DDT IN DICOFOL

Authors : E.J. van de Plassche, A.M.G.R. Schwegler, M. Rasenberg and G.

Schouten








CONTENTS

Page
1 INTRODUCTION 1
2 PRODUCTION OF DICOFOL 2
2.1 Method of synthesis of dicofol 2
2.2 Production within the UN-ECE 2
2.3 Production outside the UN-ECE 2
3 REGULATIONS WITH RESPECT TO THE TECHNICAL SPECIFICATIONS OF
COMMERCIAL DICOFOL 3
4 CONCLUSION 4
5 REFERENCES 5
APPENDIX 1 6










1 INTRODUCTION
The Protocol to the 1979 Convention on Long-Range Transboundary Air Pollution on
Persistent Organic Pollutants states in Annex II that the use of DDT is restricted to:
for public health protection from diseases such as malaria and encephalitis;
as a chemical intermediate to produce dicofol.

The Protocol requirements with respect to the first restriction are discussed elsewhere.
In relation to the use of DDT (cas number: 50-29-3) as feedstock for the production of
dicofol (cas number: 115-32-2) the Protocol states that such use shall be reassessed
no later than two years after the data of entry into force of the present Protocol.

This document describes the current use of DDT as feedstock for the production of dico-
fol. It should be stated that the Protocol has not yet entered into force.

A questionnaire was sent out by the UN-ECE secretariat by the end of 2001 to obtain
information. The questions and the responses are summarised in Appendix 1. In total 24
parties to the LRTAP Convention responded to the questionnaire. Information was also
retrieved via literature search and contacts with producers of dicofol.








2 PRODUCTION OF DICOFOL
2.1 Method of synthesis of dicofol
Dicofol - the active ingredient being a mixture of approximately 80% p,p-dicofol and
20% o,p-dicofol - is produced by hydroxylation of DDT as emulsifiable concentrate and
wettable powder formulations. This implies that:
a producer can purchase DDT and use DDT as a feedstock or starting material to
produce dicofol;
a producer can make DDT as an intermediate or precursor in house first and sub-
sequently produce dicofol from DDT. The advantage of this method is that it elimi-
nates the need to transport DDT itself. DDT was first synthesized in research on
dyes as early as 1874 by Ziedler. DDT as an insecticide was discovered by P.H.
Mller working at J.R. Geigy in 1939. DDT is produced from chloral (trichloraceti-
caldehyde), monochlorobenzene and oleum (fuming sulphuric acid: sul-
phuric(VI)acid containing an excess of sulphur trioxide).


2.2 Production within the UN-ECE
From the information obtained via the questionnaire it was concluded that dicofol is pro-
duced only by Montecinca,S.A. in Barcelona, Spain under contract to Dow Agro-
Sciences (prior owner being Rohm and Haas). Dicofol made and sold by Dow
AgroSciences carries the trademark KELTHANE

. Their production route involves the in

house production of DDT as a precursor from trichloraceticaldehyde, monochloroben-
zene and oleum.

Based on other sources two other producers within the UN-ECE were found:
- in Spain dicofol is probably also produced by Mariano Fernendez Tarrats (source:
HPV-LPV database, European Chemicals Bureau). No information could be ob-
tained on the production process. In Italy dicofol is imported but not produced by
SipCAM SpA.
- in Israel Makhteshim-Agan is probably producing dicofol (source: Internet). No in-
formation on the production process could be obtained.

Based on the information received, it can be concluded that within the UN-ECE region
dicofol is produced by certainly one and maybe two other companies. For one company
it is known that DDT is produced as an on-site intermediate in order to make dicofol. For
the other two companies no information is available.


2.3 Production outside the UN-ECE
In China dicofol is produces by the Yangzhou Pesticide Factory which reports produc-
tion quantities of 2000 ton dicofol per year (source: Internet). Production is also reported
by Hindustan Insecticide Ltd., New Delhi (India). No information on the production proc-
ess used in China or India could be obtained.

According to Dow AgroSciences dicofol is also produced in Brazil. No information on the
production process could be obtained.








3 REGULATIONS WITH RESPECT TO THE TECHNICAL SPECIFICATIONS OF
COMMERCIAL DICOFOL
In several countries or international organisations commercial dicofol has to meet stan-
dards with respect to:
the minimum content of the p,p'-isomer;
the maximum content of DDT and related substances (abbreviation: DDTr). Dico-
fol produced from DDT contains some DDT and DDT analogues, o,p-and p,p-
isomers, DDD, DDE and Cl-DDT. Up to 18 impurities of dicofol have been re-
ported.

The following (inter)national regulations excist:
EU Council Directive 79/117/EEC prohibits use and marketing of products
containing less than 78% p,p-dicofol or more than 1 g/kg (equal to 0.1%) of DDTr;
FAO Specification 123/TC/S/F (1992) requires DDTr to be less than 0.1%;
the limit of 0.1% of DDTr is also in place in the USA and Canada. According to
information from Dow AgroSciences this limit applies also in Japan, Australia and
Argentina. Information from other countries is not available.

The critical issue is if dicofol is purified to meet the stringent specifications set in many,
but no all countries worldwide. KELTHANE

produced by Dow AgroSciences is purified

on-site to meet the 0.1% DDTr limit. The DDTr content of 'raw' dicofol produced by Dow
AgroSciences and employed as feedstock for purification is unknown, but any manufac-
turing wastes - including those containing DDTr - are destroyed through appropriate
techniques like high-temperature incineration.

