5.1 Introduction

As a starting point to discussing organic pigments, it should be noted that the specific physicochemical, toxicological and ecological properties of these compounds present an uncommonly small risk potential. Pigments are not only by definition ‘practically insoluble’, but insolubility in water and organic media is a prerequisite for any application of a pigment. So in this respect, organic pigments differ from all other organic chemicals. An attempt to dissolve an organic pigment by applying extreme solvents such as dimethyl sulfoxide or hexamethylphosphoric triamide leads – if at all successful – to dyes or to decomposition.

The analysis of any substance or product that is to be marketed requires not just identification of its technical and application properties. Toxicological and ecological considerations have become a primary concern in today's industry. The pigment industry is no exception. Manufacturers, processors and customers are always faced with the question of whether the production or use of a specific product might present an unacceptably high toxicological or ecological risk for man or environment. The problem of eliminating or at least reducing these risks to legally acceptable levels is a very urgent one. The question of acceptability is not only based on one's responsibility, but criteria must be developed for each individual case with respect to legal provisions.

It is of paramount importance to evaluate the physical, chemical, toxicological and ecological properties of a pigment in order to be able to assess its influence on the environment and to estimate whether a given product presents a toxicological or ecological risk [1]. It is important also to consider the type of handling and use that a pigment is likely to undergo, the extent of human exposure that might be expected, and the amounts involved. Chemicals are typically assessed on the basis of a limited body of data, a task that is normally assigned to a specialist. More complex cases will even be judged by an interdisciplinary group of experts.

Prime considerations in pigment manufacture and use, as with any other chemical, include personnel safety, air emission and wastewater quality, and appropriate waste removal. Although basic information is supplied by the pigment manufacturer, it is the processor who is responsible for safe handling and use. The processor is also responsible for solving internal safety problems.

It has become increasingly common to provide information on safe pigment handling and use in concentrated form on safety data sheets. Apart from listing physical and chemical parameters and information as to safety and precautionary measures, fire and flammability data, first aid after contamination and accidents, and waste disposal, these sheets also provide toxicological and ecological parameters.

5.2 Chemicals Legislation

5.2.2 Legislation Concerning Organic Pigments

Important legal regulations for pigments are primarily connected with food packaging, consumer goods and toys. In this context two general principles must be considered [5]:

• - The pigment producer has to assure his customer that the pigment is toxicologically of no concern.
• - The manufacturer of the pigmented articles must guarantee that the pigment neither migrates into food nor migrates from consumer goods or toys.

The primary concern of regulations that pertain to pigments in particular is to define upper limits for impurities such as traces of heavy metals, traces of aromatic amines, polychlorobiphenyls, polychlorinated dibenzodioxins/-furans (‘dioxins’). These limits, which are defined differently by individual countries, should not be exceeded. This is of paramount importance in pigment applications that involve particularly high potential human exposure, for instance in colours for the artists' market or for children's finger paints. The same is true for low exposure applications (pigments are incorporated in coatings or plastics and thus largely protected from human contact) but, however, affect a large number of persons. This is particularly important in areas such as toys or food packaging. In Germany, for instance, the use of colourants for consumer goods is described by Recommendation IX of the Federal Institute for Risk Assessment at the Federal Health Agency (Bundesgesundheitsamt), which stipulates that no colourant may enter food at all, not even in traces [6].

Examining the ‘curriculum vitae’ of a pigment consists of the following steps:

• - production (starting materials, impurities, side products),
• - working the pigment into its application medium,
• - intended use of the finished article,
• - destruction or removal of the article after use (waste management).

The single most important factor in evaluating the toxicological and ecological properties of an organic pigment is its extreme insolubility in water and in the application media.

Pigments are therefore processed largely as solids, crystalline, and consequently are physiologically inert materials.

Since organic pigments are commonly combined with other materials, a pigmented system typically contains only a small percentage of actual pigment. It is therefore likely that other components, such as binders, solvents and various agents may more severely affect the ecological and toxicological properties of the applied product.

Table 5.3 below lists the specific legislation primarily concerning organic pigments.

