Release of PCDD/Fs from Pesticide Use ‐ Case Study Australia

Eva Holt1, Roland Weber2, Gavin Stevenson3, Caroline Gaus1 1The University of Queensland (National Research Centre for Environmental Toxicology (EnTox)), Australia 2POPs Environmental Consulting, 73035 Göppingen, Germany 3Dioxin Analysis Unit, National Measurement Institute, Pymble, Australia

National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health 3000 2500 2000 1500 1000 UNEP inventory 1998 summary 500 0 2300 A 29 150 AUS Max Best B 661

CH 181

CAN 290

D 323 19

DK 170 873

F 2737 98

FIN 198 23 HGK 33

HRO 96 2260 HUN 103

JPN 6370

N 9

NL 486 14 22

NZ 51

S 88

SR 42 560 1099

UK 2501

USA 4901 MWI IWI 8000 Small Combusters Crematories Electric Arc Sinter Zink Aluminum 6000 Other Sources Cigaretts Traffic

4000

2000

0 Dioxinemission Air (g TEQ/a) Dioxinemission 1997 1998 1999 2000 2001 2002 2003* g TEQ/Jahr 70000 PCDD/PCDF in PCP 60000 PCDD/PCDF in CNP co-PCB 50000 Other Chlororganics Industrial Waste Incineration 40000 Municipal Waste Incineration

30000 PCP

20000 CNP IWIIWI MWIMWI 10000 co-PCB 0 1958 1963 1968 1973 1978 1983 1988 1993

Masunaga et al. 1998 In the past ¾ Bans or regulations e.g. 2,4,5-T and PCP ¾ Improved production technology

Today ¾ Many pesticides still have the potential to contain dioxin impurities (US EPA list with approximately 60 suspected pesticides) ¾ Pesticides can contain dioxin precursors (and form dioxins in the environment by UV exposure or open burning) ¾ Very limited data: cannot evaluate to which extent use of pesticides contribute to dioxin emission and contamination Australian study purpose: ¾Determine whether other pesticides contain dioxin impurities (in this case current used pesticides in Australia) ¾Preliminary investigation of dioxin formation from pesticide derived precursor ¾Estimate dioxin emissions from ?? pesticide use

National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health Phenoxy herbicides:

2,4-D Mecoprop

MCPA 2,4-DB

2,4,5-T (obsolete) Other herbicides:

Triclopyr Fluroxypyr Chlorthal dimethyl

Imazamox Flumetsulam Herbicides - Secondary active constituents:

Picloram Dicamba Diflufenican Fungicides:

Chlorothalonil Quintozene

Prochloraz Insecticides:

Fenamiphos Chlorpyrifos

Cl Cl

Cl Cl

Cl Cl

Cl Lindane Chlordane Heptachlor (obsolete) (obsolete) (obsolete) 10,000 5,700 TEQ concentrations in current-use pesticides 3,900 2,400 Active Ingredient basis Formulation basis 1,000 (Middle bound)

180 180 100 100 63 56 27

13 13 12 9.4 10 8.6 6.0 5.5 5.4 4.8 4.9 4.2

1.7

TEQ (WHO 05) concentrations (pg/g) concentrations 05) (WHO TEQ 1

0

All investigated pesticides contained PCDD/PCDF !! National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health Investigated current-use pesticides – no UNEP EF UNEP Emission factors

10,000,000 2,000,000 Range EU,USA Average (or n=1) 1,000,000 Other data (Masunaga et al. 2001) 800,000 China 300,000 100,000 old technol.

10,000 5.700 7,000 4,800 1,000 2,400 700 500 700 1,000 Na-PCP 180 180 400 100 100 63 new technol. 56 94 27 31 TEQ concentrations (pg/g AI) (pg/g concentrations TEQ 9.4 13 10 5.5 5.4 4.9 4.2 8.6 4.8 1.7

1

0

Most current use pesticides have no PCDD/F emission factor

National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health Usage of 2,4-D; 2,4-DB; PCNB: • Label application rates & frequencies, • % crop area treated▲ • and cropping area +

+[ABS 2008; Australian Government 2004; USEPA 2005 & 2006]; ▲ USEPA 2001 & 2003 TEQ emission estimates to Australian land

Re‐evaluation, NationalDioxin Program, Bawden et al. 2004 This study, Holt et al. 2009 * Meyers et al. 2008 1000 ** 1,020 228 - incl. non-agricultural use 114 (~25-60% of total use) 100 110 51 49 28 82 - agricultural use only 33 22 16 13 11 10 17 13 3.8 6.0 1.8 4.3 3.6 1 1.3 1.0 0.4 0.42 0.25 0.15 0.1 0.13 0.033 0.020 0.010 0.0090 0.01

