Information dossier on DDT used for the production of Dicofol Ministerie van VROM 17 June 2004 Final report 4L0002.A1
A COMPANY OF HASKONING NEDERLAND BV ENVIRONMENT Barbarossastraat 35 P.O. Box 151 Nijmegen 6500 AD The Netherlands +31 (0)24 328 42 84 Telephone +31 (0)24 360 47 37 Fax info@nijmegen.royalhaskoning.com E-mail www.royalhaskoning.com Internet Arnhem 09122561 CoC Document title Information dossier on DDT used for the production of Dicofol Document shorttitle Status Final report Date 17 June 2004 Project number 4L0002.A1 Client Ministerie van VROM Reference Drafted by ing. M. Rasenberg and drs. E. van de Plassche Checked by drs. E. van de Plassche Date/initials check 17-6-2004 EvdP Approved by drs. E. van de Plassche Date/initials approval 17-6-2004 EvdP
0 Executive Summary The POP Protocol requires that the use of DDT as a chemical intermediate to produce dicofol be reassessed no later than two years after the date of entry into force of the POP Protocol. The introductory paragraph of Annex II of the POP Protocol provides that Annex II shall not apply to substances listed in it when they occur inter alia as sitelimited chemical intermediates in the manufacture of one or more different substances and are thus chemically transformed. A questionnaire was sent out by the UN-ECE Secretariat in 2001/2 and 2004. The table below shows the response. Table 0.1 Responses Responders Replies 2001/2 and 2004 for DDT used for production of dicofol Parties to the POP Protocol 13 Signatories to the POP Protocol 13 Parties to CLRTAP only 4 Total 30 Based on the information received and other sources, it can be concluded that within the UN-ECE region there is one active producer, which produces DDT as a non-isolated onsite intermediate to produce dicofol. In the EU the production and use of DDT as a sitelimited, closed-system intermediate for the production of dicofol is allowed until 1 January 2014 (EC Regulation 850/2004). Outside the UN-ECE region countries producing dicofol include China, Brazil and India, but no information is available on the production process. In several countries regulations exist with respect to the DDTr (DDT and related substances) content of commercial dicofol. In the EU, USA and Canada the limit of DDTr is 0.1%. No information is available for other Parties. Based on the information received from the questionnaires and from other sources, the one known remaining active producer of DDT in the UN-ECE region produces it as a non-isolated on site-intermediate in the production of dicofol. Because clause (iii) of the introductory paragraph of Annex II allows such use, the restricted use allowed in the table entry in Annex II for use of DDT as a chemical intermediate to produce dicofol technically is no longer being used. Final report - i - 17 June 2004
CONTENTS Page 0 EXECUTIVE SUMMARY i 1 INTRODUCTION 1 2 PRODUCTION, USE AND CONTROL ACTION IN THE UN-ECE REGION 2 2.1 Production of dicofol 2 2.2 Use of dicofol 2 2.3 Disposal of dicofol 2 2.4 Actions to control production and use 3 3 OTHER INFORMATION 4 4 CONCLUDING REMARKS ON THE USE AND PRODUCTION OF DICOFOL RELATIVE TO ANNEX 2 OF THE PROTOCOL 5 5 REFERENCES 6 Appendix 1: Information obtained via the questionnaires sent out by the UN-ECE Secretariat in 2001/2 and 2004 Appendix 2: Status of responders under the Convention and the POP Protocol Final report - ii - 17 June 2004
1 INTRODUCTION The Protocol to the 1979 Convention on Long-Range Transboundary Air Pollution on Persistent Organic Pollutants states in Annex 2 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 introductory paragraph of Annex I and II of the POP Protocol excludes substances such as DDT when they occur inter alia as a site-limited chemical intermediate in the manufacture of other substances such as 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 dicofol. A questionnaire was sent out by the UN-ECE secretariat in 2001/2 and the beginning of 2004 to obtain information. The questions and the responses are summarised in Appendix 1. The table below shows the response. Table 1.1 Responses Responders Replies 2001/2 and 2004 for DDT used for production of dicofol Parties to the POP Protocol 13 Signatories to the POP Protocol 13 Parties to CLRTAP only 4 Total 30 Additional information was retrieved via literature search and contacts with the producer of dicofol. Final report - 1-17 June 2004
