From pigments to coloured napkins: comparative analyses of primary aromatic amines in cold water extracts of printed tissues by LC-HRMS and LC-MS/MS

Figures & data

Table 1. Overview of the pigment colour indexes used

Pigment			Primary aromatic amine(s) – possible release
Colour Index (C.I.) Number	CAS Number	Structure	CAS Number	Name
Pigment Red 122	980–26-7		106–49-0	p-toluidine
Pigment Red 184	99402–80-9		62–53-3 95–79-4 120–35-4 2840–26-8 6358–64-1	aniline 5-chloro-o-toluidine 3-amino-4-methoxybenzanilide 3-amino-4-methoxybenzoic acid 4-chloro-2,5-dimethoxyaniline
Pigment Orange 13	3520–72-7		62–53-3 91–94-1	aniline 3,3ʹ-dichlorobenzidine
Pigment Yellow 74	6358–31–2		90–04-0 97–52-9	o-anisidine p-nitro-o-anisidine
Pigment Yellow 111	15993–42-7		95–03-4 97–52-9	5-chloro-2-methoxyaniline p-nitro-o-anisidine
Pigment Yellow 138	30125–47-4		18978–78-4	8-amino-2-methylquinoline
Pigment Yellow 155	68516–73-4		106–50-3 5372–81-6 10312–55-7 60728–41-8 85743–02-8	p-phenylenediamine dimethyl aminoterephthalate 2-amino-terephthalic acid 1-methyl-2-aminoterephthalate 2-amino-4-(MeO-carbonyl)benzoic acid

Notes:

Substructures in bold are primary aromatic amines

Table 2. Overview of the PAA analysed

PAA	CAS Number	Structure	Limit^1 µg kg^−1	Carc.^2 Class	C.I.^3 Link	PAA	CAS Number	Structure	Limit^1 µg kg^−1	Carc.^2 Class	C.I.^3 Link
p-amino-azobenzene	60–09-3		2	1B		4,4ʹ-oxy-dianiline	101–80-4		2	1B
aniline	62–53-3		10	2	all pigment	4-chloroaniline	106–47-8		2	1B
3-chloro-o-toluidine	87–60-5		10	–		p-toluidine	106–49-0		10	2	PR122
o-anisidine	90–04-0		2	1B	PY74	p-phenylene-diamine	106–50-3		10	–	PY155
2-amino-biphenyl	90–41-5		10	2		m-toluidine	108–44-1		10	–
2-naphthyl-amine	91–59-8		2	1A		3,3ʹ-dimethoxy-benzidine	119–90-4		2	1B
3,3ʹ-dichloro-benzidine	91–94-1		2	1B		3,3ʹ-dimethyl-benzidine	119–93–7		2	1B
4-amino-biphenyl	92–67-1		2	1A		3-amino-4-methoxy-benzanilide	120–35-4		10	–	PR184
benzidine	92–87-5		2	1A		p-cresidine	120–71-8		2	1B
5-chloro-2-methoxyaniline	95–03-4		10	–	PY111	2,4,5-trimethyl-aniline	137–17-7		2	1B
o-toluidine	95–53-4		2	1B		4,4ʹ-thiodianiline	139–65-1		2	1B
2,4-dimethyl-aniline	95–68-1		10	–		3,3ʹ-(Me)2–4,4ʹ-diamino-di-phenylmethane	838–88-0		2	1B
4-chloro-o-toluidine	95–69-2		2	1B		3-amino-4-methoxy-benzoic acid	2840–26-8		10	–	PR184
5-chloro-o-toluidine	95–79-4		10	–	PR184	dimethyl amino-terephthalate	5372–81-6		10	–	PY155
2,4-diamino-toluene	95–80–7		2	1B		4-chloro-2,5-dimethoxy-aniline	6358–64-1		10	–	PR184
p-nitro-o-anisidine	97–52-9		10	–	PY74 PY111	2-amino-terephthalic acid	10312–55-7		10	–	PY155
o-amino-azotoluene	97–56-3		2	1B		8-amino-2-methylquinoline	18978–78-4		10	–	PY138
2-amino-4-nitrotoluene	99–55-8		10	2		1-methyl-2-amino-terephthalate	60728–41-8		10	–	PY155
4,4ʹ-methylene-bis(2-chloro-aniline)	101–14-4		2	1B		2-amino-4-(MeO-carbonyl)-benzoic acid	85743–02-8		10	–	PY155
4,4ʹ-diamino-diphenyl-methane	101–77-9		2	1B

Notes:

¹Limit: maximum amount in the foodstuff or food simulant according to BfR recommendation XXXVI by transfer from the food contact material

²Carc.Class: carcinogenicity classification according to European Regulation (EC) No 1272/2008, Part 3, Table 3.

