EU marker polycyclic aromatic hydrocarbons in food supplements: analytical approach and occurrence

Figures & data

Table 1. List of the analysed food supplements samples with basic information.

Sample code	Name	Country of purchase	Comments	Type of pills	Group*
1	Aloe vera	NL	Concentrated extract	Solid pills	1
2	Green tea extract	NL	Standardised extract	Solid pills	1
3	Siberian ginseng	NL	Extract	Solid pills	1
4	Ginger	NL	Standardised extract	Powder in gelatine	1
5	Green coffee	NL	Green coffee extract (Robusta)	Powder in gelatine	1
6	Cat’s claw	NL	Cat’s claw powder	Powder in gelatine	1
7	Super green tea	NL	Green tea extract, caffeine	Solid pills	1
8	Valerian	NL	Root extract	Powder in gelatine	1
9	St. John’s wort	NL	Standardised extract	Powder in gelatine	1
10	Kelp	NL	Standardised extract	Solid pills	1
11	Cha-de-burge	NL	Brazilian tree (Cordia salicifolia), foliage extract	Powder in gelatine	1
12	Pu-erh tea	NL	Dark Chinese tea extract	Powder in gelatine	1
13	Cod liver oil	NL	–	Oil in gelatine	2
14	Green tiger	NL	Green tea extract, choline, taurine	Powder	1
15	Fenugreek powder	NL	Tigonella foenum-graecum	Powder	1
16	Silybum marianum	NL	Milk thistle extract	Powder in gelatine	1
17	Ginkgo biloba	AT	Dried extract of ginkgo foliage	Solid pills	1
18	Ginseng	AT	Root extract	Solid pills	1
19	Pumpkin	AT	Seed extract	Solid pills	1
20	Green tea	AT	Extract	Powder in gelatine	1
21	Propolis	AT	Propolis from the beehive	Liquid	3
22	Honey bee booster	AT	Propolis extract, royal jelly, pollen	Liquid	3
23	Valerian	AT	Root extract	Powder in gelatine	1
24	Yam-root	AT	Root extract from Mexican Yam	Powder in gelatine	1
25	Day & Night	AT	Selected plant extracts for calorie controlled diet	Solid pills	1
26	Salmon oil	AT	Omega 3 concentrate	Oil in gelatine	2
27	Omega-3 – see Fish oil	AT	See fish oil 68.7%	Oil in gelatine	2
28	Dandelion juice	AT	Extract from dandelion leaves	Liquid	1
29	Maca powder	CZ	Root extract from Peruan Maca	Powder	1
30	Maqui berry Organic	CZ	Aristotelia chilensis – dried berry	Powder	1
31	Ginseng	CZ	Panax ginseng – dried root	Dried slice of root	1
32	Pangamin	CZ	Dried Saccharomyces cerevisiae and malt extract	solid pills	1
33	Omega 3 & Omega 6	CZ	Fish oil, evening primrose oil	Liquid	2
34	Omega 3	CZ	Fish oil, orange aroma	Oil in gelatine	2
35	Oyster mushroom	CZ	Pleurotus ostreatus extract	Solid pills	1
36	Apricarc	CZ	Powder and oil from apricot kernel	Powder in gelatine	1
37	Ginkgo biloba	CZ	Ginkgo extract, soybean oil	Semi-solid in gelatine	1
38	Cranberries	CZ	Extract from berries	Powder in gelatine	1
39	St. John’s wort	CZ	Powder from haulm	Solid pills	1
40	Bovine colostrum	CZ	Kolostrum forte 500 mg	Powder in gelatine	1
41	Skeletin	CZ	Cuttle fish bone powder, fish oil	Semi-solid in gelatine	1
42	Green tea	CZ	Green tea extract	Powder in gelatine	1
43	Chlorella organic	CZ	Chlorella vulgaris – freshwater algae	Solid pills	1
44	Spirulina organic	CZ	Spirulina – freshwater algae	Solid pills	1
45	Evening primrose & borage	CZ	Evening primrose oil + borage oil	Oil in gelatine	2
46	Sea buckthorn oil	CZ	Hippophae rhamnoides oil (100% oil)	Liquid	2
47	Evening primrose oil	CZ	100% oil	liquid	2
48	Linseed oil	CZ	100% oil	Liquid	2
49	Pangamin	CZ	Saccharomyces cerevisiae + algea Chlorella vulgaris + malt extract	Solid pills	1
50	Garlic super	CZ	Garlic oil, sunflower oil	Oil in gelatine	2
51	Vegemax	CZ	Freeze-dried vegetable	Solid pills	1
52	Silybum marianum	CZ	100% granule	Powder	1
53	Young barley BIO	CZ	Powder from dried sprout of barley	Powder	1
54	Garlic	CZ	Garlic extract, soybean oil	Oil in gelatine	2
55	Yucca	CZ	Extract	Solid pills	1
