Sakiyama T1, Weber R2*, Behnisch P3, Nakano T4
1Osaka
City Institute of Public Health and Env. Sciences, Tohjo-cho 8-34, Tennojiku, Osaka 543-0026, Japan;
2 POPs Environmental Consulting, Ulmenstrasse 3, 73035 Göppingen, Germany
3BioDetection Systems BV (BDS), Kruislaan 406, 1098 SM Amsterdam, The
Netherlands,
4Osaka University, Research Center for Environm. Preservation 2-5 Yamadaoka,
Suita, Osaka 565-0871, Japan
 Dioxins and pesticide history in Japan
 Dioxin and pesticide screening Australia (2010)
 2,4,5-T and chlorpyrifos as Twins?
 Chlorpyrifos as
 Formation of Pyridin analogue 2,3,7.8-TCDD in thermal
experiments
 Analytical behaviour of 2,3,7.8-TCDD-Py
 Dioxin-like toxicity of thermal experiments
 Possible practical experience 2,3,7.8-TCDD-Py
Pesticide production, use and disposal have contributed
significantly to polychlorinated dibenzo-p-dioxin and
dibenzofuran (PCDD/F) emissions in the past.
g TEQ/Jahr
70000
Masunaga et al. 1998
PCDD/PCDF in PCP
PCDD/PCDF in CNP
co-PCB
Other Chlororganics
Industrial Waste Incineration
Municipal Waste Incineration
60000
50000
40000
30000
PCP
IWI
CNP
20000
10000
MWI
co-PCB
0
1958
1963
1968
1973
1978
1983
1988
1993
DIOXIN IMPURITIES IN PESTICIDE FORMULATIONS
Current use pesticide formulations
Obsolete pesticide formulations
100,000
Formulation basis (FL)
Active Ingredient basis
(AI)
Formulation
basis
(FL) (AI)
Active Ingredient basis
Concentration (ng TEQ kg-1)
10,000
1,000
100
10
1
0
Holt et al. ES&T. 44, 5409–5415 (2010)
UNEP
Emission
Factor
for 2,4,5-T
In 2,4,5-T production and in product high 2,3,7,8-TCDD level
Cl
OR
Cl
O
Cl
Cl
Cl
Cl
O
Cl
O
Cl
2,4,5-Trichlorphenol (R=H)
2,4,5-T (R=Essigsäure)
Cl
Cl
N
2,3,7,8-TCDD
(Seveso-Dioxin; in Agent Orange)
OR
Cl
Cl
Cl
Chlorpyrifos (R=Phosphor acid ester)
3,5,6-trichloro-2-pyridinol (R=H)
N
O
N
Cl
Production
Thermal Stress
2,4,5-Trichlorophenol (R=H)
2,4,5-T (R=Acetic Acid) (in Agent Orange)
2,3,7,8-TCDD
(Seveso Dioxin)
Production?
Thermal Stress?
Chlorpyrifos (R=Phosphor acid ester)
3,5,6-trichloro-2-pyridinol (R=H)
2,3,7,8-TCDD-pyridin-analogue
 Highest sales of chlorpyrifos of all organophosphate
pesticides worldwide, and the third among all pesticides.
 In 2010, the consumption of chlorpyrifos globally
(converted into technical) reached 80,000 tonnes with
CAGR of about 12% in the past five years (2005 to 2010).
 Chinese production capacity was 116,000 tonnes (2010).
Chlorpyrifos
Chlorpyrifos-Methyl
 In Vietnam about 37,000 tonnes of 2,4,5-T have been
sprayed in total containing 366 kg TEQ to 1123 kg TEQ
(Stellmann et al., Nature 422, 681-687 (2003)
 All pyrolysis experiments were carried out in sealed brown
glass ampoules (10 ml; air) with about 2 mg of respective
chemical chlorpyrifos, chlorpyrifos-methyl and the major
degradation product of chlorpyrifos, 3,5,6-trichloro-2pyridinol (TCPy) at temperatures between 300ºC and 380ºC.
Chlorpyrifos
Chlorpyrifos-Methyl
Analytical grade chlorpyrifos, TCPy (both Dr. Ehrenstorfer
GmbH, Augsburg/Germany) and chlorpyrifos-methyl
(Wako Pure Chemicals, Osaka/Japan) were used.