³ C.I. Link: corresponding pigment Colour Index.

Table 3. Analytical parameters – part Ferro Be (LC-MS/MS)

									Regression
PAA	CAS Number	Mode	Ion	Adduct m/z	fragment m/z	CV V	CE V	Ret.time Min	r|r²	coeff.	curvature a	slope b (x10^3)	LOD µg L^−1	LOQ µg L^−1
aniline	62–53-3	ES+	[M + H]^+	94.0	77.0	25	15	2.19	r²	0.9999	−114 ± 8	71.2 ± 0.1	0.06	0.21
o-anisidine	90–04-0	ES+	[M + H]^+	124	92	30	15	4.31	r²	0.9998	−697 ± 77	183 ± 6	0.03	0.11
				124	109	30	14
3,3ʹ-dichlorobenzidine	91–94-1	ES+	[M + H]^+	253	182	60	27	11.2	r²	0.9999	−100 ± 21	24.1 ± 0.2	0.09	0.30
				253	217	60	18
5-chloro-2-methoxyaniline	95–03-4	ES+	[M + H]^+	157.9	80	20	30	9.21	r²	0.9999	−356 ± 88	196 ± 12	0.01	0.05
5-chloro-o-toluidine	95–79-4	ES+	[M + H]^+	142	107	40	13	9.78	r²	0.9999	−73 ± 10	42.4 ± 0.8	0.04	0.14
				142	125	40	20
p-nitro-o-anisidine	97–52-9	ES+	[M + H]^+	169	122	35	18	8.03	r²	0.9997	−442 ± 25	139 ± 2.9	0.16	0.54
				169	152	35	12
p-toluidine	106–49-0	ES+	[M + H]^+	108	91	20	15	4.20	r²	0.9998	−244 ± 21	73.0 ± 0.4	0.09	0.29
				108	93	20	15
3-amino-4-methoxybenzanilide	120–35-4	ES+	[M + H]^+	243	124	40	15	8.72	r²	0.9995	−1223 ± 24	257 ± 5	0.03	0.12
				243	150	40	20
3-amino-4-methoxybenzoic acid	2840–26-8	ES+	[M + H]^+	168	136	25	23	5.60	r²	0.9999	−305 ± 9	107 ± 2	0.01	0.03
				168	153	25	15
dimethyl aminoterephthalate	5372–81-6	ES+	[M + H]^+	210	135	25	25	10.35	r²	1.0000	−1628	545	0.05	0.16
				210	178	25	8
4-chloro-2,5-dimethoxyaniline	6358–64-1	ES+	[M + H]^+	188	130	20	30	8.81	r²	0.9983	−409 ± 24	78.7 ± 1.5	0.10	0.31
				188	173	20	15
2-amino-terephthalic acid	10312–55-7	ES-	[M – H]^−	180	92	30	16	5.50	r	0.9997	–	287	0.31	1.04
				180	136	30	10
8-amino-2-methylquinoline	18978–78-4	ES+	[M + H]^+	159.1	91	35	26	6.48	r²	0.9999	−137	34.9	0.02	0.07
				159.1	115	25	30
1-methyl-2-aminoterephthalate	60728–41-8	ES+	[M + H]^+	196	108	12	25	8.90	r	0.9999	–	46.5	0.08	0.26
				196	164	12	10
2-amino-4-(MeO-carbonyl)-	85743–02-8	ES+	[M + H]^+	196	135	12	9	8.61	r	0.9999	–	113	0.01	0.04
benzoic acid				196	178	12	23

Notes:

CV: Cone Voltage

CE: Collision Energy

Coeff: Correlation coefficient r or coefficient of determination r² of the corresponding linear or negative quadratic regression curve

Regression curve: according to formula y = a.x2 + b.x + c with x the concentration in µg L⁻¹ and y the peak area of the quantifier.