Legislation	Country
Regulation (EC) No 1935/2004 on materials and articles Intended to come into contact with Foodstuff (Framework)	EU
European Norm EN 71-Part 3: Safety of Toys	EU
Matériaux au contact des denrées alimentaire produits de nettoyage de ces	EU
Directive 2009/48 on the Safety of Toys (June 2009), last amendment 2015	EU
European Council Resolution AP(89)1: Colourants in plastic materials (1989)	Council of Europe
Matériaux, No. 1227, Direction des Journaux Officiels, Paris	FR
Circulaire No 176 relative aux pigments et colourants des matières plastiques du 2 décembre 1959	FR
Matériaux mis au contact des denrées alimentaires Lettre-circulaire (1979–1985)	FR
Projet d'arrêté relatif à la colouration des matériaux et objets en matière plastique, des vernis et des revêtements destinés à entrer en contact avec les denrées, produits et boissons pour l'alimentation de l'homme et des animaux (2010)	FR
Entwurf zur Änderung der Bedarfsgegenständeverordnung vom 26.06.2016	DE
Verwaltungsvorschrift wassergefährdende Stoffe (Änderung 2011)	DE
817.02 Lebensmittel- und Gebrauchsgegenständeverordnung (February 2016)	CH
817.023.21 Verordnung des EDI 2005 über Bedarfsgegenstände (1 April 2013)	CH
Self-Restrictive Requirements on food-contacting Articles made of polyolefins and certain polymers, part 2, Positive lists, Colourants. 8th edition (May 2004)	JA
GB 9685-2008, Hygienic Standards for Uses of Additives in Food Containers and Packaging Material	CN
FDA Regulation 21CFR 178.3297. Colourants for Polymers	USA
Safe Handling of Colour Pigments, edited by CPMA	USA

The European Commision has published the August 2014 version of “Addresses of European and National European Authorities” related to ‘General Health and Consumers’ as well as a list of the National Governmental Authorities in Europe.These documents can be obtained from: http://ec.europa.eu/food/food/chemicalsafety/foodcontact/auth_ref_en.pdf

Brochures on Safe Handling of Pigments have been published in the USA [7] and in Europe [8, 9] summarizing general health effects, hazard communication, environmental concern and providing information on safety data of the most important pigment classes.

5.2.2.1 Food Packaging/Food Contact

Food packaging plays an important role in context of food contact. The number of regulations considering food contact materials like plastics, metals, coatings, paper and board, rubbers and others alone amounts to more than 4700 regulations worldwide, although the EU legislation has lead to a considerable unification of laws.

5.2.2.1.1 Europe

Materials and articles intended to come into contact with foodstuff are generally regulated in the EU by Framework Regulation (EC) No. 1935/2004/EEC. The principle underlying this regulation is that any material or article intended to come into contact directly or indirectly with food must be sufficiently inert to preclude substances from being transferred to food in quantities large enough to endanger human health.

Council Directive 89/109/EEC and Commission Directive 90/128 have been repealed.

Single Directives, laws and resolutions are released under Regulation (EC) 1935/2004, such as given below.

5.2.2.1.2 Plastic Material

• - Directive 2002/72/EC with its 6^th Amendment Regulation 975/2009/EC. The existing list of additives contained in Directive 2002/72/EC was incomplete in as much as it did not contain all substances currently accepted in one or more Member States.
• - Therefore, a new Commission Regulation (EU) No 10/2011 has been released and repeals 2002/72. Regulation 10/2011, Amendments 202/2014; 321/2011; 1282/2011; 1183/2012; 2015/174 established the specific rules for plastics and articles.
• - It is now a complete list of monomers, other starting substances and additives.
• - Only substances authorized at EU level may be used.
• - Colourants in plastics are not part of the new regulations and should therefore remain subject to national law.
• - Resolution AP (89) 1 (Council of Europe): On the use of colourants in plastic materials coming into contact with food [10].

5.2.2.1.3 Paper and Board

• - Resolution AP (2002)1 on Paper and Boards: Council of Europe: Policy Statement Version 4 4-12.02.2009.
• - Council of Europe, Technical document No. 5 – Practical Guide for users of Resolution AP (2002) 1 on paper and board materials and articles intended to come into contact with foodstuffs (18.09.2002).
• - Council of Europe: Policy statement concerning tissue paper kitchen towels and napkins, Version 1 (2004).