As stated in chapter 2 no information could be obtained from other producers - in or out-
side the UN-ECE - on the production process of dicofol. Subsequently, the content of
DDTr in commercial dicofol made by these producers is unknown. A content of 3.5%
DDTr of dicofol produced by a company in India has been reported, however.








4 CONCLUSION
Based on the information received it can be concluded that within the UN-ECE region
dicofol is produced by certainly one and maybe two other companies. Dicofol is also
produced outside the UN-ECE region. For Dow AgroSiences in Spain it is known that
DDT is produced as a site-limited intermediate which is used as feedstock to produce
dicofol. For the other companies no information is available.

The way of production used by Dow AgroSciences proves that DDT is not an essential
component in order to make dicofol. The allowed use of DDT as feedstock is from a
technical point of view therefore no longer necessary. Socio-economic considerations
like unfair trade issues may lead to the decision to maintain the exempted use of DDT
for the production of dicofol in the Protocol. This discussion is outside the scope of the
present dossier, however.








5 REFERENCES
Anonymous (2000). Pesticide Information Profiles. EXTOXNET, Extension Toxicology
Network. http://ace.orst.edu/info/extoxnet/pips/dicofol.htm.

Council Directive 90/533/EEC of 15 October 1990 amending the annex to Directive
79/117/EEC prohibiting the placing on the market and use of plant protection products
containing certain active substances. Official Journal L 296, 27/10/1990, p. 63.

E-mail from K. Racke (Dow AgroSciences) to E. van de Plasssche (Royal Haskoning)
29 May 2002.

Racke, D.R. (2002). Dow AgroSciences' Comments on "Information dossier on DDT
used for the production of Dicofol, Final Report, 26 April 2002" prepared by Ministry of
VROM/DGM.















Appendix 1




Information obtained via the questionnaire sent out by the UN-
ECE Secretariat.









Table 1: Questions and responses with respect to the use of DDT as feedstock for the production of dicofol.
UN-ECE mem-
ber state
Is dicofol produced in your
country?
Is DDT used for the produc-
tion of dicofol?
What other production proc-
ess is used?
Is the amount of DDT in commercial dicofol
regulated?
What is the actual amount of
DDT in commercial dicofol?
Albania
Armenia No production No information on use avail-
able.

Austria No production
Belgium No production
Bosnia &
Herzegovina

Bulgaria
Canada No production Use is allowed, amount of DDT is regulated (max
0.1 %)

Croatia No production Dicofol is included in Poison list, but as a product
it is not registered. Active substance is still in
official Poison list, but product made with this
active substance has no use licence because of
unacceptable toxicology and metabolic problems.
Procedure for removing active substance from the
Poison list is in progress.

Cyprus
Czech Republic No production
Denmark No production
Estonia
Finland No production
Former Yugo-
slav Republic of
Macedonia

France No production Concentration DDT is regulated to be < 0.1 %.
Georgia No production Dicofol is not used for (agricultural or) any pur-








UN-ECE mem-
ber state
Is dicofol produced in your
country?
Is DDT used for the produc-
tion of dicofol?
What other production proc-
ess is used?
Is the amount of DDT in commercial dicofol
regulated?
What is the actual amount of
DDT in commercial dicofol?
poses, it is not included in the list of substances
allowed for the use, there is no traditional use
among parties involved (custom, distribution,
storage, end-use)
Germany No production Dicofol is no longer used for agricultural pest
control since 1992. Other application areas as
well as amounts are not known.

Greece
Hungary
Iceland
Ireland
Israel
Italy No production, Dicofol is im-
ported as raw material and is
used after purification for the
formulation of products con-
taining dicofol.

Kazakhstan No production No regulation for the maximum amount of DDT in
Dicofol.

Latvia No production No use
Luxembourg
Monaco, Prin-
cipality of
No production
Netherlands No production Use is banned
Norway No production No use
Poland No production Dicofol is banned from use
Portugal
Republic of
Moldova
No production Dicofol not included in register of permitted sub-
stances for use in agriculture, including individual









UN-ECE mem-
ber state
Is dicofol produced in your
country?
Is DDT used for the produc-
tion of dicofol?
What other production proc-
ess is used?
Is the amount of DDT in commercial dicofol
regulated?
What is the actual amount of
DDT in commercial dicofol?
farms, forestry and household.
Romania
Russian Fed-
eration

Slovakia No production
Slovenia
Spain Production around 1500 tons
per year. All production is sent
to an Italian plant for process-
ing.
No Reaction of chloral (trichloraceti-
caldehyde, CAS 75-87-6),
monochlorobenzene and oleum
(SO3 and H2SO4)
Use around 100 150 tonnes in 2000. According
to observers data, these quantities are decreas-
ing.
Maximum amount of DDT (and related com-
pounds) in commercial dicofol < 1 g/kg.

Sweden No production No use
Switzerland No production There is no registration of dicofol in Switzerland. It
means that this product is not used or produced.

Turkey
Turkmenistan
Ukraine
United King-
dom
No information that dicofol is
produced in the UK
Dicofol is used at 1ton per year. Importers of dicofol were re-
luctant to disclose typical
analysis.
United States No production Use is allowed, amount of DDT is regulated (max
0.1 %)

Uzbekistan
Yugoslavia