Transitions in bold were used for quantification.

Table 4. Formulation overview of the pigment base and extender used for the preparation of the inks

Ingredient (by weight)	Pigment Base	Extender
Pigment	35–45%	-
Filler	-	10–20%
Water	20–30%	20–30%
Dispersant	10–25%	-
Styrene acrylic resin	5–10%	30–40%
Other resin	-	15–25%
Humectant	0-7%	3-7%
Additives	0–2%	0.5–1%
Wax	-	2–5%
pH corrector	0–0.5%	1-2%

Table 5. Analytical parameters – part Siegwerk Fr (LC-HRMS)

PAA	CAS Number	Mode	Ion	Adduct m/z	Δm/z at 2 µg L^−1 ppm	Ret.Time min	Correl. Coeff. r	LOD µg L^−1	LOQ µg L^−1
p-aminoazobenzene	60–09-3	ES+	[M + H]^+	198.10257	−1.09	7.15	0.9996	0.1	0.33
aniline	62–53-3	ES+	[M + H]^+	94.06513	5.94	1.15	0.9997	0.5	1.65
3-chloro-o-toluidine	87–60-5	ES+	[M + H]^+	142.0418	−0.28	5.73	0.9990	0.1	0.33
o-anisidine	90–04-0	ES+	[M + H]^+	124.07569	1.08	2.06	0.9992	0.1	0.33
2-aminobiphenyl	90–41-5	ES+	[M + H]^+	170.09643	−0.91	6.41	0.9993	0.1	0.33
2-naphthylamine	91–59-8	ES+	[M + H]^+	144.08078	−0.67	4.52	0.9994	0.1	0.33
3,3ʹ-dichlorobenzidine	91–94-1	ES+	[M + H]^+	253.02938	−1.36	7.05	0.9996	0.2	0.66
4-aminobiphenyl	92–67-1	ES+	[M + H]^+	170.09643	−1.18	5.43	0.9996	0.1	0.33
benzidine	92–87-5	ES+	[M + H]^+	185.10732	−0.69	1.17	0.9993	0.2	0.66
5-chloro-2-methoxyaniline	95–03-4	ES+	[M + H]^+	158.03672	−0.64	5.64	0.9995	0.1	0.33
o-toluidine	95–53-4	ES+	[M + H]^+	108.08078	3.41	2.41	0.9982	0.2	0.66
2,4-dimethylaniline	95–68-1	ES+	[M + H]^+	122.09643	1.35	3.71	0.9992	0.1	0.33
4-chloro-o-toluidine	95–69-2	ES+	[M + H]^+	142.0418	−0.31	5.20	0.9996	0.1	0.33
5-chloro-o-toluidine	95–79-4	ES+	[M + H]^+	142.0418	−0.35	6.02	0.9996	0.2	0.66
2,4-diaminotoluene	95–80-7	ES+	[M + H]^+	123.09167	1.17	1.03	0.9993	0.1	0.33
p-nitro-o-anisidine	97–52-9	ES+	[M + H]^+	169.06077	−1.14	5.62	0.9995	0.2	0.66
o-aminoazotoluene	97–56-3	ES+	[M + H]^+	226.13387	−1.25	8.03	0.9994	0.1	0.33
2-amino-4-nitrotoluene	99–55-8	ES+	[M + H]^+	153.06585	−0.75	5.85	0.9995	0.1	0.33
4,4ʹ-methylenebis(2-chloroaniline)	101–14-4	ES+	[M + H]^+	267.04503	−1.38	7.19	0.9997	0.2	0.66
4,4ʹ-diaminodiphenylmethane	101–77-9	ES+	[M + H]^+	199.12298	−0.90	1.94	0.9993	0.2	0.66
4,4ʹ-oxydianiline	101–80-4	ES+	[M + H]^+	201.10224	−1.16	1.22	0.9993	0.1	0.33
4-chloroaniline	106–47-8	ES+	[M + H]^+	128.02615	0.60	3.76	0.9996	0.2	0.66
p-toluidine	106–49-0	ES+	[M + H]^+	108.08078	3.49	2.61	0.9998	0.2	0.66
p-phenylenediamine	106–50-3	ES+	[M + H]^+	109.07602	3.07	0.60	0.9998	0.5	1.65
m-toluidine	108–44-1	ES+	[M + H]^+	108.08078	3.42	2.75	0.9984	0.2	0.66
3,3ʹ-dimethoxybenzidine	119–90-4	ES+	[M + H]^+	245.12845	−0.28	3.56	0.9980	0.2	0.66
3,3ʹ-dimethylbenzidine	119–93-7	ES+	[M + H]^+	213.13863	−1.25	3.56	0.9993	0.2	0.66
3-amino-4-methoxybenzanilide	120–35-4	ES+	[M + H]^+	243.1128	−1.02	5.13	0.9977	0.1	0.33
p-cresidine	120–71-8	ES+	[M + H]^+	138.09134	−0.32	3.63	0.9994	0.1	0.33
2,4,5-trimethylaniline	137–17-7	ES+	[M + H]^+	136.11208	−0.20	4.28	0.9987	0.1	0.33
4,4ʹ-thiodianiline	139–65-1	ES+	[M + H]^+	217.0794	−0.96	4.41	0.9996	0.1	0.33
3,3ʹ-(Me)2–4,4ʹ-diaminodiphenylmethane	838–88-0	ES+	[M + H]^+	227.15428	−1.38	3.67	0.9996	0.2	0.66
dimethyl aminoterephthalate	5372–81-6	ES+	[M + H]^+	210.07608	n.a.	6.40	0.9990	0.1	0.33
4-chloro-2,5-dimethoxyaniline	6358–64-1	ES+	[M + H]^+	188.04728	−1.07	5.33	0.9996	0.1	0.33
8-amino-2-methylquinoline	18978–78-4	ES+	[M + H]^+	159.09167	n.a.	4.07	0.9990	0.5	1.65

