CO-FORMULANTS UNACCEPTABLE FOR INCLUSION IN PLANT PROTECTION PRODUCTS IN SPAIN

CO-FORMULANTS UNACCEPTABLE FOR INCLUSION IN PLANT PROTECTION PRODUCTS IN SPAIN The purpose of the No 1107/2009 of the European Parliament and of the Council of 21 October concerning the placing of plant protection products on the market and repealing Council Directives 79/117 EEC and 91/414/EEC, is to increase the free movement of such products and the availability of these products in the Member States, taking into account the general principles of protection of human and animal health and the environment. In order to remove, as far as possible, obstacles to trade in existing Plant Protection Products (PPP) due to the different levels of protection in the Member States (MS), the mentioned Regulation lays down harmonised rules for the approval of active substances, safeners and synergists included in PPP, and also rules for adjuvants and co-formulants. The principle of mutual recognition is one of the means of ensuring the free movement of goods within the Community. Thus, the above mentioned Regulation includes requirements and conditions for approval coformulants. Besides, Annex III will provide a list of co-formulants which are not accepted for inclusion in PPP as referred to in Article 27. At the moment, this list is empty, and it is for this reason that a MS shall inform the other MS and the Commission where it considers that a co-formulant has been considered unacceptable and will propose the withdrawal or the inclusion with amended conditions. In this context, as a general rule since 1992 in Spain the co-formulants substances classified as carcinogens, mutagens or substances toxic to reproduction (C/M/R) are not accepted for inclusion in PPP. Neither are they accepted substances which have proved to show other chronic effects or neurotoxicity (see Table 1). It has to be noted that Table 1 includes unacceptable co-formulants usually found over the years in PPP formulations. Therefore, in Spain, co-formulants (oil derived substances, diatomaceous earth, kaolinite, talc, clays ) containing impurities with toxicological relevance such as benzene, 1,3-butadiene, polycyclic aromatics, benzo(a)-pyrene, crystalline silica or asbestiform fibres are controlled. Besides, coformulants containing other components of concern such as naphthalene or toluene are also controlled. The same rule is applied to adyuvants. Consequently, when one of these co-formulants or adyuvants is going to be used in PPP, the impurity certificate or the product containing components of concern is required to demonstrate that it doesn t contain impurities with toxicological relevance or specific components of concern and if not, the coformulant must be replaced by another with less risk. Furthermore, co-formulants (commercial samples such as palygorskite (attapulgite), sepiolite and wollastonite) containing fibres of concern are controlled according to the length of their fibres. This document can be updated based on the evolution of scientific knowledge and European Union legislation Rev.1 25.10.2018 Page 1 of 7