5.2.2.1.4 Printing Inks

• - A German Draft Ordinance on printing inks with a positive list of food contact printing is under development. The Fifth Draft (14.07.2014) would apply to printing inks to both food contact and non-food contact sides of food contact material. Meanwhile the German Authorities tend to compose a corresponding European regulation. Therefore a final regulation may not be available before 2 or more years. It is absolutely too premature to request “compliance” with the requirements of the German Draft Printing Ink Ordinance (EuPIA, II February 2015).
• - Council of Europe: Resolution AP (2005)2 on packaging inks applied to the non-food contact surface of food packaging materials and articles intended to come into contact with foodstuffs and others.
• - Council of Europe: Policy Statement concerning inks applied to the non-food contact surface of food packaging, Version 2 – 10.10.2007.
• - Switzerland: Verordnung des EDI über Bedarfsgegenstände – Anhang 6, Verpackungstinten (SR 817.023.21, April 2010, Änderung vom 1 April 2013).

5.2.2.1.5 Coatings

• - Council of Europe: Resolution AP (2004)1 Coatings.
• - Council of Europe: Policy statement concerning coatings Version 2 (2008).

5.2.2.1.6 Regenerated Cellulose

• - Directive 93/10/EC relating to materials and articles made of regenerated cellulose film intended to come into contact with foodstuffs.
• - Directive 93/111/EC amending Directive 93/10/EEC.

5.2.2.1.7 Elastomers and Rubber

• - Directive 93/11/EEC.
• - Policy Statement concerning Rubber Products intended to come into contact with foodstuffs, Version 1 – 10.06.2004.

5.2.2.1.8 Ceramic Articles

• - Directive 2005/31/EC (Amendment to Directive 84/500/EEC).

5.2.2.2 Purity Criteria

5.2.2.2.1 Colourants

Regarding colourants no uniform EU regulation exists so far concerning the colouration of food packing. The European Resolution AP (89)1 [10] aims at a harmonized EU regulation. The required purity criteria for colourants to be used for the colouration of food packing materials made from plastics are:

• - The maximum threshold limits of metals or metal ions soluble in 0.1m hydrochloric acid are as follows:

  Council of Europe Resolution AP (89) 1 (1989):

  Metal	Limit (ppm)	Metal	Limit (ppm)
  As	100	Hg	50
  Ba	100	Pb	100
  Cd	100	Sb	500
  Cr	1000	Se	100

  Belgium, France, Great Britain, Germany, Greece, Portugal and Switzerland are in accordance with these limit values. Deviations exist in the Netherlands for Cd (1000) and Sb (2000) and in Spain for Ba (1000) and Cd (2000) [11].

• - European Parliament and Council Directive 94/62/EC on packaging and packaging waste (with Amendments 2004/12/EC, 2005/20/EC): The concentration limits of lead, cadmium, mercury and chromium(VI) in packaging material or components of packaging material are not allowed to exceed 100 ppm (cumulative).
• - The trace amount of primary aromatic amines, which are soluble in 1m hydrochloric acid, must be lower than 500 ppm (expressed as aniline). ETAD¹⁾ has developed a testing method for aromatic amines [12].
• - The threshold limit for aromatic aminosulfonic acids, expressed as aniline sulfonic acid, must be below 500 ppm.
• - For benzidine, 2-naphthylamine and 4-aminodiphenyl the threshold limit is 10 ppm.
• - The trace amount of polychlorinated biphenyls (PCB) should not exceed 25 mg kg⁻¹.
• - ETAD¹ and VdMi (German Association of Inorganic Pigments) have published a review on colourants for food contact plastics [13].
• - The Scientific Committee for Food (SCF) has laid down for toxicological evaluation of food contact substances three levels of toxicological tests dependent on the amount of migration (mg kg⁻¹ food simulant): level 1: <0.05; level 2: 0.05-5; level 3: >5.

5.2.2.2.2 Other Countries

Several non-European countries have released identical or similar regulations to the European Regulation AP (89)1 regarding the threshold limits for metals, aromatic amines, aromatic aminosulfonic acids and PCB.

5.2.2.2.3 USA

• - A comprehensive study, performed in the USA by DCMA (Dry Colours Manufacturing Association)²⁾ showed that the metal impurity in organic pigments is markedly below legal standards [14].
• - 21 CFR 178.3297 Colourants for polymers. The maximum migration level is 10 mg kg⁻¹ of food.
• - CONEG Regulation: The Coalition of Northeastern Governors (CONEG) has released in a regulation nearly the same requirements as written in 94/62/EEC (see above): ‘Aggregate heavy metal³⁾ limits apply to cadmium, mercury, lead and hexavalent chromium in packaging or packaging components. The total weight of such metals should not exceed 100 ppm’.