Table 6. Within sample repeatability and intra-lab reproducibility – Ferro BE

PAA	CAS Number	Repeatability rsd.avg^1 per duplicate	Reproducibility Sample count	(Σrsd²)^1/2 all combined
aniline	62–53-3	3.00%	5	7.53%
o-anisidine	90–04-0	2.71%	< 3	*
3,3ʹ-dichlorobenzidine	91–94-1	*	*	*
5-chloro-2-methoxyaniline	95–03-4	1.21%	< 3	*
5-chloro-o-toluidine	95–79-4	1.86%	4	4.05%
p-nitro-o-anisidine	97–52-9	3.14%	< 3	*
p-toluidine	106–49-0	1.88%	< 3	*
3-amino-4-methoxybenzanilide	120–35-4	2.57%	4	7.53%
3-amino-4-methoxybenzoic acid	2840–26-8	<0.01%	< 3	*
dimethyl aminoterephthalate	5372–81-6	*	*	*
4-chloro-2,5-dimethoxyaniline	6358–64-1	4.77%	4	11.35%
2-amino-terephthalic acid	10312–55-7	*	*	*
8-amino-2-methylquinoline	18978–78-4	*	*	*
1-methyl-2-aminoterephthalate	60728–41-8	*	*	*
2-amino-4-(MeO-carbonyl)-benzoic acid	85743–02-8	*	*	*

Notes:

¹Rsd.avg: average relative standard deviation per duplicate analysis (two printed tissues per sample, 2 injections per tissue)

*: not calculated because of lack of data

Figure 1. Ferro Be - Recovery after standard addition by spiking at 5 and 10 µg L^-1_.

Figure 2. Siegwerk Fr - Recovery after standard addition by spiking at 2 and 5 µg L⁻¹_.

Table 7. Overview PAA analyses from the CWE at Siegwerk and Ferro and Pigments analyses for the Pigments Red