Estimated emission (g TEQ TEQ annum-1) (g emission Estimated 0.0100.012 0.0026 Low-high emission estimate 0.001 0.0019 Best emission estimate 0.0011 0.0014

0.0001

**Not yet in official inventory

*Emissions for pesticides were calculated based on pesticide minimum and maximum label application rates, land area and application frequency using middle bound TEQ concentrations. No volume of use could be estimated for other pesticides National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health ¾ PCNB formulation increased TEQ 3 to 4 times when exposed to sunlight for some days ¾ Potential for significant dioxin formation after application (how to address in emission inventory?)

National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health ¾All investigated pesticides contained PCDD/F ¾Pentachloronitrobenzene (PCNB, Quintozene) contained high levels of PCDD/F (suggested EF 4.8 mg TEQ/t; average of three different formulations) and close to EF of 2,4,5-T. ¾The emission from PCNB could be the single highest PCDD/F source in Australia (up to 82 - 228 g TEQ/a). Preliminary results suggest that post application formation (UV light) might result in 3 to 4 times higher release. ¾ + contribution of all other pesticides. National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health ¾The precursor quality of pesticides and post application formation need to be considered for total environmental pollution ¾ How to consider this in the toolkit? ¾Pesticides need to be screened for their PCDD/PCDF/UPOPs content to establish emission factors ¾Contribution of pesticides need to be considered in PCDD/F inventories.

