Upload
others
View
5
Download
0
Embed Size (px)
Citation preview
Stefan Gafner, PhD
CSO, American Botanical Council
November 18, 2015
Oryx Hotel, Aqaba
BRAMA
Botanical Risk Assessment Training
Session VI
Introduction into adulteration
The American Botanical Council
•Non-profit educational organization
•Provides information on responsible and safe use of
medicinal herbs
•Members include consumers, healthcare
professionals, researchers, educators, industry
•Founded in 1988 with James A. Duke, Norman R.
Farnsworth and Mark Blumenthal as first Trustees of
ABC board
The ABC-AHP-NCNPR Botanical Adulterants
Program
•Program to educate herbal and dietary supplement industry
members about ingredient and product adulteration
• Initiated by three non-profit organizations:
• American Botanical Council (ABC)
• American Herbal Pharmacopoeia (AHP)
• National Center for Natural Products Research (NCNPR) at the
University of Mississippi
Adulteration
Adulteration is the action that results in accidental,
negligent, or intentional variations in identity, strength,
purity, and expected outcomes from a named or at least
implied identity of a herbal medicine, even if the standard
of identity was merely an organoleptic (sensory
observation) expectation
Adulteration of Botanical Ingredients
• Accidental: Substitution with/admixture of other
botanicals due to human error
• Economically-motivated: Substitution with/addition of
materials of substandard quality for financial gain
• Consequences: Adverse side effects, lack of efficacy, loss
of consumer confidence
Herbal DS Sales – Mainstream Multi-Outlet
Channel -- 2014
1. Horehound
2. Cranberry*
3. Echinacea
4. Black Cohosh*
5. Flaxseed and/or Oil
6. Valerian
7. Yohimbe**
8. Bioflavonoid Complex
9. Saw Palmetto*
10. Ginger***Subject to known spiking w/ Rx drugs
11. Aloe*
12. Milk Thistle*
13. Garlic
14. Cinnamon
15. Rhodiola*
16. Horny Goat Weed
17. Ginkgo*
18. Plant Sterols
19. Red Yeast Rice**
20. Elderberry*
Source: Symphony IRI & HerbalGram #107
*Subject to known or alleged/suspected adulteration
**Subject to known spiking w/ Rx drugs
Herbal DS Sales – Natural Channel -- 2014
1. Turmeric*2. Grass (wheat or barley)3. Flax seed and/or oil 4. Aloe*5. Spirulina6. Milk thistle*7. Elderberry*8. Maca*/**9. Echinacea*10. Oregano (oil & tincture)
Source: SPINS & HerbalGram #107
11. Saw Palmetto*12. Chia Seed and/or Oil13. Valerian 14. Garlic15. Echinacea-Goldenseal*16. Chlorophyll/Chlorella17. Cranberry*18. Ginkgo*19. Stevia20. Red Yeast Rice**
*Subject to known or suspected/alleged adulteration
**Subject to known spiking w/ Rx drugs
“Since the beginnings of civilization, once commerce develops, adulteration follows”
HerbalGram
Publications(As of September 2015)
Botanical Adulterant
Bulletins
• Arnica Flower
• Ashwagandha Root & Extract
• Bilberry Fruit Extract
• Black Cohosh Root & Rhizome
• Cranberry Fruit Extract
• Ginkgo Leaf Extract
• Ginseng, American & Asian Root & Extract
• Goldenseal Root & Rhizome
• Grapefruit Seed Extract
• Grape Seed Extract
• Maca Root
• Pomegranate Fruit & Extract
• Saw Palmetto
• Skullcap Herb
• Tea Tree Oil
• Vitex (Chaste Tree Berry)
Ginkgo biloba
Adulteration of Ginkgo biloba extracts
2003: Canada - 9 samples, 1 adulterated (11%)
2005: Canada - 14 samples, 4 likely adulterated (29%)
2006: China - 19 samples, 3 adulterated (16%)
2006: USA - 21 samples, 10 adulterated (48%)
2010: Germany - 10 samples, 7 likely adulterated (70%)
2011: USA - 8 samples, 3 adulterated (38%)
2012: Japan - 22 samples, 3 likely adulterated (14%)
2012: USA - 18 samples, 7 adulterated (39%)
2014: USA - 37 samples, no evidence of adulteration
2014: Australia - 8 samples, 3 adulterated (38%)
2015: UK – 30 samples, 12 adulterated (40%)
2015: USA - 25 samples, 11-19 adulterated (44-76%)
2015: Canada, in press - 14 samples, 11 adulterated (79%)
Ginkgo biloba Leaf Extract
Common Ginkgo Quality Concerns
• Commonly used adulterants of Ginkgo biloba:– Quercitin or kaempferol
– Rutin
– Flavone glycoside-rich extracts (e.g., Fagopyrum esculentum, Styphnolobiumjaponicum)
• These materials are relatively inexpensive & widely available.