Colour Index Pigment Supplier(-grade-batch-ink)	CAS Number	Link with Colour index	PR122 A	PR122 B	PR184 A-1-1-1	PR184 A-1-2-1	PR184 A-1-2-2	PR184 A-2-1-1
CWE Ferro BE (LC-MS/MS)			Results in µg L^−1 according to EN 645
Number of CWE			2	2	2	2	–	2
aniline	62–53-3	all pigments	0.61	6.61	1.12	0.79	*	0.64
o-anisidine	90–04-0	PY74	*	*	<LOQ	*	*	*
3,3ʹ-dichlorobenzidine	91–94-1	PO13	<LOQ	<LOQ	<LOQ	*	*	*
5-chloro-2-methoxyaniline	95–03-4	PY111	*	*	*	<LOD	*	<LOD
5-chloro-o-toluidine	95–79-4	PR184	*	*	3.60	4.48	*	5.18
p-nitro-o-anisidine	97–52-9	PY74 PY111	*	*	<LOQ	<LOQ	*	<LOQ
p-toluidine	106–49-0	PR122	5.05	6.45	*	*	*	*
3-amino-4-methoxybenzanilide	120–35-4	PR184	*	*	9.03	7.00	*	2.50
3-amino-4-methoxybenzoic acid	2840–26-8	PR184	*	*	0.12	0.12	*	0.18
4-chloro-2,5-dimethoxyaniline	6358–64-1	PR184	*	*	2.71	2.84	*	1.23
Sum of PAA			5.66	13.05	16.58	15.21	*	9.72
CWE Siegwerk Fr (LC-HRMS)	CAS	Link C.I.	Results in µg L^−1 according to EN 645
Number of CWE			2	2	2	2	2	2
p-aminoazobenzene	60–09-3		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
aniline	62–53-3	all pigments	<LOQ	5.64	<LOQ	<LOQ	<LOQ	<LOQ
3-chloro-o-toluidine	87–60-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-anisidine	90–04-0	PY74	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-aminobiphenyl	90–41-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-naphthylamine	91–59-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dichlorobenzidine	91–94-1	PO13	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-aminobiphenyl	92–67-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
benzidine	92–87-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
5-chloro-2-methoxyaniline	95–03-4	PY111	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-toluidine	95–53-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4-dimethylaniline	95–68-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloro-o-toluidine	95–69-2		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
5-chloro-o-toluidine	95–79-4	PR184	<LOQ	<LOQ	3.60	1.32	2.36	3.04
2,4-diaminotoluene	95–80-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	0.40
p-nitro-o-anisidine	97–52-9	PY74 PY111	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-aminoazotoluene	97–56-3		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-amino-4-nitrotoluene	99–55-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-methylenebis(2-chloroaniline)	101–14-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-diaminodiphenylmethane	101–77-9		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-oxydianiline	101–80-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloroaniline	106–47-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
p-toluidine	106–49-0	PR122	6.53	8.77	<LOQ	<LOQ	<LOQ	<LOQ
p-phenylenediamine	106–50-3	PY155	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
m-toluidine	108–44-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dimethoxybenzidine	119–90-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dimethylbenzidine	119–93-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3-amino-4-methoxybenzanilide	120–35-4	PR184	<LOQ	<LOQ	3.71	<LOQ	0.48	<LOQ
p-cresidine	120–71-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4,5-trimethylaniline	137–17-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-thiodianiline	139–65-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-(Me)2–4,4ʹ-diaminodiphenylmethane	838–88-0		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloro-2,5-dimethoxyaniline	6358–64-1	PR184	<LOQ	<LOQ	2.80	1.38	2.13	1.34
Sum of PAA			6.53	14.41	10.11	2.70	4.97	4.78
Pigment impurity profile			Results in mg kg^−1 pigment according to AP (89) 1
aniline	62–53-3	all pigments	2.5	4.7	2.1
5-chloro-o-toluidine	95–79-4	PR184			8.5	7.2	7.2	6.5
p-toluidine	106–49-0	PR122	31.0	27.7
3-amino-4-methoxybenzanilide	120–35-4	PR184			29.7	41.6	41.6	20.9
3-amino-4-methoxybenzoic acid	2840–26-8	PR184			<LOQ	<LOQ	<LOQ	<LOQ
4-chloro-2,5-dimethoxyaniline	6358–64-1	PR184			4.5	7.18	7.2	1.3
Sum of PAA			33.5	32.4	44.8	56.0	56.0	28.7

Notes:

* Not measured

¹Pigment supplier: A = supplier 1, B = Supplier 2, … | grade: grade type x from supplier | Batch: batch number from grade x | ink: ink number prepared with pigment batch number x

Table 8. Overview PAA analyses from the CWE at Siegwerk and Ferro and Pigments analyses for the Pigments Yellow