56	Acai berry	CZ	Acai berry + green tea extract + Garcina cambogia	Powder in gelatine	1
57	Garcinia	CZ	Garcinia cambogia	Powder in gelatine	1
58	Ganoderma lucidum	CZ	Spore powder of fungi	Powder in gelatine	1
59	Birch	CZ	Birch leaves powder	Solid pills	1
60	Cat’s claw	CZ	Uncaria tomentosa dried inner bark	Solid pills	1
61	Propolis intense	FR	Tincture, propolis extract	Liquid	3
62	Fish oil	CZ	Mixture of 3 species – salmon, mackerel, sardines	Oil in gelatine	2
63	Echinacea forte	BE	Echinacea extract	Powder in gelatine	1
64	St. John’s wort	BE	Standardised extract	Powder in gelatine	1
65	Ginkgo complex	BE	Ginkgo extract, rice powder	Powder in gelatine	1
66	Garlic	BE	Garlic extract, mistletoe extract	Powder in gelatine	1
67	Omega 3	BE	Fish oil, rosemary extract	Oil in gelatine	2
68	Maca forte	BE	Maca extract, rice powder	Solid pills	1
69	Cranberry	BE	Extract	Solid pills	1
70	Ginseng forte + maca	BE	Extract of ginseng root and maca	Solid pills	1
71	Cat’s claw	BE	Cat’s claw, Echinacea, quarana powder	Solid pills	1
72	Shark’s oil	PL	Oil from shark’s liver + garlic	Oil in gelatine	2
73	Propolis mixture	IE	Honey powder, propolis extract	Liquid	3
74	Spirulina	IE	100% pure powder	Powder	1
75	Bioactive Spirulina	IE	100% pure powder	Powder	1
76	Premium Spirulina	IE	100% pure powder	Solid pills	1
77	Propolis herbal	IE	Honey, propolis extract, peppermint oil	Liquid	3
78	Propolis liquid	IE	Propolis extract	Liquid	3
79	Bioactive Spirulina	IE	–	powder	1
80	Spirulina	IE	Blue-green algae	Solid pills	1
81	Children’s propolis herbal	IE	Honey, propolis extract	Liquid	3
82	Propolis extract	IE	Purified propolis extract	Liquid	3
83	Evening primrose oil	IE	–	Oil in gelatine	2
84	Acidophilus	IE	Lactobacillus	Powder in gelatine	1
85	Spirulina	IE	100% pure powder	Powder	1
86	Propolis liquid	IE	Propolis extract	Liquid	3
87	Propolis liquid	IE	Propolis extract	Liquid	3
88	Premium Spirulina	IE	100% pure powder	Powder	1
89	Blood capsules	IE	Vitamins and minerals for better blood formation	Powder in gelatine	1
90	Dietary supplements – B1	IE	Peppermint, fennel, ginger, chamomile, ginseng, aniseed, oregano	Powder in gelatine	1
91	Dietary Supplements – C1	IE	Psyllium husk, buskthorn bark, sweet flag root, dandelion, chamomile, etc.	Powder in gelatine	1
92	Dietary supplements – L1	IE	Psyllium husk, dandelion, ginger root, ginseng, centaury herb	Powder in gelatine	1
93	Dietary supplements – Y1	IE	Burdock powder, myrrh gum, garlic, slippery elm powder, oregano powder, olive leaf	Powder in gelatine	1
94	Spirulina	IE	100% Hawaiian spirulina	Solid pills	1
95	Primrose oil	IN	Evening primrose oil	Oil in gelatine	2
96	Germ & cod liver oil	IN	Wheat germ oil, cod liver oil + vitamins/others	Semi-solid in gelatine	2
97	Multicomponent extract	IN	Ginseng, Ginkgo biloba, citrus bioflavonoids, green tea, garlic powder + vitamins/minerals	Semi-solid in gelatine	1
98	Green tea & garlic	IN	Green tea, garlic powder + vitamins/minerals	semi-solid in gelatine	1
99	Multicomponent extract	IN	Polypodium leucotomos, green tea, French marine pine bark, konjac powder + vitamins/minerals	Semi-solid in gelatine	1
100	Grape & green tea	IN	Grape seed, green tea + vitamins/minerals	Semi-solid in gelatine	1
101	Botanicals extract	IN	Gulancha, Anantamul, shetverenda, Sajina, Rakta Punarnava	Solid pills	1
102	Wheat germ plus	IN	Wheat germ oil, citrus bioflavonoids, green tea + vitamins/minerals	Semi-solid in gelatine	2
103	Grape seed plus	IN	Grape seed extract + vitamins/minerals	Solid pills	1
104	Ginseng	IN	Ginseng extract powder + vitamins/minerals	Semi-solid in gelatine	1
105	Ginseng	IN	Ginseng extract + vitamins and Zn	Powder in gelatine	1

