Chemical methods are the most important and widely used traditional plant identification techniques recommended by national and international pharmacopoeias. We have reviewed the successful use of different chemical methods for the botanical authentication of 2,386 commercial herbal products, sold in 37 countries spread over six continents. The majority of the analyzed products were reported to be authentic (73%) but more than a quarter proved to be adulterated (27%). At a national level, the number of products and the adulteration proportions varied very widely. Yet, the adulteration reported for the four countries, from which more than 100 commercial products were purchased and their botanical ingredients chemically authenticated, was 37% (United Kingdom), 31% (Italy), 27% (United States), and 21% (China). Simple or hyphenated chemical analytical techniques have identified the total absence of labeled botanical ingredients, substitution with closely related or unrelated species, the use of biological filler material, and the hidden presence of regulated, forbidden or allergenic species. Additionally, affecting the safety and efficacy of the commercial herbal products, other low quality aspects were reported: considerable variability of the labeled metabolic profile and/or phytochemical content, significant product-to-product variation of botanical ingredients or even between batches by the same manufacturer, and misleading quality and quantity label claims. Choosing an appropriate chemical technique can be the only possibility for assessing the botanical authenticity of samples which have lost their diagnostic microscopic characteristics or were processed so that DNA cannot be adequately recovered.
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