Colour index (C.I.) Pigment Supplier	CAS Number	Link with Colour index	PY74 A	PY74 B	PY74 C	PY111 A	PY138 A	PY155 A	PY155 B
CWE Ferro BE (LC-MS/MS)			Results in µg L^−1 according to EN 645
Number of CWE			-	2	2	2	1	1	1
aniline	62–53-3	all pigments	*	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-anisidine	90–04-0	PY74	*	7.33	9.00	*	<LOQ	<LOQ	<LOQ
5-chloro-2-methoxyaniline	95–03-4	PY111	*	*	*	7.14	*	*	*
5-chloro-o-toluidine	95–79-4	PR184	*	<LOQ	*	<LOQ	*	*	*
p-nitro-o-anisidine	97–52-9	PY74 PY111	*	2.02	6.70	0.57	<LOQ	<LOQ	<LOQ
3-amino-4-methoxybenzanilide	120–35-4	PR184	*	<LOQ	*	<LOQ	*	*	*
3-amino-4-methoxybenzoic acid	2840–26-8	PR184	*	<LOQ	*	<LOQ	*	*	*
dimethyl aminoterephthalate	5372–81-6	PY155	*	*	*	*	<LOQ	0.40	10.30
4-chloro-2,5-dimethoxyaniline	6358–64-1	PR184	*	<LOQ	*	<LOQ	*	*	*
2-amino-terephthalic acid	10312–55-7	PY155	*	*	*	*	<LOQ	<LOQ	5.05
8-amino-2-methylquinoline	18978–78-4	PY138	*	*	*	*	2.92	<LOQ	<LOQ
1-methyl-2-aminoterephthalate	60728–41-8	PY155	*	*	*	*	<LOQ	<LOQ	2.97
2-amino-4-(MeO-carbonyl)benzoic acid	85743–02-8	PY155	*	*	*	*	*	0.88	1.48
Sum of PAA			*	9.35	15.70	7.71	2.92	1.28	19.8
CWE Siegwerk Fr (LC-HRMS)			Results in µg L^−1 according to EN 645
Number of CWE			2	2	2	2	2	2	2
p-aminoazobenzene	60–09-3		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
aniline	62–53-3	all pigments	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3-chloro-o-toluidine	87–60-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-anisidine	90–04-0	PY74	78.0	14.24	12.70	<LOQ	<LOQ	<LOQ	<LOQ
2-aminobiphenyl	90–41-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-naphthylamine	91–59-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dichlorobenzidine	91–94-1	PO13	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-aminobiphenyl	92–67-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
benzidine	92–87-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
5-chloro-2-methoxyaniline	95–03-4	PY111	<LOQ	<LOQ	<LOQ	6.09	<LOQ	<LOQ	<LOQ
o-toluidine	95–53-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4-dimethylaniline	95–68-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloro-o-toluidine	95–69-2		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
5-chloro-o-toluidine	95–79-4	PR184	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4-diaminotoluene	95–80-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
p-nitro-o-anisidine	97–52-9	PY74 PY111	55.00	1.28	2.90	<LOQ	<LOQ	<LOQ	<LOQ
o-aminoazotoluene	97–56-3		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-amino-4-nitrotoluene	99–55-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-methylenebis(2-chloroaniline)	101–14-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-diaminodiphenylmethane	101–77-9		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-oxydianiline	101–80-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloroaniline	106–47-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
p-toluidine	106–49-0	PR122	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
p-phenylenediamine	106–50-3	PY155	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
m-toluidine	108–44-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dimethoxybenzidine	119–90-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dimethylbenzidine	119–93-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3-amino-4-methoxybenzanilide	120–35-4	PR184	*	*	*	<LOQ	<LOQ	<LOQ	<LOQ
p-cresidine	120–71-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4,5-trimethylaniline	137–17-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-thiodianiline	139–65-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-(Me)2–4,4ʹ-diaminodiphenylmethane	838–88-0		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
dimethyl aminoterephthalate	5372–81-6	PY155	*	*	*	*	*	<LOQ	2.94
4-chloro-2,5-dimethoxyaniline	6358–64-1	PR184	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
8-amino-2-methylquinoline	18978–78-4	PY138	*	*	*	*	<LOQ	*	*
Sum of PAA			133.0	15.52	15.60	6.09	<LOQ	<LOQ	2.94
Pigment purity profile			Results in mg kg^−1 pigment according to AP (89) 1
o-anisidine	90–04-0	PY74	193		13.7
5-chloro-2-methoxyaniline	95–03-4	PY111				18.74
p-nitro-o-anisidine	97–52-9	PY74 PY111	125		16.5	0.20
dimethyl aminoterephthalate	5372–81-6	PY155						1.21
2-amino-terephthalic acid	10312–55-7	PY155						<LOQ
8-amino-2-methylquinoline	18978–78-4	PY138					41.40
1-methyl-2-aminoterephthalate	60728–41-8	PY155						0.24
Sum of PAA			318		30.2	18.94	41.40	1.45