National Research Centre for Environmental Toxicology: a joint venture of The University of Queensland and Queensland Health Bromophos; Dimethylamine 2,3,5- triiodobenzoate; Neburon; Crufomate; MCPB, 4- butyric acid [4-( 2- Methyl- 4- chlorophenoxy) Dichlorodifluoromethane; Bromophos; Dimethylamine 2,3,5- triiodobenzoate; Neburon; Crufomate; MCPB, 4- butyric acid [4-( 2- Methyl- 4- chlorophenoxy) butyric acid]; MCPB, Na salt [Sodium 4-( 2- methyl- 4- chlorophenoxy) butyrate]; 4- Chlorophenoxyacetic acid; Chloroxuron; Dichlobenil; Propanil; Dichlofenthion; DDT; Dichlone; Ammonium chloramben; Disul, DCNA, Potassium 2-( 2- methyl-4-chlorophenoxy) propionate; MCPP, DEA Salt; MCPP, IOE; Dicapthon; Monuron trichloroacetate; Diuron; Linuron; Metobromuron; Methyl parathionl; Dichlorophene; Dichlorophene, sodium salt; 1,2,4,5- Tetrachloro- 3- nitrobenzene; Ethyl parathionl; Carbophenothion; Ronnell; Mitin FF; Orthodichlorobenzene; Paradichlorobenzene; Chlorophene; Potassium 2- benzyl- 4- chlorophenate; Sodium 2- benzyl- 4- chlorophenate; Chlorophenol; 2- Chloro- 4- phenylphenol; Potassium 2- chloro- 4- phenylphenate; 4- Chloro- 2- phenylphenol; 4- Chloro- 2- phenylphenol, potassium salt; 6- Chloro- 2- phenylphenol; 6- Chloro- 2- phenylphenol, potassium salt; 4- Chloro- 2- phenylphenol, sodium salt; 6- Chloro- 2- phenylphenol, sodium salt; 4 and 6- Chloro- 2- phenylphenol, diethanolamine salt; 2- Chloro- 4- phenylphenol, sodium salt; 4- Chloro- 2- cyclopentylphenol; Fentichlor; 4- Chloro- 2- cyclopentylphenol, potassium salt; 4- Chloro- 2- cyclopentylphenol, sodium salt; Chlorophacinone; ADBAC; Niclosamide; 5- Chlorosalicylanilide; 2- Methyl- 4- isothiazolin- 3- one; Tetradifon; 6- Chlorothymol; Anilazine; Chlorothalonil; Fenac; Chlorfenvinphos; O-( 2- Chloro- 1-( 2,5- dichlorophenyl) vinyl) O, O- diethyl phosphorothioate; PCMX; Piperalin; Fenamiphos; p- Chlorophenyl diiodomethyl sulfone; Metribuzin; Bifenox; Methazole; Diflubenzuron; Oxadiazon; Fenvaler Bromothalin ate; Fluvalinate; Iprodione; Triadimefon; Diclofop – methyl; Profenofos; Oxyfluorfen; Imazalil; Vinclozolin; Fenridazon; Tridiphane; Paclobutrazol; Linalool; [a-( 2- chlorophenyl)- a-( 4- chlorophenyl)- 5- pyrimidinemethanol]; Dicamba dimethylamine; Diethanolamine dicamba; 2,4-D; Lithium 2,4-dichlorophenoxyacetate; Potassium 2,4- dichlorophenoxyacetate; Sodium 2,4- dichlorophenoxyacetate; Ammonium 2,4- dichlorophenoxyacetate; Alkanol* amine 2,4- dichlorophenoxyacetate *( salts of the ethanol and ispropanol series); Alkyl* amine 2,4-dichlorophenoxyacetate *( 100% C12); Alkyl* amine 2,4 dichlorophenoxyacetate *( 100% C14); Alkyl* amine 2,4- dichlorophenoxyacetate *(as in fatty acids of tall oil); Diethanolamine 2,4- dichlorophenoxyacetate; Diethylamine 2,4- dichlorophenoxyacetate; Dimethylamine 2,4- dichlorophenoxyacetate; N, N- Dimethyloleylamine2,4- dichlorophenoxyacetate; Ethanolamine 2,4- dichlorophenoxyacetate; Heptylamine 2,4- dichlorophenoxyacetate; Isopropanolamine 2,4- dichlorophenoxyacetate; Isopropylamine 2,4- dichlorophenoxyacetate; Morpholine 2,4- dichlorophenoxyacetate; N- Oleyl- 1,3- propylenediamine 2,4- dichlorophenoxyacetate; Octylamine 2,4- dichlorophenoxyacetate; Triethanolamine 2,4- dichlorophenoxyacetate; Triethylamine 2,4- dichlorophenoxyacetate; Triisopropanolamine 2,4- dichlorophenoxyacetate; N, N- Dimethyl oleyl- linoleyl amine 2,4- dichlorophenoxyacetate; Butoxyethoxypropyl 2,4- dichlorophenoxyacetate; Butoxyethyl 2,4- dichlorophenoxyacetate; Butoxypropyl 2,4- dichlorophenoxyacetate; Butyl 2,4- dichlorophenoxyacetate; Isobutyl 2,4- dichlorophenoxyacetate; Isooctyl( 2- ethylhexyl) 2,4- dichlorophenoxyacetate; Isooctyl( 2- ethyl- 4- methylpentyl) 2,4- dichlorophenoxyacetate; Isooctyl( 2- octyl) 2,4- dichlorophenoxyacetate; Isopropyl 2,4- dichlorophenoxyacetate; Propylene glycol butyl ether 2,4- dichlorophenoxyacetate; 4-( 2,4- Dichlorophenoxy) butyric acid; Sodium 4-( 2,4- dichlorophenoxy) butyrate; Dimethylamine 4-( 2,4- dichlorophenoxy) butyrate; Butoxyethanol 4-( 2,4- dichlorophenoxy) butyrate; Butyl 4-( 2,4- dichlorophenoxy) butyrate; Isooctyl 4-( 2,4- dichlorophenoxy) butyrate; 2-( 2,4- Dichlorophenoxy) propionic acid ; Dimethylamine 2-( 2,4- dichlorophenoxy) propionate; Butoxyethyl 2-( 2,4- dichlorophenoxy) propionate; Isooctyl 2-( 2,4- dichlorophenoxy) propionate; Isooctyl 2-( 2,4- dichlorophenoxy) propionate; MCPP, DMA; Bromoxynil; Hexachlorophene, sodium salt; Hexachlorophene, potassium salt; Irgasan; Tetrachlorophenols; Tetrachlorophenols, sodium salt; Tetrachlorophenols, alkyl* amine salt*( as in fatty acids of coconut oil); Tetrachlorophenols, potassium salt; Bithionolate sodium; Phenachlor; Potassium 2,4,6- trichlorophenate; 22,4,5-T,4,6- Trichlorophenol, sodium salt; Phenothiazine; Endosulfan; Silvex; Tetrachlorvinphos; Edolan; 2,4- DB; Dimethyl-(2,3,5,6-tetrachloro-1,4-benzodicarbonate); MCPA; Chloroneb; Erbone; Daconil “More dirt!“ “The“The dirtydirty dozen”dozen” PFOS, PFOA, PFHxS PCDD PBDE, PBB, HBCD, PCDF PBDD/F, HBBz PBP PCBs•PCBs TBBPA, TBPAE, Aldrin•Dieldrin Chlordane SCCP, MCCP, LCCP DDT PeCB, PCN, HCH, Dieldrin Chlordecone, Endrin Endosulfan, HCBs PAHs, Nitro-PAH Heptachlor Halogenated PAHs Toxaphene Sn-Organics Mirex Hg, Cd. Pb et al. www.pops.int; www.ospar.org; www.ihpa.info, www.ipen.orgPesticides, Biocides http://www.springerlink.com/content/9032774680846044/fulltext.pdf Pharmaceuticals http://www.springerlink.com/content/0q10km8582605r1x/fulltext.pdf g TEQ/Jahr 70000 PCDD/PCDF in PCP 60000 PCDD/PCDF in CNP co-PCB 50000 Other Chlororganics Industrial Waste Incineration 40000 Municipal Waste Incineration