Identical threshold limit values for metals with the data of the Council of Europe Resolution AP (89)1 exist in:

Country
Australia:	Australian Standard 2070-1999 Plastic materials for food contact use
Japan:	Japan Hygienic PVC Association (JHPA) PVC for Food Contact Applications: for As, Cd, Hg and Pb.
Belgium	Arrêté royal modifiant l'arrêté royal du 3 juillet 2005 relatif aux matériaux et aux objets en matière plastique destinés à entrer en contact avec les denrées alimentaires (18 September 2008).
Germany:	Empfehlung IX. Farbmittel zum Einfärben von Kunststoffen und anderen Polymeren für Bedarfsgegenstände (01.02.2015) (Rec. IX. Colourants for Plastics and other Polymers Used in Commodities (2015)).
United Kingdom:	Statutory instruments 2009 No. 205. The Plastic Materials and Articles in Contact with Food Regulations 2009.
Switzerland:	Kunststoffverordnung, (June 2015).

The Council of Europe Resolution AP (89) 1 also regulates the contents of the following substances:

1. Primary aromatic amines, soluble in 1 molar hydrochloric acid, must not exceed 500 ppm (mg kg⁻¹) (expressed as aniline).
2. Benzidine, 2-naphthylamine, 4-aminobiphenyl and 2-methyl-4-chloroaniline must not exceed a limit value of 10 ppm in total.
3. Aromatic aminosulfonic acids must not exceed a limit value of 500 ppm, calculated as anilinesulfonic acid. This limit value is identical for the United Kingdom and for Switzerland.

Limit values for a specific country should be viewed in the corresponding listed references.

5.2.2.3 Toys

On a national basis, toys require compliance of limits for the same impurities as outlined under food packaging/food contact. In particular, trace metal amounts have to be considered as well as threshold limits for aromatic amines, soluble in 0.07M hydrochloric acid. The trace amount of cancerogenic amines should, depending on the various countries, not exceed 5 or 10 ppm.

Incorporation of the EU regulation into national laws has reduced the number of national laws in this field.

EU Directive 2009/48/EC [15] on the safety of toys contains a list of migration limits of 19 ‘elements’ (metals), a list of allergenic fragrances with <100 mg kg⁻¹ and a corresponding list with >100 mg kg⁻¹.

The following region- or nation-specific regulations apply for toys, with most of the EU countries transposed.

5.2.2.3.1 European Union

• - European Standard EN 71/3 (2002) defines the purity criteria of toys, with two threshold limit levels of metals for different kinds of toys.
• - Directive on Safety of Toys 2008/112/EC (December 2008).

5.2.2.3.2 European Countries

Country
Belgium:	Koninklijk besluit van 4 maart 2002 - Wijziging: Koninklijk besluit van 30 december 2009, veiligheidvan speelgoed.
Germany:	EN/DIN 71-3: Part 3: Migration of certain elements (November 2002).
	BfR Rec. 47 [XLVII.] Toys from plastics and from paper and paperboard (2003).
France:	Décret no 2010-166 du 22 février 2010 relatif à la sécurité des jouets.
Switzerland:	Verordnung über die Sicherheit von Spielzeug (2002); Änderung vom 13 January 2011.

5.2.2.3.3 Other Countries

Country
Australia:	Australian Standard 1647 (1982) Children Toys, Parts 3, Toxicological Requirements, Parts 3.
Canada:	Hazardous Products (Toys) Regulations (2007).
Japan:	Specifications, Standards and Testing Methods for Foodstuffs, Implements, Containers and Packaging, Toys, Detergents (January 2009).
USA:	16 CFR 1130 Requirements for consumer registration of durable infant or toddler products (plus parts 1-9).
	Standard Consumer Safety Specification on Toy Safety: ASTM F 963-08.

5.2.2.3.4 Metal Impurities in Toys [16]

5.2.2.4 Consumer Goods

Consumer Goods are defined and regulated in Germany according to the Lebensmittel-, Bedarfsgegenstände- und Futtermittelgesetzbuch (latest version 26 January 2016) and Bedarfsgegenständeverordnung (Consumer Goods Ordinance, latest amendment 24 June 2013).