Note: *1, botanical/herbal food supplement; 2, fish/edible oil supplement; 3, propolis extract/bee products.

Table 2. Relative standard uncertainties and relative expanded uncertainties for the whole method working range.

Analyte	Combined relative standard uncertainty (%)	Expanded relative uncertainty (%)
BaA	13.1	26.1
CHR	9.7	19.5
BbF	18.3	36.5
BaP	16.2	32.3

Figure 1. Example of quality control chart for benzo[a]pyrene measured in quality control sample (St. John’s Wort).

Table 3. Quantifier and qualifier ions of the four target PAHs with respective ratios and calculated relative permitted tolerance for the analyte identification.

	Quantifier ion Q1 m/z	Qualifier ion Q2 m/z	Qualifier ion Q3 m/z	Peak area ratio (Q2/Q1)	Peak area ratio – permitted tolerance	Peak area ratio (Q3/Q1)	Peak area ratio – permitted tolerance
BaA	228	226	114	28	24–32	10	5–15
CHR	228	226	114	29	25–33	9	4–14
BbF	252	250	126	23	19–26	10	5–15
BaP	252	250	126	20	16–24	15	12–18

Figure 2. Example of calibration for benzo[a]pyrene prepared from calibration standards and SRM® 2260a.

Figure 3. (colour online) Chromatographic separation of 4 target PAHs in food supplement of Ginkgo biloba with calculated chromatographic resolution (R_s) for critical pairs of PAHs (m/z 228 and m/z 252).

Table 4. Measured concentrations (μg/kg) of four EU marker PAHs in food supplements products and their sum (ƩPAH4) including the measurement uncertainties (μg/kg).