2 PRODUCTION, USE AND CONTROL ACTION IN THE UN-ECE REGION 2.1 Production 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 subsequently produce dicofol from DDT. The advantage of this method is that it eliminates 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. Müller working at J.R. Geigy in 1939. DDT is produced from chloral (trichloraceticaldehyde), monochlorobenzene and oleum (fuming sulphuric acid: sulphuric(vi)acid containing an excess of sulphur trioxide). From the information obtained via the questionnaire it was concluded that dicofol is produced only by Montecinca,S.A. in Barcelona, Spain under contract to Dow Agro- Sciences (prior owner being Rohm and Haas). Subsequently, dicofol is transported to Italy and purified by SipCAM SpA. 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, monochlorobenzene and oleum. Based on other sources two other producers within the UN-ECE were found: In Spain dicofol was probably also produced by Mariano Fernendez Tarrats appearing in the HPV-LPV database in 2001. The present version of the data base doesn t contain this company anymore (source: HPV-LPV database, European Chemicals Bureau); In Israel Makhteshim-Agan is probably producing dicofol (source: Internet). However, this appeared to be purchases from Dow AgroSciences. Based on the information received, it can be concluded that within the UN-ECE region dicofol is produced by one company where DDT is produced as an on-site intermediate in order to make dicofol. 2.2 Use of dicofol Not relevant. 2.3 Disposal of dicofol Not relevant. Final report - 2-17 June 2004
2.4 Actions to control production and use In several countries or international organisations commercial dicofol has to meet standards with respect to: The minimum content of the p,p'-isomer; The maximum content of DDT and related substances (abbreviation: DDTr). Dicofol 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 reported. The following (inter)national regulations exist: In the EU the requirements for purity of dicofol are laid down in 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: it 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, Brazil, Australia and Argentina. Information from other countries is not available. In the EU the Commission has in June 2003 proposed a Regulation of the European Parliament and the Council on Persistent Organic Pollutants (COM(2003) 333 final) which contains a ban of production, placing on the market and use of DDT. The Parliament has in February 2004 adopted a legislative resolution on the Regulation. The Regulation was adopted in April 2004 (Regulation EC 850/2004). According to Annex I Member States may allow the existing production and use of DDT as a site-limited, closed-system intermediate for the production of dicofol until 1 January 2014 in accordance with Article 4(3) of the Regulation. The Commission shall review this exemption by 31 December 2008 in the light of the outcome of the evaluation in the framework of Directive 91/414/EEC (the EU Directive concerning the placing of plant protection products on the market). The critical issue is if dicofol is purified to meet the stringent specifications set in many, but not 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 manufacturing wastes including those containing DDTr are destroyed through appropriate techniques like high-temperature incineration. From other producers in or outside the UN-ECE no information could be obtained 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. Final report - 3-17 June 2004
3 OTHER INFORMATION In China dicofol is produced by the Yangzhou Pesticide Factory which reports production 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 process used in China or India could be obtained. Dicofol is also produced in Brazil by NORTOX and sold as DICOFOL NORTOX. According to Dow AgroSciences during July of 2002 the Brazil Ministry of Health (ANVISA) concluded the first step of the reevaluation of dicofol products, and concluded that it will adopt and enforce the FAO specification of <0.1% DDT-related (DDTr) impurities as a national standard. Thus, NORTOX had its registration suspended until the company can produce dicofol to meet this standard. Final report - 4-17 June 2004
4 CONCLUDING REMARKS ON THE USE AND PRODUCTION OF DICOFOL RELATIVE TO ANNEX 2 OF THE PROTOCOL Based on the information received it can be concluded that within the UN-ECE region dicofol is produced by one company: Dow AgroSciences. Dicofol is also produced outside the UN-ECE region. For Dow AgroSiences it is known that DDT is produced as a site-limited intermediate which is used as feedstock to produce dicofol. 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. Final report - 5-17 June 2004
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-mails from K. Racke (Dow AgroSciences) to E. van de Plasssche (Royal Haskoning) 29 May 2002 and 16 February 2004. European Parliament legislative resolution on the proposal for a European Parliament and Council regulation on persistent organic pollutants and amending Directives 79/117/EEC and 96/59/EC (COM(2003) 333 C5 0273/2003 2003/0119(COD)). Minutes of 26/2/2004 Provisional Edition. P5_TA-PROV(2004)0109. A5-0017/2004. Internet site NORTOX: http://www.nortox.com.br/. Proposal for a Regulation of the European Parliament and of the Council on persistent organic pollutants and amending Directives 79/117/EEC and 96/59/EC. COM(2003) 333 final. 2003/0119 (COD), 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. Regulation (EC) No. 850/2004 of the European Parliament and of the Council of 29 April 2004 on persistent organic pollutants and amending Directive 79/117/EEC. Final report - 6-17 June 2004