Impurity	Europe 1a)	Europe 2b)	UK	USA	Australia (T)
Lead	90 (T)	90	250 T	600c)	100
Arsenic	25 (T)	25	100 T	100	100
Mercury	60	25	100	100	100
Cadmium	75	50	100	100	100
Selenium	500	500	—	—	100
Barium	500	250	500	500	100
Chromium	60	25	250	250	100
Antimony	60	60	50	25	100
a) Europe 1: surface coatings, polymers, paper and board, textiles, glass/ceramic/metallic materials. b) Europe 2: modelling compounds, paints, varnishes, lacquers. c) In paints.

Annex 1 Nr.7 of the Consumer Goods Ordinance introduced a prohibition on the production, import and sale of certain garments and fabrics dyed with azo colourants that may split to cancerogenic aromatic amines. There are 24 prohibited amines in total (see TRGS 614 [17]).

Hydrazone pigments were also excluded, because by application of the official testing method none of the listed aromatic amines could be detected [18].

This German restriction inevitably stimulated similar restrictions in other EU member states, and finally a harmonization at EU level was reached through the EU Directive 2002/61/EC, now repealed and replaced by Reach Annex XVII [19]. Table 5.2 lists the 22 prohibited aromatic amines.

5.2.2.4.1 Polychlorobiphenyls (PCBs)

PCB (polychlorobiphenyl) traces may be found in two groups of organic pigments, namely, in:

1. hydrazone pigments derived from chloroaniline or dichloro- or tetrachlorodiaminodiphenyl, which may undergo various side reactions that produce traces of PCBs;
2. pigments that are manufactured in the presence of dichlorobenzene or trichlorobenzene as a solvent; in this case, traces of PCB may be formed through radical reactions.

Strict legal limits have been defined in several countries, because of the persistency and wide distribution of polychlorobiphenyls. These regulations have primarily been issued to protect the environment, and less so because of a direct hazard for humans.

A threshold limit value for polychlorinated biphenyls (PCBs) of 25 mg kg⁻¹, expressed as decachlorobiphenyl, is recommended by the Council of Europe and exists, for instance, throughout the European Union, Switzerland, USA [20] and China.

In many countries any content of polychlorobiphenyls in food or food packing material is banned or restricted to 0.5-2 mg kg⁻¹, which means not detectable in this concentration range.

Hexachlorobenzene is principally treated and classified as a polychloropbiphenyl.

5.2.2.4.2 Polychlorinated Dioxins/Furans (‘Dioxins’)

Starting from chlorine-containing compounds, similar to the formation of PCBs, pigment synthesis might lead to the formation of trace amounts of polychlorinated dibenzodioxins (PCDDs) and/or polychlorinated dibenzofurans (PCDFs) (‘dioxins’). Some 75 PCDD and 135 PCDF cogeners can be formed. The toxicological effect of these compound is quite different; dioxins with at least tetrachloro (or bromo) substitution in 2,3,7,8-positions are of most concern [21].

The German Hazardous Substances Ordinance (Chemikalien-Verbotsverordnung) prohibits products to be placed on the market for which very low limits of dioxin traces are exceeded [22]. Regulated substances are chlorinated and brominated dioxins. The stringent limit are detailed in Table 5.5.

5.2.2.4.3 Barium Pigments

Barium pigments, which are the barium salts of 1-azo-2-hydroxy-naphthalenyl-arylsulfonic acid, are excluded from the generic classification of barium salts as ‘harmful’ [Reg. 1272/2008, Annex 1, Classification and Labelling for Hazardous Substances and Mixtures]: ‘056-002-00-7 barium salts, with the exception of…1-azo-2-hydroxynaphthalenyl aryl sulphonic acid…’. This classification for barium salts results in the non-labelling of other barium pigments [23]. Table 5.6 lists a few industrially used barium pigments.