• The addition of flavonoids enhance total flavonoid content of the extract.
• Adulterated products may go undetected, if
total flavone glycosides content is used as the
only QC criteria.
Asian Ginseng (Panax ginseng) Root Extract
Adulterated with Leaf Extract
• Companies are marketing Asian ginseng root extract
standardized to relatively high levels of ginsenosides at what
appear to be relatively low prices:
– 10-24%
• Analysis reveals:
– presence of chlorophyll in some samples
– uncharacteristic profiles of ginsenosides,
indicating presence of ginseng leaf extract
PomegranatePunica granatum, Punicaceae
http://blogs.knoxnews.com/knx/constantine/pomegranate.jpg
Pomegranate & Ellagic Acid
• Ellagic acid (EA) is an antioxidant compound
found in many fruits.
• Pomegranate extracts claim 40-70% EA.
• EA found in pomegranate: ca. 3%
– Up to 5% EA upon hydrolysis during extraction
• EA is inexpensive; made chemically and/or via
extraction from wood pulp.OH O O
O O
OH
OH
OH
Ellagic acid
Adulteration of Cranberry (Vaccinium macrocarpon)
Extract
• In the United States, cranberry is the third best-selling herb in the mass market and # 13 in natural channel with sales over $ 50 Mio*
• Beneficial effects for preventing urinary tract infection reportedly due to proanthocyanidins (PACs), in particular A-type
• Cranberries at 100 g fresh weight provide ca. 420 mg total flavan-3-ols, of which 56% (235 mg) are polymers**
• Other plants contain higher amounts of PACs and present cheaper sources
*Lindstrom A, Ooyen C, Lynch ME, Blumenthal M, Kawa K. HerbalGram. 2014;103:52-56.
** USDA database for proanthocyanidin content of selected foods. Beltsville (MD): Nutrient Data Laboratory, Agricultural Research Service, USDA 2004.
Adulteration of Cranberry (Vaccinium
macrocarpon) Extract
Mainly A-type PACs B-type PACs A-type and B-type PACs
Vaccinium macrocarpon Vitis vinifera Arachis hypogaea
Analysis of Commercial Cranberry Samples
• Fresh fruits (cranberries, blueberries, grapes, and raisins) and juices (cranberry, grape) purchased from markets1
• 10 commercial cranberry products obtained from manufacturer
• Samples analyzed by capillary zone electrophoresis and HPLC and subsequently clustered by statistical means (PCA)
• One cranberry extract aligned within grape cluster: absence of A-type PACs confirmed by high-resolution mass spectrometry
1Navarro M, Nunez O, Saurina J, Hernandez-Cassou S, Puignou L. J Agric Food Chem. 2014;62(5):1038-1046.
Procyanidin A2 Procyanidin B1
• Canadian cranberry extract manufacturer documented cranberry extract adulteration (likely with peanut skin extract) by HPLC-MS
Saw Palmetto Fruit / Berry ExtractSerenoa repens
Adulteration of Saw Palmetto
1Lindstrom A, Ooyen C, Lynch ME, Blumenthal M, Kawa K. HerbalGram. 2014;103:52-56.2Myers S. Nat Prod Ins. September 11, 20093Little DP, Jeanson ML. Scientific Reports 2013:3; DOI:doi:10.1038/srep03518
• Among 10 best-selling herb in mass market and natural channels
in the United States1
• Saw palmetto extracts often standardized to fatty acid content
• Palm, canola, olive, and coconut oils have been found as
adulterants in report from 20092
http://www.sfrc.ufl.edu/4h/Saw_palmetto/serrepws.jpg
• Occurrence tends to escalate
after a supply shortage
• Berries of close relative,
Acoelorrhaphe wrightii
reportedly sold as saw palmetto
based on DNA analysis3
Adulteration of
Arnica (Arnica montana) [a]
with
“Mexican Arnica” (Heterotheca inuloides) [b]
[both Asteraceae]
Walker KM, Applequist WL.
