By Elaine Watson Nutra Ingredients USA
If last month’s paper in the Journal of Analytical Toxicology was seen by some observers as the ‘final nail in DMAA’s coffin’, a new paper published in Drug Testing and Analysis this month appears to drive that nail home.
In a study entitled 1,3-Dimethylamylamine (DMAA) in supplements and geranium products: natural or synthetic? scientists from the University of Texas, Arlington, tested 13 dietary supplements purporting to contain DMAA or geranium extract, plus eight commercially available geranium extracts.
The analysis was led by Dr Daniel W. Armstrong, who holds the Robert A. Welch Chair in Chemistry at the University of Texas, Arlington.
Stereoisomeric ratios of DMAA in synthetic standards and in dietary supplements were indistinguishable
The geranium extracts were examined by high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). No DMAA was detected in any of the samples with a limit of detection of 10 parts per billion.
For the supplements (which included USPLabs’ Jack3d and Nutrex Research’s Hemo Rage), the enantiomeric and diastereomeric ratios of two different known synthetic DMAA compounds, as well as the total concentrations of DMAA and its stereoisomeric ratios, were determined by chiral gas chromatography (GC).
The stereoisomeric ratios of DMAA in the synthetic standards and in all the commercial supplements were “indistinguishable”, said the authors.
No DMAA was detected at a level of ≥10 ppb in any of the 8 geranium oil samples
They conclude: “It appears unlikely that the DMAA in supplements originates from natural sources such as geranium oils for three reasons: The DMAA extracted from these supplement products had diastereomeric ratios that were indistinguishable from the synthetic DMAA standards; they are all racemic; and no DMAA was detected at a level of ≥10 ppb in any of the 8 geranium oil samples.”
NSF International: No quality independent, credible data has shown DMAA is in geranium plants
Ed Wyszumiala, general manager of dietary supplements programs at analytical testing firm NSF International, said: “It’s good to see that the independent research that has been underway and now being published is confirming that DMAA is not derived for geraniums. No quality independent, credible data has shown DMAA is in geranium plants.”
He added: “I just got back from China and spent time looking for DMAA suppliers… The couple I found and the data they sent me show that the production of the raw materials are synthetically produced and not sourced from geranium derived materials.
“I was unable to locate a bulk raw material supplier of geranium as a large scale crop where I could purchase raw material for extraction.”
Commercial geranium oils are commonly adulterated
James Neal-Kababick, director of Flora Research Laboratories, said: "The authors do a good job of demonstrating that all the products containing DMAA that they tested all were racemic (had equal levels of all four isomers) which is typical of a synthetic compound and not a natural product."
But he added: "While the authors went to great effort to show that the commercial geranium oils tested did not contain any detectable DMAA down to PPB levels by using a combination of LCMS techniques, it is unfortunate that they did not authenticate the essential oils prior to testing.
"Commercial geranium oils are commonly adulterated and thus the oils may have been cut with synthetic diluents. This weakens this aspect of the study which I regret to even mention as I know this statement will be taken out of context by those struggling to hold on to the myth of natural geranium derived DMAA...
"That said, I still feel this is an important paper with a very strong finding regarding the diastereomeric ratios showing that the alleged naturally derived DMAA product claims are unsubstantiated."
Why it matters
The source of DMAA is at the heart of the dispute between the Food and Drug Administration (FDA) and supplement makers, and could be key to the outcome of a string of class action lawsuits filed against USPLabs and others since the FDA sent warning letters to 10 manufacturers and distributors of supplements containing DMAA in April.
According to the FDA, synthetically-produced DMAA is "not a dietary ingredient and is not, therefore, eligible to be used as an active ingredient in dietary supplements".
However, if DMAA exists naturally in geranium, USPLabs et al can argue that synthesized DMAA is a lawful dietary ingredient as it is a synthetic copy of something found in nature that has been in the food supply for years.
The challenge for these firms has been proving it, however.
According to an analysis by Chinese researchers reportedly using gas chromatography-mass spectrometry (GC-MS) techniques and published in the Journal of Guizhou Institute of Technology (1996, Vol. 25, pp. 82-85) – ‘The Ping Paper’ – DMAA is a constituent of geranium oil, but no other published analysis has reported its presence.
USPLabs: New study to be published this week 'definitively demonstrates the presence of DMAA in geranium'
All eyes are now on USP Labs, which has commissioned new research it claims corroborates Ping’s findings.
While the research has not yet been published, it has already been cited by USPLabs and Nutrex Research as proof that the DMAA in their supplements is legal.
A USPLabs spokeswoman said: "We are reviewing the Armstrong study and and will have a statement for you later this afternoon [See NutraIngredients-USA tomorrow for USPLabs' full response]."
But she claimed that a new study in the journal Analytical Chemistry Insights entitled 'Identification and Quantification of Dimethylamylamine in Geranium by Liquid Chromatography Tandem Mass Spectrometry' would be "released within the week".
This, she argued, "definitively demonstrates the presence of DMAA in geranium".
She added: "We continue to work with the FDA to confirm that DMAA is a nutritional supplement. USPlabs continues to stand by the safety and efficacy of our DMAA products, and our customers worldwide continue to purchase and enjoy them."
Source: Drug Testing and Analysis
Published online ahead of print, doi/10.1002/dta.1368/
“1,3-Dimethylamylamine (DMAA) in supplements and geranium products: natural or synthetic?”
Authors: Ying Zhang, Ross M. Woods, Zachary S. Breitbach and Daniel W. Armstrong