CAS-No.	C.I. Pigment	Chemical name	C.I. Const. No.
15782-04-4	P. Orange 17	Benzenesulfonic acid, 4-[(2-hydroxy-1-naphthalenyl)azo]-, barium salt (2 : 1)	15510:1
67801-01-8	P. Orange 46	Benzenesulfonic acid, 5-chloro-4-ethyl-2-[(2-hydroxy-1-naphthalenyl)azo]-, barium salt (2 : 1)	15602
7585-41-3	P. Red 48:1	2-Naphthalenecarboxylic acid, 4-[(5-chloro-4-methyl-2-sulfophenyl)azo]-3-hydroxy-,barium salt (1 : 1)	15865:1
5850-87-3	P. Red 51:1	Benzenesulfonic acid, 4-[(2-hydroxy-1-naphthalenyl)azo]-2-methyl-, barium salt (2 : 1)	15580:1
17814-20-9	P. Red 52:3	2-Naphthalenecarboxylic acid, 4-[(4-chloro-5-methyl-2-sulfophenyl)azo]-3-hydroxy-,barium salt (1 : 1)	15860:3
5160-02-1	P. Red 53:1	Benzenesulfonic acid, 5-chloro-2-[(2-hydroxy-1-naphthalenyl)azo]-4-methyl-, barium salt (2 : 1)	15585:1
17852-98-1	P. Red 57:2	2-Naphthalenecarboxylic acid, 3-hydroxy-4-[(4-methyl-2-sulfophenyl)azo]-, barium salt (1 : 1)	15850:2
61013-97-6	P. Red 151	Benzenesulfonic acid, 2-[[2-hydroxy-3-[[(4-sulfophenyl)amino]carbonyl]-1-naphthalenyl]azo]-, barium salt (1 : 1)	15892

Table 5.5 lists important regulations that are related to organic pigments.

The European Commission has published the July 2013 version of ‘Addresses of European and National European Authorities’ related to ‘General Health and Consumers’ as well as a list of the National Governmental Authorities in Europe. These documents can be obtained from: http://ec.europa.eu/food/food/chemicalsafety/foodcontact/auth_ref_en.pdf

5.3 Ecology

Although pigments, because they are practically insoluble in water and – if at all – only sparingly soluble in common solvents, are largely biologically inert, it is the responsibility of the pigment manufacturer and producer to comply with legal requirements.

Ecological considerations include air emissions and wastewater.

Air emissions: Organic pigments are basically subject to a general limit to particulate emission: the concentration of fine dust in the air may not exceed 3 mg m⁻³ [24]. Although an organic pigment dust is not considered a health hazard, emission control includes filtering waste air after manufacture to remove the pigment dust. Suitable methods involve using dust filters or adsorption techniques. Generally, to avoid possible exposure to pigment dust, individuals involved in the manufacture of a pigment must wear additional protective equipment (dust mask).

Wastewater: The danger of contaminating free-running water with organic pigments may be met with measures such as filtration, sedimentation, adsorption or, if necessary, with biological treatment. By means of these techniques, wastewater pollution may be practically avoided. As a result of their negligible solubility, organic pigments are probably nontoxic to fish – at least there is no evidence to the contrary. Fish toxicity is conceivable only if the receiving water cannot offer a sufficiently high dilution factor and thus accumulates such quantities of pigment as to cause gill failure.

Although the bacteria used in biological treatment are not effective in degrading organic pigments, the compounds are likely to decompose slowly under anaerobic conditions.

Legal limitations placed upon the use of all newly launched non-biodegradable chemicals in Japan require testing each product for accumulation in fish before it can be marketed. These regulations have stimulated corresponding studies about the bioaccumulation of pigments [25]. The distribution coefficient P_ow between n-octanol and water may be used to indicate the tendency of a chemical to accumulate in biological systems [26].

An empirical rule, which also applies to dyes, predicts a bioaccumulation factor of <100 in fish, if the P_ow is below 1000. Notably, however, this rule does not apply to organic pigments, since they are only very sparingly soluble in water and in lipids (for instance in the lipid simulant solvent n-octanol) and consist of comparatively large molecules. Although the theoretical log P_ow is very high for pigments (up to 10), the compounds do not accumulate in fish [27].

Persistent organic pollutants (POPs) are characterized by their toxicity, their resistance to degradation and their capacity to accumulate in living organisms and be transported over long distances; their restriction and elimination are the subject of two international legal instruments: the Stockholm Convention 2 [28] and the POPs Protocol of the Geneva Convention (4^th Meeting, May 2009), whose obligations are implemented in the EU through a specific European regulation(Commission Regulation (EC) No 465/2008).

Since the properties of most organic pigments make the possibility of their bioaccumulation very unlikely, these pigments should therefore not classified as POPs, nor as persistent, bioaccumulative and toxic (PBT) substances [29].