Appendix 1 Information obtained via the questionnaires sent out by the UN-ECE Secretariat in 2001/2 and 2004. Final report 17 June 2004
Table A1.1 Questions and responses with respect to the use of DDT as feedstock for the production of dicofol. UN-ECE member state Is dicofol produced in your country? Is DDT used for the production of dicofol? What other production process is used? Is the amount of DDT in commercial dicofol regulated? Armenia No production No approval of dicofol. Austria No production Belgium No production Bulgaria No production Canada No production Use is allowed, level of DDT is not permitted to exceed 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 No production Czech No production Republic Denmark No production Estonia European Commission Yes Dicofol containing less than 78 % of p.p.1-dicofol or more than 1 g/kg DDT and DDT related compounds is prohibited. Finland No production France No production Concentration DDT is regulated to be < 0.1 %. What is the actual amount of DDT in commercial dicofol? Final report - A1.1-17 June 2004
UN-ECE member state Is dicofol produced in your country? Is DDT used for the production of dicofol? What other production process is used? Is the amount of DDT in commercial dicofol regulated? Georgia No production Dicofol is not used for (agricultural or) any purposes, 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. Ireland No production Italy No production, Dicofol is imported as raw material and is used after purification for the formulation of products containing dicofol. No production No regulation for the maximum amount of DDT in Dicofol. Latvia No production No use Lithuania No production Monaco No production Kazakhstan Netherlands No production No authorisation for the use of dicofol. Norway No production No use Poland No production Dicofol is banned. Portugal Republic of Moldova No production Dicofol not included in register of permitted substances for use in agriculture, including individual farms, forestry and household. What is the actual amount of DDT in commercial dicofol? Final report - A1.2-17 June 2004
UN-ECE member state Is dicofol produced in your country? Slovakia No production Spain Production around 1500 tons per year. All production is sent to an Italian plant for processing. Is DDT used for the production of dicofol? What other production process is used? No Reaction of chloral (trichloraceticaldehyde, CAS 75-87-6), monochlorobenzene and oleum (SO3 and H2SO4) Is the amount of DDT in commercial dicofol regulated? Use around 100 150 tonnes in 2000. According to observers data, these quantities are decreasing. Maximum amount of DDT (and related compounds) in commercial dicofol < 1 g/kg. Sweden No production No use of dicofol in Sweden. Switzerland Turkey No production United Kingdom United States No production There is no registration of dicofol in Switzerland. It means that this product is not used or produced. What is the actual amount of DDT in commercial dicofol? No production Dicofol is used at 1 ton per year. UK contacted trade associations who do not hold information on either quantities of dicofol used in the UK or the realistic DDT contamination present. Importers of dicofol were reluctant to disclose typical analyses. No production Use is allowed. Unknown. Amount of DDTr is regulated (max 0.1 % by weight) Final report - A1.3-17 June 2004
Appendix 2 Status of responders under the Convention and the POP Protocol Final report 17 June 2004
Country Party to the Convention Signatory POP Party to the POP Protocol Response 2001/2 Response 2004 Protocol Armenia X X X X Austria X X X X X Azerbaijan X Belarus X Belgium X X X X Bosnia and Herzegovina X Bulgaria X X X X Canada X X X X X Croatia X X X Cyprus X X X Czech Republic X X X X X Denmark X X X X X Estonia X Finland X X X X X France X X X X X Georgia X X Germany X X X X X Greece X X Holy See Hungary X X X Iceland X X X Ireland X X X Italy X X X X Kazakhstan X X Kyrgyzstan X Latvia X X X X Liechtenstein X X X Lithuania X X X Luxembourg X X X Malta X Monaco X X Netherlands X X X X X Norway X X X X X Poland X X X X Portugal X X Republic of Moldova X X X X Romania X X X Russian Federation X San Marino Slovakia X X X X Slovenia X X Spain X X X Sweden X X X X X Switzerland X X X X X The Former Yugoslav Republic of Macedonia X Final report - A2.1-17 June 2004
Country Party to the Convention Signatory POP Party to the POP Protocol Response 2001/2 Response 2004 Protocol Turkey X X Ukraine X X UK X X X X USA X X X X European Community X X X Total: 49 36 19 25 24 Final report - A2.2-17 June 2004