Adulteration of Selected Unprocessed
Botanicals in the U.S. Retail Herbal
Trade. Econ Bot, 2012.
Adulteration of
Thyme in Egyptian markets
• European Pharmacopoeia lists thyme (Thymus vulgaris) and
Spanish thyme (T. zygis) as acceptable species
• Most thyme traded as spice is a mixture of T. capitatus, T.
serpyllum, and T. vulgaris
• Statistical model with authentic samples was constructed using
UV spectrophotometry
Gad HA, El-Ahmady SH, Abou-Shoerb MI, Al-Azizia MM. A modern approach to the
authentication and quality assessment of thyme using UV spectroscopy and
chemometric analysis. Phytochem Anal. 2013;24(6):520-526.
• Commercial samples (n=12) collected
in Cairo and Aswan clustered around
T. vulgaris (9), Satureja montana (1)
or were of unknown identity (2)
Thymus vulgaris (Lamiaceae)
Adulteration of African mango seed Irvingia gabonensis (Irvingiaceae)
• Popularity in weight-loss
products.
• Currently no quality standards
• Methyl gallate, ellagic acid, &
derivatives as main
components.
• UHPLC/HRMS screening of 7
commercial materials indicated
adulteration, including regular
mango (Mangifera indica).
Sun J, Chen P. Ultra high-performance liquid chromatography with high-resolution mass
spectrometry analysis of African mango (Irvingia gabonensis) seeds, extract, and related dietary
supplements. J Agric Food Chem. 2012;60:8703−8709.
http://www.africanmangoguide.org/
#4
top-selling
herbal DS
in
mainstream
retail stores
in 2014
Black Cohosh Adulterants
Chinese cimicifuga • Sheng ma
Actaea dahurica
Xing an sheng ma
Actaea cimicifuga
Sheng ma
Actaea heracleifolia
Da san ye sheng ma
Black Cohosh AdulterationRecent Reports
2006: HPLC-ELSD (n=4): 25% adulterated1
2006: HPLC-MS (n=11): 36% adulterated2
2012: DNA barcoding (n=36): 25% adulterated3
2014: HPLC-MS/MS & DNA sequencing (n=25): 28% adulterated4
2015: FIMS, NMR & DNA (Sanger) sequencing5
Chinese Actaea raw materials (n=11): 85% adulterated
Finished products (n=14): authentication not possible by NMR, FIMS; DNA found in 5 samples: 20% adulterated
1He K, Pauli GF, Zheng B, et al., J Chromatogr A 2006;1112(1-2):241-2542Jiang B, Kronenberg F, Nuntanakorn P. et al., J Agric Food Chem 2006;54(9):3242-32533Baker DA, Stevenson DW, Little DP. J AOAC Int. 2012;95(4):1023-10344Masada-Atsumi S, Kumeta Y, Takahashi Y, et al., Biol. Pharm. Bull. 2014;37(3):454–460 5Harnly JM, Chen P, Sun J et al., Planta Med. 2015; in press
1He K, Pauli GF, Zheng B, et al., J Chromatogr A 2006;1112(1-2):241-2542Jiang B, Kronenberg F, Nuntanakorn P. et al., J Agric Food Chem 2006;54(9):3242-32533Baker DA, Stevenson DW, Little DP. J AOAC Int. 2012;95(4):1023-10344Masada-Atsumi S, Kumeta Y, Takahashi Y, et al., Biol. Pharm. Bull. 2014;37(3):454–460 5Harnly JM, Chen P, Sun J et al., Planta Med. 2015; in press
The botanical supply chain is global;
adulteration is a global challenge.
http://http://www.erau.edu