5.4 Toxicology

Toxicological studies are concerned with various aspects, primarily with the following factors:

• - acute toxicity,
• - irritation of skin and mucous membrane,
• - toxicity after repeated application,
• - sensitization,
• - mutagenicity,
• - chronic toxicity, especially carcinogenicity.

References for Chapter 5

1. 1 Cowley, A.C.D. (August 1985) Polym. Paint Colour J., 7–21.
2. 2 Hunger, K. (1993) Am. Ink Maker, 71 (II), 22–31, 75–76.
3. 3 US Department of Labour (2010) A Guide to The Globally Harmonized System of Classification and Labelling of Chemicals (GHS). Available at http://www.osha.gov/dsg/hazcom/ghs.html (accessed on 6 November 2014).
4. 4 European Agency for Safety and Health at Work (2006) Regulation (EC) No 1907/2006 (amended and Annexes till 2015).
5. 5 (December 2013) Lebensmittel-und Futtermittelgesetzbuch (last update 13th Dec 2014).
6. 6 Federal Institute for Risk Assessment Empfehlung (Recommendation) BfR IX (2015) and BfR XLVII (2003), (Germany).
7. 7 Colour Pigments Manufacturers Association (1993) Safe Handling of Colour Pigments, 1st edn, CPMA, Alexandria, Virginia.
8. 8 ETAD/BCMA/VdMI/EPSOM (eds) (1995) Safe Handling of Pigments, European Edition, in English, French, German and Spanish language, ETAD/BCMA/VdMI/EPSOM.
9. 9 Eurocolor, ETAD, VdMI (2002) Colourants for Food Contact Plastics: Aspects of Product Safety, Eurocolor, ETAD, VdMI.
10. 10 Council of Europe (1989) Council of Europe Resolution AP (89)1 on the use of colourants in plastic materials coming into contact with food, September 19.
11. 11 Clariant (2004) Colourants for the colouration of consumer goods, food packaging and toys.
12. 12 ETAD (September 1986) ETAD Analytical Method No. 212 (ETAD, ref. footnote p. 590); DIN 55610.
13. 13 ETAD/VdMi (2002) Colourants for Food Contact Plastics, ETAD/VdMi.
14. 14 National Association of Printing Ink Manufacturers, Trace Metals in Organic Pigments, Am. Ink Maker (1973) (DCMA Annual Meeting, White Sulphur Springs W. Va., June 18–20, 1973); (1973) Am. Ink Maker 51 (10), 31–35.
15. 15 European Parliament (2009) Directive 2009/48/EC of the European Parliament and of the Council, on the safety of toys, last amended by the Amendment Reg. 681/2013).
16. 16 European Committee for Standardization (CEN) (2013) European Standard EN 71-3 Migration of certain elements.
17. 17 German Federal Ministry of Labour (März 2001) TRGS 614 (Technische Regeln für Gefahrstoffe).
18. 18 BfR (2009) Amtliche Sammlung von Untersuchungsverfahren nach § 64 German Food and Feed Code (LFGB).
19. 19 EU 1907 (2006) Annex XVII: Restriction on the manufacture, placing on the market and use of certain dangerous substances, preparation and articles – Appendix 8 Entry - Azocolourants.
20. 20 US FDA (Revised as of 1 April 2014) Code of Federal Regulations Title 21: 21CFR 109.30 Tolerances for polychlorinated biphenyls (PCB's); US FDA (Revised as of 1 April 2014) Code of Federal Regulations 21CFR 509.30 Subpart B – Tolerances for unavoidable poisonous or deleterious substances.
21. 21 Federal Republic of Germany (2012) Annex to § 1 of the Chemicals Prohibition Regulation (Chemikalienverbots-Verordnung Germany Draft Notification 2016/28/D of 18.01.2016.
22. 22 German Federal Institute for Occupational Safety and Health (2012) Chemikalienverbotsverordnung, last amended 20 Anhang zu § 1, Abschnitt 4 (German Hazardous Substances Ordinance).
23. 23 EC (2008) Regulation (EC) 1272/2008, Annex 1: 056-002-00-7: barium salts, with the exception of barium sulphate, salts of 1-azo-2-hydroxynaphthalenyl aryl sulphonic acid, and of salts specified elsewhere in this Annex.
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