Table 1. List of co-formulants unacceptable for inclusion in PPP. Co-formulant CAS No. Classification Reference 1,1,2-trichloroethane 79-00-5 Carc. 2; H351 2-pyrrolidone Aniline 62-53-3 Disodium tetraborate decahydrate; borax decahydrate Disodium octaborate tetrahydrate 616-45-5 Repr.2; H361d 1303-96- 4 12280-03-4 Carc. 2; H351 Muta 2; H341 STOT RE 1; H372 Repr. 1B; H360DF Repr. 1B; H360DF Available studies at national level Concentration limits following Repr.2; H361d: C 3 % Muta 2; H341: C 1 % (*) STOT RE 1; H372: C 1 % (*) STOT RE 2;H373:0.2 % C < 1 % (*) Repr. 1B; H360DF: C 8.5 % Repr. 1B; H360DF: C 0.3% Disodium octaborate anhydrate 12008-41-2 Repr. 1B; H360DF Repr. 1B; H360DF: C 0.3% Pentasodium (carboxylatomethyl)iminobis (ethylenenitrilo)tetraacetate 140-01-2 Repr.2; H361d STOT RE 2; H373 (inhalation) RAC opinion (June 2017) Repr. 1B; H360D: C 0.3% STOT RE 2; H373 (inhalation): C 10 % Dibutyl phthalate; DBP 84-74-2 Repr. 1B: H360Df Repr. 1B: H360D: C 0.3% Repr. 1B: H360Df: C 3% Dichloromethane; methylene chloride 75-09-2 Carc. 2; H351 Diethylene glycol monomethyl ether; 2-(2-methoxyethoxy)- ethanol Diethyl Phthalate; 1,2-benzenedicarboxylic acid, diethyl ester 111-77-3 84-66-2 Repr.2; H361d Repr.2; H361d: C 3 % Repr.2; H361d Literature search Repr.2; H361d: C 3 % Dimethyl formamide; N,N-dimethylformamide 68-12-2 Repr. 1B: H360D Repr. 1B: H360D: C 0.3% Epichlorhydrin; 1-chloro-2,3-epoxypropane 106-89-8 Carc. 1B; H350 Carc. 1B; H350: C 0.1 % Ethylene glycol monoethyl ether; 2-ethoxyethanol 110-80-5 Repr. 1B: H360FD Repr. 1B: H360FD: C 0.3% Ethylene glycol monomethyl ether; 2-methoxyethanol 109-86-4 Repr. 1B: H360FD Repr. 1B; H360FD: C 0.3% Formaldehyde...% 50-00-0 Carc. 1B; H350 Muta.2; H341 Carc. 1B; H350: C 0.1 % Muta. 2 ; H341: C 1 % Isophorone; 3,5,5-trimethylcyclohex-2- enone 78-59-1 Carc. 2; H351 Rev.1 25.10.2018 Page 2 of 7

Methanol; methyl alcohol Co-formulant CAS No. Classification Reference 67-56-1 STOT SE 1; H370 Naphthalene 91-20-3 Carc. 2; H351 Concentration limits following (*) STOT SE 1; H370: C 10 % (*) STOT SE 2; H371: 3 % C < 10 % N-ethyl-2-pyrrolidone; 1-ethylpyrrolidin-2-one 2687-91- 4 Repr. 1B; H360D Repr. 1B; H360D: C 0.3 % N-hexane 110-54-3 Repr. 2; H361f STOT RE 2; H373 Repr. 2; H361f: C 3% (*) STOT RE 2; H373: C 5 % N-methyl-2-pyrrolidone; 1-methyl-2-pyrrolidone 872-50-4 Repr. 1B; H360D Repr. 1B; H360D: C 0.3% Nonylphenol; [1] 4-nonylphenol, branched [2] 25154-52-3 [1] 84852-15-3 [2] Repr. 2; H361fd Repr. 2; H361fd: C 3% Toluene 108-88-3 Repr. 2; H361d STOT RE 2; H373 Repr. 2; H361d: C 3% STOT RE 2; H373: C 10 % Tributyl phosphate Tetrahydrofurfuryl alcohol; Tetrahydro-2-furylmethanol Ethoxylated tallow amine 126-73-8 Carc. 2; H351 97-99-4 Repr. 1B; H360Df 61791-26-2 The reproductive and developmental toxicity information suggests that classification might be considered regarding these endpoints. Its genotoxicity, long term toxicity/carcinogenicity, reproductive/developmental toxicity and endocrine disrupting potential should be further clarified. EFSA Journal 2015;13(11):4303 Repr. 1B: H360D: C 0.3% Repr. 1B: H360Df: C 3% Not currently listed in Annex VI of 1272/2008. According to Regulation EU 2016/1313 formulant POEtallowamine (CAS No 61791-26-2) is excluded for the use in plant protection products containing glyphosate. It has to be also excluded from any PPP. (*) Specific concentration limits for the substance under consideration in Annex VI of 1272/2008 Rev.1 25.10.2018 Page 3 of 7