Table 9. Overview PAA analyses from the CWE at Siegwerk and Ferro and Pigments analyses for Pigment Orange and extenders

Colour Index Pigment Supplier-grade-batch-ink	CAS Number	Link with Colour index	PO13 A-1-1-1	PO13 A-1-2-1	PO13 A-1-3-1	Extender-T –	Extender –
CWE Ferro BE			Results in µg L^−1 according to EN 645
Number of CWE			1	1	1	2	2
aniline	62–53-3	all pigments	4.95	13.40	11.80	<LOQ	0.53
o-anisidine	90–04-0	PY74	*	*	*	0.57	0.71
3,3ʹ-dichlorobenzidine	91–94-1	PO13	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
5-chloro-o-toluidine	95–79-4	PR184	*	*	*	<LOQ	<LOQ
p-nitro-o-anisidine	97–52-9	PY74 PY111	*	*	*	<LOQ	<LOQ
p-toluidine	106–49-0	PR122	<LOQ	<LOQ	<LOQ	*	*
3-amino-4-methoxybenzanilide	120–35-4	PR184	*	*	*	<LOQ	<LOQ
3-amino-4-methoxybenzoic acid	2840–26-8	PR184	*	*	*	<LOQ	<LOQ
4-chloro-2,5-dimethoxyaniline	6358–64-1	PR184	*	*	*	<LOQ	<LOQ
Sum of PAA			4.95	13.4	11.8	0.57	1.24
CWE Siegwerk Fr			Results in µg L^−1 according to EN 645
Number of CWE			2	2	2	2	2
p-aminoazobenzene	60–09-3		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
aniline	62–53-3	all pigments	4.36	6.70	6.70	<LOQ	<LOQ
3-chloro-o-toluidine	87–60-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-anisidine	90–04-0	PY74	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-aminobiphenyl	90–41-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-naphthylamine	91–59-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dichlorobenzidine	91–94-1	PO13	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-aminobiphenyl	92–67-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
benzidine	92–87-5		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
5-chloro-2-methoxyaniline	95–03-4	PY111	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-toluidine	95–53-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4-dimethylaniline	95–68-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloro-o-toluidine	95–69-2		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
5-chloro-o-toluidine	95–79-4	PR184	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4-diaminotoluene	95–80-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
p-nitro-o-anisidine	97–52-9	PY74 PY111	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
o-aminoazotoluene	97–56-3		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2-amino-4-nitrotoluene	99–55-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-methylenebis(2-chloroaniline)	101–14-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-diaminodiphenylmethane	101–77-9		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-oxydianiline	101–80-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloroaniline	106–47-8		<LOQ	<LOQ	<LOQ	*	*
p-toluidine	106–49-0	PR122	<LOQ	<LOQ	<LOQ	*	*
p-phenylenediamine	106–50-3	PY155	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
m-toluidine	108–44-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dimethoxybenzidine	119–90-4		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-dimethylbenzidine	119–93-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3-amino-4-methoxybenzanilide	120–35-4	PR184	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
p-cresidine	120–71-8		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
2,4,5-trimethylaniline	137–17-7		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4,4ʹ-thiodianiline	139–65-1		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
3,3ʹ-(Me)2–4,4ʹ-diaminodiphenylmethane	838–88-0		<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
4-chloro-2,5-dimethoxyaniline	6358–64-1	PR184	<LOQ	<LOQ	<LOQ	*	*
Sum of PAA			4.36	6.70	6.70	<LOQ	<LOQ
Pigment purity profile			Results in mg kg-^1 pigment according to AP (89) 1
aniline	62–53-3	all pigments	1.2
3,3ʹ-dichlorobenzidine	91–94-1	PO13	<LOQ
p-toluidine	106–49-0	PR122	<LOQ