Code	Name	BaA	± U*	CHR	± U*	BbF	± U*	BaP	± U*	Ʃ4PAHs	± U*
1	Aloe vera	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
2	Green tea extract	1.2	0.3	1.8	0.4	1.0	0.4	1.2	0.4	5.2	0.7
3	Siberian ginseng	1.0	0.3	1.4	0.3	0.8	0.3	0.7	0.2	3.8	0.5
4	Ginger	n.d.	–	1.0	0.2	<0.5	–	n.d.	–	1.0	0.2
5	Green coffee	< 0.5	–	0.9	0.2	n.d.	–	n.d.	–	0.9	0.2
6	Cat’s claw	n.d.	–	<0.5	–	n.d.	–	n.d.	–	–	–
7	Super green tea	<0.5	–	0.7	0.1	<0.5	–	<0.5	–	0.7	0.1
8	Valerian	36.5	9.5	41.3	8.1	34.3	12.5	31.1	10.0	143.1	20.3
9	St. John’s wort	31.6	8.2	49.5	9.6	30.1	11.0	15.4	4.9	126.5	17.5
10	Kelp	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
11	Cha-de-burge	1.6	0.4	3.1	0.6	1.3	0.5	0.7	0.2	6.7	0.9
12	Pu-erh tea	15.6	4.1	18.4	3.6	9.0	3.3	7.6	2.4	50.7	6.8
13	Cod liver oil	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
14	Green tiger	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
15	Fenugreek powder	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
16	Silybum marianum	0.7	0.2	1.0	0.2	<0.5	–	<0.5	–	1.7	0.3
17	Ginkgo biloba	0.5	0.1	1.3	0.3	<0.5	–	<0.5	–	1.9	0.3
18	Ginseng	0.9	0.2	1.2	0.2	0.5	0.2	0.6	0.2	3.2	0.4
19	Pumpkin	n.d.	–	<0.5	–	n.d.	–	n.d.	–	–	–
20	Green tea	n.d.	–	<0.5	–	n.d.	–	n.d.	–	–	–
21	Propolis	8.31	2.2	12.4	2.4	8.1	2.9	6.4	2.0	35.1	4.8
22	Honey bee booster	1.8	0.5	3.9	0.8	1.6	0.6	1.0	0.3	8.3	1.1
23	Valerian	10.7	2.8	14.1	2.7	8.4	3.1	3.9	1.3	37.1	5.1
24	Yam-root	1.3	0.3	2.0	0.4	1.4	0.5	0.8	0.3	5.5	0.8
25	Day & Night	2.6	0.7	3.10	0.6	2.0	0.7	1.6	0.5	9.3	1.3
26	Salmon oil	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
27	Omega-3 – see Fish oil	0.6	0.1	0.9	0.2	<0.5	–	n.d.	–	1.4	0.2
28	Dandelion juice	n.d.	–	< 0.5	–	n.d.	–	n.d.	–	–	–
29	Maca powder	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
30	Maqui berry organic	2.7	0.7	3.6	0.7	1.0	0.4	0.9	0.3	8.1	1.1
31	Ginseng	1.0	0.3	1.5	0.3	<0.5	–	n.d.	–	2.5	0.4
32	Pangamin	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
33	Omega-3 & omega-6	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
34	Omega 3	0.9	0.2	1.4	0.3	0.7	0.3	0.6	0.2	3.6	0.5
35	Oyster mushroom	0.8	0.2	1.0	0.2	0.6	0.2	< 0.5	–	2.4	0.4
36	Apricarc	1.1	0.3	1.9	0.4	1.0	0.4	0.5	0.2	4.5	0.6
37	Ginkgo biloba	2.7	0.7	4.6	0.9	2.4	0.9	1.8	0.6	11.6	1.6
38	Cranberries	1.0	0.3	1.1	0.2	0.6	0.2	<0.5	–	2.7	0.4
39	St. John’s wort	<0.5	–	0.7	0.1	<0.5	–	n.d.	–	0.7	0.1
40	Bovine colostrum	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