Relative abundance of 2,3,7,8-TCDD-pyridine-analogues
formed in thermal experiments (ampoule; air;15 min)
2378-TCDD-pyridineanalogue (1)*
2378-TCDD-pyridineanalogue (2)**
300ºC
340ºC
380ºC
300ºC
340ºC
380ºC
chlorpyrifos
0
0
1x10^5
0
0
3x10^5
chlorpyrifosmethyl
0
0
6x10^5
0
0
3x10^6
3,5,6-trichloro-2pyridinol
1x10^5 6x10^6 3x10^7
1x10^5
1x10^7 1x10^8
*trans-isomer of 2,3,7,8-TCDD-Py; **cis-isomer of 2,3,7,8-TCDD-Py
①
⑤
②
④
③
Peak
⑤
Peak ①
＆ Peak ③
Peak ②
＆ Peak ④
2,3,7,8- TeCDD-N Analogues from TCPy pyrolysis
(m/z:323.8841)
1,3,6,8
-
2,3,7,81,2,3,4-
13C labeled
12
TeCDDs
(m/z:333.9338)
TeCDDs in Flyash
(m/z:321.8937)
MCounts
254.0>
DiCDD
1.0
piridinol-380C-10mi.XMS 254.0> Filtered
N-analogue
0.5
0.0
MCounts
2.0 256.0>
1.5
DiCDD
1.0
0.5
0.0
kCounts
600 288.0>
400
piridinol-380C-10mi.XMS 256.0> Filtered
N-analogue
piridinol-380C-10mi.XMS 288.0> Filtered
TriCDD N-analogue
200
0
MCounts
1.00 290.0>
0.75
TriCDD
0.50
0.25
0.00
MCounts
60 322.0>
40
piridinol-380C-10mi.XMS 290.0> Filtered
N-analogues
piridinol-380C-10mi.XMS 322.0> Filtered
2,3,7,8-TCDD- N-analogues
20
0
MCounts
75 324.0>
piridinol-380C-10mi.XMS 324.0> Filtered
2,3,7,8-TCDD N-analogues
50
25
0
MCounts
358.0>
1.5
1.0
0.5
0.0
15.0
17.5
piridinol-380C-10mi.XMS 358.0> Filtered
PentaCDD N-analogue
20.0
22.5
25.0
27.5
30.0
32.5
minutes
 The 2,3,7,8-TCDD-Py does not elute gogether with
PCDD/PCDF in the following clean-up columns: (mention which
columns
 The Pyridin-analogues as base are adsorbed on the column
and need specific elution in the clean-up
 Therefore PCDD-Py are not transfered to GC/MS with (most?)
current clean-up columns and would therefore not be detected
in GC/MS (even in scan mode).
 Dioxin-like toxicities were assessed with the DR-CALUXTM assay.
 Extremely high dioxin-like toxicity was detected from the treatment
at 380ºC of TCPy (143,000 ng 2,3,7,8-TCDD bio-TEQ/g treated
TCPy).
 The 48 h kinetic indicated that the dioxin-like active compounds
were stable.
DR CALUX, 24 hours exposure
DR CALUX, 48 hours exposure
Chlorpyrifos, 380 C
Cl-piridinol, 380 C
Cl-piridinol, 340 C
100
50
0
-10
150
% Max TCDD Response
% Max TCDD Response
150
Chlorpyrifos, 380 C
Cl-piridinol, 380 C
Cl-piridinol, 340 C
100
50
0
-8
-6
-4
Log dilution
-2
0
-8
-6
-4
Log dilution
-2
0
 2,3,7,8-TCDD-Py (having dioxin-like toxicity) is formed from
chlorpyrifos, chlorpyrifos-methyl and in particular their
major degradation product (TCPy) in heating experiments
highlighting the need to investigate the formation of
2,3,7,8-TCDD-Py in real world scenarios with thermal
stress e.g.
cigarette smoking (chlorpyrifos used in tobacco
cultivation)
the combustion of post-harvest residues
fires in pesticide production or storage.
 Furthermore, 2,3,7,8-TCDD-Py is a high volume pesticide
used for e.g. should be screened in chlorpyrifos pesticide
formulations. With the background that 2,4,5-TCP based
pesticides (Agent Orange, Pink, Purpule, White contained
extreme high 2,3,7,8-TCDD levels).
 Such assessments should include bio-assays for
quantitative toxicity information on the extent of dioxin-like
activity considering that also compounds other then
2,3,7,8-TCDD-Py seem to have dioxin-like activity in
thermal treatment of chlorpyrifos.
Evil Endosulfan
“The dirty dozen” Assessment:
PFOA, PFXSi, PFHxS
DeBDE,HBCDD,PBB
PBDD/F, HBBz, PBP,
•Dieldrin
Aldrin
TBBPA, TBPAE,
Chlordane
SCCP, MCCP,
DDT
PCN, HCBD, OCS,
Dieldrin
PCP, PCNB
Endrin
PAHs, Nitro-PAH
HCB
Halogenated PAHs
Heptachlor
Toxaphene
PT-Pesticides,
Mirex
PT-Biocides
“The nasty nine” alpha-, beta-, gamma-HCH, PT-Pharmaceuticals
PeCB, Chlordecone, PeBDE, OBDE, HBB, PFOS PT-Siloxanes
www.pops.int www.saicm.org www.ipen.org
Sn-Organics
http://www.springerlink.com/content/0q10km8582605r1x/fulltext.pdf
Hg, Cd. Pb et al.
PCDD
PCDF
•PCBs
PCB
 Litres of herbicides sprayed over 1962–1971. The data are
taken from the corrected HERBS file
Stellmann et al., Nature 422, 681-687 (2003)