food stuff (pg/g-wet)Fish

20-<0.2 - 14.2

0.62

0.56 - 0.72

2012

Vegetable

26.7

5.5 - 8.00.68

0.65 - 0.71

2013

Urban area, Osaka

11-<0.5 - 660--

Sediments !(ng/g-dry)
Soil !(ng/g-dry)
Outdoor dust (ng/g-dry)

Human milk (pg/g-fat)fanti: Ratio of the anti-Dechlorane Plus to the Dechlorane Plus concentration.

)

1983-2011

Concentrations of Dechlorane Plus (ng/g-dry)
0.01!

Sediments
SoilDust

Indoor dust. Canada-2!

Indoor dust. Canada-1!

Indoor dust. China-4!

Indoor dust. China-3!

Indoor dust. China-2!

Indoor dust. China-1!

Indoor door dust. Japan!

Out door dust. Japan-2!

Out door dust. Japan-1!

Soil. China-11!

Soil. China-10!

Soil. China-9!

Soil. China-8!

Soil. China-7!

Soil. China-6!

Soil. China-5!

Soil. China-4!

Soil. China-3!

Soil. China-2!

Soil. China-1!

Soil. Japan!

Sediments. Lake Huron!

Sediments. Lake Superior!

Sediments. Lake Michigan!

Sediments. Lake Erie!

Sediments. Lake Winnipeg!

Sediments. Lake Ontario-3!

Sediments. Lake Ontario-2!

Sediments. Lake Ontario-1!

Sediments. China-5!

Sediments. China-4!

100!

Sediments. China-3!

100000!

Sediments. China-2!

Sediments. China-1!

Sediments. Japan!

Environmental overview:

Comparison with worldwide data

Mean!

10000!

1000!
min!

max!

10!

1!

0.1!

Environmental overview:

GC/MS Chromatogram (m/z: 271.8102) ofDechlorane Plue(DP) and Mirex(Dechlorane)

STD

Mirex (Dechlorane)(10 ng/mL)

Sediment-25
Sediment-18
Sediment-11
Sediment-04

syn-DP(20 ng/mL)

anti-DP(20 ng/mL)

Environmental overview:

Relationship of DP Concentrations tothe Ratio of anti-DP(fanti) in Various Samples.
0.90

Ratio of the anti-DP to the total DP (fanti)

0.85
0.80
0.75
0.70
0.65

Ambient air (pg/m3)-Ref.10
Sediments (ng/g-dry)
Soil (ng/g-dry)
Fish (pg/g-wet)-Ref.11,12
Vegetable (pg/g-wet)
Plant Leaf (ng/g-dry)
Out.Dust-Window (ng/g-dry)
Out.Dust-Road (ng/g-dry)
In.Dust (ng/g-dry)

0.60
0.55
0.50
0.45
0.40








Concentrations of total DP





今後の課題★ 人や生物への影響➡ 暴露経路と量、残留蓄積性、毒性★ 環境挙動➡ 給源、媒体別濃度分布、経年変化、越境汚染★ 使用実態➡ 用途、使用量、流通量★ 関連物質➡ 類似構造を持つハロゲン化難燃剤