41	Skeletin	1.3	0.3	1.9	0.4	1.1	0.4	0.6	0.2	4.9	0.7
42	Green tea	<0.5	–	1.4	0.3	<0.5	–	n.d.	–	1.4	0.3
43	Chlorella organic	0.9	0.2	2.5	0.5	1.7	0.6	0.7	0.2	5.8	0.9
44	Spirulina organic	6.8	1.8	17.1	3.3	14.7	5.4	5.6	1.8	44.2	6.8
45	Evening primrose & borage	n.d.	–	<0.5	–	n.d.	–	n.d.	–	–	–
46	Sea buckthorn oil	5.1	1.3	9.1	1.8	3.7	1.3	3.0	1.0	20.9	2.8
47	Evening primrose oil	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
48	Linseed oil	n.d.	–	<0.5	–	n.d.	–	n.d.	–	–	–
49	Pangamin	<0.5	–	0.5	0.1	<0.5	–	n.d.	–	0.5	0.1
50	Garlic super	0.7	0.2	0.8	0.2	<0.5	–	n.d.	–	1.5	0.2
51	Vegemax	<0.5	–	1.2	0.2	0.6	0.2	n.d.	–	1.8	0.3
52	Silybum marianum	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
53	Young barley BIO	6.9	1.8	11.4	2.2	9.9	3.6	4.1	1.3	32.2	4.8
54	Garlic	1.3	0.3	1.6	0.3	0.7	0.3	0.5	0.2	4.1	0.5
55	Yucca	n.d.	–	0.6	0.1	<0.5	–	n.d.	–	0.6	0.1
56	Acai berry	0.8	0.2	1.4	0.3	0.7	0.3	<0.5	–	3.0	0.4
57	Garcinia	1.6	0.4	2.8	0.5	1.6	0.6	1.0	0.3	6.9	0.9
58	Ganoderma lucidum	15.2	4.0	45.3	8.8	32.7	11.9	6.2	2.0	99.4	15.5
59	Birch	8.9	2.3	16.1	3.1	11.1	4.1	6.4	2.0	42.5	6.0
60	Cat’s claw	n.d.	–	<0.5	–	n.d.	–	n.d.	–	–	–
61	Propolis intense	214.0	55.6	239.8	46.8	115.8	42.3	87.3	27.9	656.9	88.6
62	Fish oil	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
63	Echinacea forte	5.6	1.4	13.5	2.6	4.8	1.8	3.0	0.9	26.9	3.6
64	St. John’s wort	3.4	0.9	9.0	1.8	3.9	1.4	1.5	0.5	17.8	2.5
65	Ginkgo complex	4.1	1.1	13.2	2.6	2.0	0.7	1.1	0.3	20.4	2.9
66	Garlic	0.6	0.2	1.0	0.2	1.0	0.4	< 0.5	–	2.7	0.5
67	Omega 3	n.d.	–	n.d.	–	n.d.	–	< 0.5	–	–	–
68	Maca forte	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
69	Cranberry	16.8	4.4	22.9	4.5	10.3	3.8	8.2	2.6	58.1	7.7
70	Ginseng forte + maca	2.7	0.7	3.7	0.7	2.6	0.9	1.4	0.4	10.4	1.4
71	Cat’s Claw	2.5	0.6	4.0	0.8	2.1	0.8	1.5	0.5	10.1	1.4
72	Shark’s oil	0.7	0.2	1.0	0.2	0.5	0.2	0.5	0.2	2.7	0.4
73	Propolis mixture	2.6	0.7	3.6	0.7	1.8	0.7	1.5	0.5	9.4	1.3
74	Spirulina	2.3	0.6	7.7	1.5	6.9	2.5	1.6	0.5	18.5	3.0
75	Bioactive Spirulina	n.d.	–	0.8	0.2	<0.5	–	n.d.	–	0.8	0.2
76	Premium Spirulina	1.4	0.4	4.1	0.8	4.4	1.6	1.2	0.4	11.2	1.9
77	Propolis herbal	2.3	0.6	2.6	0.5	1.3	0.5	1.5	0.5	7.7	1.0
78	Propolis liquid	157.7	41.0	280.1	54.6	187.4	68.4	84.3	27.0	709.4	100.3
79	Bioactive Spirulina	n.d.	–	<0.5	–	n.d.	–	n.d.	–	–	–
80	Spirulina	29.9	7.8	39.6	7.7	34.9	12.7	23.5	7.5	128.0	18.4
81	Children’s propolis herbal	<0.5	–	0.7	0.1	n.d.	–	n.d.	–	0.7	0.1