Control of impurities or components with toxicological relevance in co-formulants used in the preparation of PPP. Impurities with toxicological relevance in Oil derived substances In Spain, oil derived co-formulants containing impurities with toxicological relevance, such as benzene, 1,3-butadiene, benzo[a]-pyrene and DMSO extract, are controlled according to the notes related to the identification, classification and labelling of certain complex oil-derived substances in Part 3 of the (see table 2). Consequently, when one of these oil derived substances is going to be used in PPP, an impurity certificate is required to ensure that the amount of impurity is below the level allowed in this coformulant. When the amount of impurity is above the level allowed, the co-formulant must be replaced by another with less risk. The of 16 December 2008 on classification, labelling and packaging of substances and mixtures, contains the classification of complex oil derived substances, which are very often used in the preparation of PPP. These substances have specific effects on human health and are classified as carcinogenic or mutagenic unless specific impurities are below certain levels in these substances. The following notes relating to the identification, classification and labelling apply only to certain complex oil-derived substances in Part 3 of the : Note J: The classification as a carcinogen or mutagen need not apply if it can be shown that the substance contains less than 0.1 % w/w benzene (EINECS No 200-753-7). This note applies only to certain complex coal- and oil derived substances in Part 3. Note K: The classification as a carcinogen or mutagen need not apply if it can be shown that the substance contains less than 0.1 % w/w 1,3-butadiene (EINECS No 203-450-8). If the substance is not classified as a carcinogen or mutagen, at least the precautionary statements (P102-) P210-P403 or the S-phrases (2-)9-16 should apply. This note applies only to certain complex oil-derived substances in Part 3. Note L: The classification as a carcinogen need not apply if it can be shown that the substance contains less than 3 % DMSO extract as measured by IP 346 Determination of polycyclic aromatics in unused lubricating base oils and asphaltene free petroleum fractions Dimethyl sulphoxide extraction refractive index method, Institute of Petroleum, London. This note applies only to certain complex oil-derived substances in Part 3. Note M: The classification as a carcinogen need not apply if it can be shown that the substance contains less than 0.005 % w/w benzo[a]-pyrene (EINECS No 200-028-5). This note applies only to certain complex coal-derived substances in Part 3. Rev.1 25.10.2018 Page 4 of 7

Note P: The classification as a carcinogen or mutagen need not apply if it can be shown that the substance contains less than 0.1 % w/w benzene (EINECS No 200-753-7). When the substance is not classified as a carcinogen at least the precautionary statements (P102-)P260-P262- P301 + P310-P331 or the S- phrases (2-)23-24-62 shall apply. This note applies only to certain complex oil-derived substances in Part 3. Components of concern in Oil derived substances In oil-derived co-formulants used in the preparation of PPP, some components of concern, such as naphthalene (classified as Carc. 2 in the regulation (EC) ) and toluene (Toluene is classified as Repr. 2 in the ), are often present. If one of these oil derived substances is going to be used in PPP, in Spain the amount of naphthalene or toluene in the co-formulant is controlled (see table 2). Consequently, oil-derived co-formulants with a content above the concentration limits laid down in CLP (1% of naphthalene or 3% of toluene) leading to its classification as carcinogenic or toxic to reproduction respectively, are not allowed. A certificate with the content of naphthalene or toluene is required to ensure that the amount is below the level allowed in the co-formulant. When the content is above the level allowed, the co-formulant must be replaced by another with less risk. Content of crystalline silica in Quartz sand, kieselgur, aluminium silicate and other mineral and clays used in PPP containing dust These substances could be classified as carcinogenic depending on the content of respirable crystalline silica in the form of quartz or cristoballite. According to the IARC [IARC Monographs Volume 68 (1997) and Volume 100C (2012)], respirable crystalline silica in the form of quartz or cristoballite causes cancer of the lung in humans and it is carcinogenic in humans (Group 1). In application of, if respirable crystalline silica is present in the mixture as an ingredient at a concentration 0.1 % the product should be classified as carcinogen with the category 1A and the hazard statement H350i: May cause cancer by inhalation. The Spanish Authority considers that, taking into account the whole available data in the IARC documents and other scientific literature, this respirable fraction is the one of special concern for the carcinogenicity of crystalline silica in the form of quartz or cristobalite. Consequently, if one of these co-formulants is going to be used in PPP containing dust, in Spain the amount of respirable crystalline silica in the form of quartz or cristobalite is controlled (see Table 2). Rev.1 25.10.2018 Page 5 of 7