30000 PCP

20000 CNP IWIIWI MWIMWI 10000 co-PCB 0 1958 1963 1968 1973 1978 1983 1988 1993 Masunaga et al. 1998 Leaching of the PCDD/F into sea: Tokyo basin 4500 50 PCDD/PCDFs (kg/y) PCP-dioxin load 4000 45 to the basin 3500 PCDD/DFs in sediment 40 (ng/g) 3000 35 PCP-dioxin 30 2500 sediment concentration 25 2000 20 1500 15 1000

PCDD/PCDF load toPCDD/PCDF load the Basin (kg) 10 500 5 0 0 1935 1945 1955 1965 1975 1985 1995 Year PCP-originating in PCDD/PCDF sediment (ng/g) Masunaga S. (2004), China-Japan-Korea symposium on environmental analytical chemistry, October 18-21 2004, Shanghai, China.* Emission Sources Environmental Exposure Transport Routes Inter- Chlorine/Bromine/ Thermal/Indust. (e.g. incineration, (e.g. Chlor/Brom-alkali, Atmosphere generational cement, metal industry, historical processes) industrial fires) Inhalation Plants Food ingestion

Chlorine/Bromine Reservoirs (e.g. Occupational Use (e.g. pulp & Land paper, water treatm., contaminated TiO , Magnesium etc.) sites, stockpiles 2 landfills, soil) Animals/ Accidental Cattle

Organohalogen Products Fish & Manufacture (e.g. pesticides, Aquatic Indoor (e.g. pesticides, flame flame retardants, Shellfish retardants, PCBs, PVCs) PCBs, PVCs)

Weber et al 2009. Trichloroethylene; perchloroethylene; epichlorohydrin; hexachlorobutadiene; 4- Chlorotoluene; Dioxazine dyes (Direct Blue 106, Direct Blue 108, and Violet 23); N- phthalocyanine dye; Printing inks (unidentified); Aluminum chloride; Ferric chloride; Cuprous chloride; Cupric chloride; 2-Chloro-1,4-diethoxy-5-nitrobenzene; 5-Chloro-2,4-dimethoxyaniline; 3,5-Dichlorosalicylic acid; o-Chlorofluorobenzene; 3-Chloro-4-fluoronitrobenzene; Chloropentafluorobenzene; 1,2-Dichloro-4- nitrobenzene; 3-Chloro-4-fluorophenol; 4-Chloro-2-nitrophenol; o-Benzyl-p- chlorophenol; 2,3,6-Trichlorobenzoic acid; 2,3,6-Trichlorophenylacetic acid, and sodium salt; 3,4-Dichloroaniline; 3,4-Dichlorobenzaldehyde; 3,4- Dichlorobenzotrichloride; 3,4-Dichlorobenzotrifluoride; 3,4- Dichlorophenylisocyanate; Pentachloroaniline; Pentachlorocyclohexane; Pentabromochlorocyclohexane; Tetrachlorophthalic anhydride; *Phenol (from chlorobenzene); *1,2-Dihydroxybenzene-3,5-disulfonic acid, disodium salt; *2,5- Dihydroxybenzenesulfonic acid; *2,5-Dihydroxybenzenesulfonic acid, potassium salt; *2,4-Dinitrophenol; *2,4-Dinitrophenoxyethanol; *3,5-Dinitrosalicylic acid; *o- Nitroanisole; *2-Nitro-p-cresol; *o-Nitrophenol; *2,4,6-Trinitroresorcinol; *Fumaric acid; *Maleic acid; *Maleic anhydride; *o-Phenetidine; *Phenyl ether; *Phthalic anhydride; *Picric acid; *Sodium picrate; *Non-chlorinated chemicals produced via routes involving chlorinated chemicals.