The Floyd Fairness Fund held a fund-raising event in San Francisco a couple of days ago, attended by approximately 100 people. At the event, Arnie Baker presented his latest slideshow, highlighting problems with the data in the anti-doping case against Floyd Landis. TBV was in attendance, and gives this summary:
Arnie Baker’s slide show and commentary had information being released for the first time. The major points were that:
- Landis got non-S17 test reports from USADA this week.
- Landis had gotten another copy of the LDP from AFLD, and it is different from the one obtained from USADA, though both claim to be “original” documents.
- One of the sample numbers believed to be a typo in the original LDP for Landis was in fact a sample for a different number tested at the same time.
- LNDD did not have operating manuals for their mass spectrometers, and ran them at incorrect operating pressures.
It’s interesting that the Landis defense team has finally gotten copies of the other lab results from the 2006 Tour de France, which they requested more than four months ago. As TBV notes, the logjam has broken, perhaps due to public pressure on USADA. Whatever the reason, it’s definitely good to see forward movement. TBV expects that at some point in the future, this information will be posted on the Internet, for all to see.
Another interesting new twist is that one sample number, originally thought to be a typo, turns out to be a sample from a different rider whose sample appears to have been analyzed at the same time as Landis’.
Two disturbing items from these new revelations are the differences in “original” lab documentation from LNDD (the lab documentation information from the AFLD versus the information provided by USADA), and the claim that LNDD was operating their mass spectrometer at too high a pressure.
Let’s look at the lab documentation packs first. Discrepancies between the data contained within the documentation would be a huge problem for the anti-doping side. Two original documents from the same set of tests showing the same set of data should be identical in every respect (other than such mundane details as the color paper it might be printed on). If, as it appears, there are some actual discrepancies in the data itself, then there is a serious problem with the prosecution’s case. Which data are we supposed to believe? Which data is the true data and which is an error?
No matter what, this would be extremely sloppy work from an accredited, esteemed anti-doping lab such as LNDD. It could well resurrect the ghost of Johnnie Cochran, who may yet appear at the hearing in May to say, “If the data don’t fit, you must acquit.”
According to TBV, except for a few minor examples, not much else has been said about what the differences are between the AFLD and USADA lab documentation. In good time, we will probably know, but for the moment it remains a bit of a mystery.
Another mystery is how LNDD could have been operating their mass spectrometer incorrectly. Baker told his audience that LNDD did not even have the manufacturer’s manuals for the instrument. Baker, however, was able to find and download that documentation from the Internet. From what TBV tells us, Baker’s claim is that the instrument was operated at too high a pressure. As TBV observes:
This is important, because it affects where peaks become registered.
In turn, this would affect the identification of the substance being analyzed. Or perhaps lead to the misidentification of the substance being analyzed.
I’ve asked one of my sources, a microbiologist familiar with mass spectrometry exactly how running the equipment at too high a pressure would affect the results. While waiting for her response, I found an interesting article called GC/MS Analysis by Frederic Douglas. Douglas is an attorney who wrote the article for other attorneys working on cases where gas chromatography and/or mass spectrometry are an issue. The article is written so that it should be understandable to most non-scientists.
In the article, Douglas addresses what happens when a mass spectrometer is run at too high a pressure, saying:
If the interior pressure in an MS instrument is too high, erroneous results may occur. [Note: italics added] As the specimen molecule breaks up, the fragments accelerate. If a fragment collides with another fragment, then these two fragments may combine to make a new particle. In this event, the detector will register the mass of this new particle on the mass spectrum. The reference spectra for comparison are produced under low pressure conditions which minimize collisions between fragments. A technician would find a spectral peak where one is not expected. … This is similar to finding pieces from a different puzzle in your box and trying to make these extraneous pieces fit. As this is impossible, any MS analysis under high pressure conditions would depend greatly on guesswork by the technician. [Note: italics added]
So it would appear that this could have a significant impact on the identification of the compound under study.
Update: In an email from my microbiologist source, comes the following:
If you have too much pressure going into the mass spectrometer, you may not get sufficient separation of ions. So, it may look like your desired sample, but really not be it.
One example of this is when the Centers for Disease Control (CDC) first started using a mass spectrometer for identifying a nerve agent in blood. They used GC/MS, but instead of seeing the nerve gas metabolites in the blood that they were looking for they saw a natural metobolite that looked similar and came off at the same time on the column. In other words, the sample didn’t separate well and therefore came out of the column at the same time as the what they were looking for. This can happen if the pressure is too high. You might think you have something there, when actually you don’t.
By having too high a pressure, you may get a peak for something you are not looking for, such as a naturally occurring compound that comes off (the column) at the same time and behaves similarly to the desired sample.
So, if I’m understanding my source correctly, regardless of whether the control samples were run under the higher pressure, the fact that the ions might not separate properly can lead to an incorrect conclusion about what compound has been detected.
If this is correct, then all bets are off. And in that case, the Landis side would have a very good argument, as it would be difficult to determine with any accuracy whether the lab found what they claimed to have found.
At first glance, it looks like a big plus for the Landis defense. But more information is needed before any real conclusions can be drawn about how accurate the data is. One conclusion that can be drawn right away, however, is that this is yet another illustration of sloppy technique at LNDD. Not having the manuals for an important piece of equipment, especially when they are fairly easily obtained, is inexcusable. As is not running the mass spectrometer at the correct pressure.
It seems to me that both of the lack of manuals and improper use of the mass spectrometer would be a violation of any ISO or other accreditation the lab possesses. But whether this revelation invalidates the data obtained at LNDD using mass spectrometry is yet to be seen. It certainly has the potential.
With these latest revelations about LNDD’s lab procedures, one has to wonder: Is Mickey Mouse their lab technician?
Micky Mouse their lab technician? Noooo, He’s American. Everyone knows its Pepe Le Pew stinking up the LNDD joint with bad science.
Thank you so much for posting this. Since TBV shared his bulleted list with us yesterday, I’ve been waiting and hoping someone would help me, the non-scientist, understand what if anything this means. From your post about the MS, I can imagine several different scenarios. Doesn’t it make you wonder what Arnie Baker knows that they’re not sharing just yet, to save for the hearing?!
I understand the improper ion separation argument, and look forward to deeper analysis. At the same time, I wonder if it might also be completely innocuous, and arguably an improvement in the technique recommended by the manufacturer. You’d want documentation to show that it was an improvement, really, but it might be. It seems to me possible for the pressure to be like a “gain” knob on an amplifier. Adjusting the pressure might bring things into a more accurate or convenient range on the column. If it separates correctly, and is calibrated against known samples accurately, then it might work better than the original spec. We don’t know without the calibration data deBoer requested and has never received, and possible examination of the electronic data files rather than printouts.
On the other hand, it might be like setting the amplifier to 11.
-dB
Debby,
If you want the equivalent of “Physics for poets” you are at the right place. Rant does a great job of making the complex clear and compelling. Thanks Daniel.
Sorry about the physics comment. 😉