Table 2. List of co-formulants, which can contain impurities with toxicological relevance or components of concern. Concentration limits Requirements for Co-formulant Classification following No national registration 1272/2008 Oil derived substances Quartz sand (CAS: 14808-60-7; Quartz, Silicium dioxide, Silica, Silicon dioxide, SiO 2 ) Kieselgur (CAS: 61790-53-2; diatomaceous earth) Aluminium silicate (CAS: 1332-58-7; Kaolin) Smectite group minerals (CAS 12199-37-0); bentonite (CAS 1302-78-9); montmorillonite (CAS 1318-93-0); sepiolite (CAS 63800-37-3); pumice (CAS 1332-09- 8), talc and attapulgite An impurity certificate is required to ensure that the amount of impurity is below the level allowed in this coformulant. Certificate with the content of naphthalene Certificate with the content of toluene Certificate with the total content of crystalline silica (in the form of quartz or cristobalite) and the content of the respirable fraction of crystalline silica. Some of these substances are classified as carcinogenic or mutagenic in the Regulation (EC) unless specific impurities are below certain levels Some of these substances could be classified as carcinogenic depending on the content of Naphthalene (classified as Carc. 2 in the Regulation No (EC) 1272/2008) Some of these substances could be classified as toxic to reproduction depending on the content of Toluene (classified as Repr. 2 in the Regulation No (EC) 1272/2008) This substance could be classified as carcinogenic depending on the content of crystalline silica (considered as carcinogenic to humans Group 1 by IARC) Concentration in oil derived substances of the following impurities equal or exceeding these limits is not allowed:* 0.1% w/w benzene 0.1% w/w 1,3-butadiene 3.0% w/w DMSO extract 0.005% w/w benzo [a]-pyrene Concentration 1% w/w of naphthalene leading these coformulants to be regarded as Carc.2 is not allowed. Concentration 3% w/w of toluene leads these coformulants to be regarded as Repr.2 is not allowed. Concentration 0.1% w/w of respirable crystalline silica in the form of quartz or cristobalite leading these coformulants to be regarded as possible Carc. 1A is not allowed. * Concentration limits of impurities established according to notes related to the identification, classification and labelling applying only to certain complex oil-derived substances ( ). Rev.1 25.10.2018 Page 6 of 7

Co-formulants, which can contain fibres of concern Attapulgite in PPP containing dust The International Agency for Research on Cancer (IARC) has ruled Attapulgite fibres > 5 µm as possibly carcinogenic to humans (Group 2B). Attapulgite with fibres > 5 µm is not allowed to be used in PPP containing dust in Spain (Table 3). A certificate with the content and length of the fibres is required. Talc The International Agency for Research on Cancer (IARC) has ruled that talc containing asbestiform fibres is carcinogenic to humans (Group 1). Talc containing asbestiform fibres is not allowed to be use in PPP in Spain (Table 3). A certificate of absence of asbestiform fibres is required. Table 3. List of co-formulants, which can contain fibres of concern whose length is being controlled. Attapulgite Talc Co-formulant (1) See Table 2 for other requirements Requirements for national registration Certificate with the content and length of the fibres (1) Certificate of absence of asbestiform fibres (1) Classification Attapulgite with long fibres (> 5 µm) is possibly carcinogenic to humans (considered Group 2B by IARC) Talc with asbestiform fibres is considered as carcinogenic to humans Group 1 by IARC Concentration limits Absence of fibres > 5 µm Absence of asbestiform fibres ------------------------------------------------ Rev.1 25.10.2018 Page 7 of 7