82	Propolis extract	79.6	20.7	91.6	17.9	46.1	16.8	48.1	15.4	265.5	35.6
83	Evening primrose oil	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
84	Acidophilus	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
85	Spirulina	19.8	5.2	36.6	7.1	23.3	8.5	16.8	5.4	96.5	13.4
86	Propolis liquid	22.9	5.9	37.0	7.2	17.9	6.5	13.6	4.4	91.4	12.2
87	Propolis liquid	25.6	6.6	37.6	7.3	19.1	7.0	15.3	4.9	97.6	13.1
88	Premium Spirulina	58.6	15.2	96.6	18.8	52.5	19.1	67.5	21.6	275.2	37.7
89	Blood capsules	1.7	0.4	2.8	0.6	3.0	1.1	0.6	0.2	8.1	1.3
90	Dietary supplements – B1	9.6	2.5	22.4	4.4	9.1	3.3	1.9	0.6	42.9	6.1
91	Dietary supplements – C1	3.4	0.9	5.7	1.1	3.2	1.2	2.2	0.7	14.4	2.0
92	Dietary supplements – L1	3.0	0.8	6.6	1.3	2.4	0.9	1.5	0.5	13.6	1.8
93	Dietary Supplements – Y1	4.1	1.1	8.6	1.7	4.4	1.6	2.7	0.9	19.8	2.7
94	Spirulina	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
95	Primrose oil	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
96	Germ & cod liver oil	1.0	0.3	2.0	0.4	4.6	1.7	7.8	2.5	15.4	3.0
97	Multicomponent extract	1.5	0.4	3.7	0.7	1.1	0.4	0.9	0.3	7.1	0.9
98	Green tea & garlic	n.d.	–	0.6	0.1	n.d.	–	n.d.	–	0.6	0.1
99	Multicomponent extract	<0.5	–	0.7	0.1	<0.5	–	<0.5	–	0.7	0.1
100	Grape & green tea	<0.5	–	0.7	0.1	<0.5	–	<0.5	–	0.7	0.1
101	Botanicals extract	0.7	0.2	1.7	0.3	0.6	0.2	<0.5	–	3.1	0.4
102	Wheat germ plus	<0.5	–	0.9	0.2	<0.5	–	0.6	0.2	1.6	0.3
103	Grape seed plus	n.d.	–	n.d.	–	n.d.	–	n.d.	–	–	–
104	Ginseng plus	<0.5	–	0.8	0.2	<0.5	–	<0.5	–	0.8	0.2
105	Ginseng plus	n.d.	–	0.6	0.1	n.d.	–	n.d.	–	0.6	0.1

Note: * Uncertainties are given as expanded (k = 2) uncertainties according to the ISO Guide to the Expression of Uncertainty (GUM), corresponding to an approximate 95% confidence interval; n.d., below LOD.

Table 5. Examples of daily intake levels of BaP and ΣPAH4 by the 10 most contaminated food supplements when assuming an intake of the maximum daily dose recommended by the manufacturers.

Code	Name	BaP (μg/kg)	Ʃ4PAHs (μg/kg)	Maximum dose (g/day)	Intake BaP (ng/day)	Intake ΣPAH4 (ng/day)
78	Propolis liquid	84.3	709.4	0.3	29	245
61	Propolis intense	87.3	656.9	2.3	197	1486
88	Premium Spirulina	67.5	275.2	9.0	608	2477
82	Propolis extract	48.1	265.5	1.0	47	258
8	Valerian	31.1	143.1	1.6	50	230
80	Spirulina	23.5	128.0	1.6	38	205
9	St. John’s wort	15.4	126.5	1.9	29	236
58	Ganoderma lucidum	6.2	99.4	2.0	13	203
87	Propolis liquid	15.3	97.6	0.3	5	34
85	Spirulina	16.8	96.5	2.0	34	193