Milwaukee Journal Sentinel Attacks Vaping Again

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Jman8

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I agree wholeheartedly with this sentiment. The "dangerous levels" are entirely impossible to quantify right now, everyone agrees, we don't really know how much will or won't hurt you. The safest option is to simply cut it out entirely before someone can link some disease directly to diketones. That would be the strongest platform any government agency has towards outright banning e-liquid/vaping.

Like the ban on alcohol, other stuff and combustibles? All linked to diseases. All recreational choices for reasonable people to make own determinations.

My first thought response was, you could say the same thing about the nicotine in eLiquid. But I went with my second response first. The safest political option would be to cut nicotine out of eLiquid.
 

Kurt

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Comments are closed for the article. So here are my opinions.

First off, I do not fault a journalist for trying to communicate a known important problem in vaping. This problem is potentially very serious, and people do need to know about DA and AP. If I did not believe that I would not have been part of the team that first published this a year ago. Nor do I at all fault Dr. Reid of Marquette for taking an honest crack at testing for these compounds. I applaud his efforts, and I hope he can bring another validated method online in this big effort to make vaping as safe as possible. But there are some very profound problems with many details of this article out of the Milwaukee Journal Sentinel by Raquel Rutledge.

From the article:
"Marquette and Enthalpy said their analyses passed their quality control measures and that they stand by their results.

The discrepancy highlights differences in testing methodology and desired levels of detection. Marquette's approach used a more sensitive technique that scientists say can detect lower levels, down to parts per billion. The Journal Sentinel consulted with three independent experts who said the university's method was superior.

The problem is, it is also more time-consuming and costly.
"

No, this is NOT the problem, and the author has been informed of this, because Enthalpy has contacted her and tried to explain the science. A lower LOD (Limit of detection) or LOQ (limit of quantification) is certainly preferred, but ONLY if the method assay is validated against other methods, and the lab has a lot of experience doing this particular test. Diketones are notoriously difficult to get accurate levels of, and it can take a lot of time and effort to get trustworthy data, especially when there are other flavor compounds present, as in an e-liquid. WAY more time and cost than is implied that Marquette went through for their 5 samples, which are the only samples that they have tested for DA and AP, as in ever. The difference between an LOD of 1 ppm or 0.5 ppm is NOT significant, and certainly does not define a "superior" method, especially if the following information is taken into account.

The Marquette lab (Dr. Scott Reid) used GC-MS with a derivative method (converts DA and AP to specific nitrogen compounds that are then analyzed). This is fine, but they had NEVER done this assay before, and it is not a validated method. Meaning they never did any other known valid method for checking their numbers. Nor did they use an internal standard to measure against which is common practice for qualitative GC-MS assays. They also ran the samples on a GC-MS column shared by others in the department, with the original stock column, instead of using a dedicated instrument, like that which is used at Enthalpy Analytical.

Marquette asked the Journal Sentinel to have Enthalpy to verify their results, not the other way around. Enthalpy has years of experience with their methods, which are validated, and have run these tests 1000s of times. Not only this, but Enthalpy verified their own results with two methods: GC-MS and derivative HPLC, and those two methods got matching results between them for each sample given that per ml and per gram can differ by up to 30% depending on sample density. Enthalpy Analytcial’s methods are validated, accredited, and they run these assays over 500 times a month. Dr. Reid has run a total of 5 samples ever, all for this article, and with a method not validated for e-liquid samples, but instead is recommended for the analysis of diketones in beer. I have not spoken with him myself, but I am told by Gene Gillman (Director of Enthalpy Analytical) that Dr. Reid is a very nice and reasonable man, and he is not happy with how this story ended up, and certainly does not agree that his method is "superior", no matter what the unspecified "experts" said in the article. Enthalpy is currently working with Dr. Reid to understand the differences between the methods. This is how science is done!

Here are the results of the two labs:
GASPING21G1-01.png


The units for the data are given as “ug/mL”. I will assume she means “μg/mL”, micrograms per milliliter, since ug is not an actual unit. Did Ms. Rutledge or the Sentinel’s editor not know this? Given the focus on small LOD differences between the two labs, I am troubled by this unit error.

Enthalpy was asked to run for verification 3 samples. They ran and got, using two different methods, reproduced results for Foghorn Randy, Matik Pomegranate, and Radioactive Vapes Grape. The last two were measured as ND (non-detects, zero within the method's LOD), while the Randy had 61.8 μg/mL DA and 207 μg/mL AP, again, results matching between two methods. This is the GOLD STANDARD for such a test: to have results matched between two different validated methods, in this case GC-MS and derivative-HPLC. These results are somewhat different than Marquette's first time ever doing a DA or AP test, and with an unvalidated method, and without an internal standard, let alone a 5-point calibration curve.

But according to Raquel, who is clearly not an analytical chemist, none of that matters at all. Marquette claims a slightly lower LOD, so it is superior, end of story. Forget verification. Forget years of intense and voluminous experience working out dilutions and flavor-matrix problems. Forget published methods for testing DA and AP in e-liquids in peer-reviewed journals. Forget that LOD and LOQ are practically invalid terms if the method is not validated, and you have essentially zero experience running it.

It should also be noted that while Ms. Rutledge seems to be trying to insult Enthalpy as being inferior to Marquette, which is not based in any data whatsoever, and makes zero sense, it was Enthalpy that helped first bring this problem of diketones into the open, and was the first to publish peer-reviewed validated tests to determine their concentrations in e-liquids. They also were the ones that measured DA in cigarette smoke (acknowledged in Pierce, J.S., et al., Crit. Rev. Toxicol., 2014), which is on average about 100x the exposure from vapor from positive-testing e-liquids, something that Raquel evidently does not find important. It should also be noted that there are no data to suggest that levels of DA or AP in e-liquids below 1-5 μg/mL have any negative health impact.

Now, based on the implications of the article, Matik and Radioactive Vapes think they have been selling two DA- and AP-positive e-liquids, when these compounds are almost certainly not present at all.

Now Dr. Reid is in, for an ethical chemist, the very uncomfortable position of having essentially preliminary data of an assay still in development being labeled as superior to an established commercial lab using two validated methods for verification of results, something Dr. Reid himself does not agree with.

Now an established commercial analytical lab that has specialized for years in e-liquids and tobacco products, and has been a long trusted vanguard for accuracy in testing for AEMSA for this very problem, and who was integral to first publishing this DA/AP problem, is being attacked because their validated and verified results do not match that of a lab that has no experience with this assay, using an unvalidated and uncalibrated method. How can this possibly be? What is the purpose of this complete lack of regard for rigorous analytical chemistry?

Now this story is being carried by other outlets with a new title that is meant to slander Enthalpy Analytical, Inc. If these results were part of a manuscript submitted to a scientific journal for publication, and the conclusions Ms. Rutledge has put forth were the conclusions of the paper, it would be rejected upon peer-review based on profoundly faulty logic and a complete lack of understanding of fundamental analytical chemistry, starting with the use of incorrect units.

If Ms. Rutledge wanted the industry to solve this problem, she has gone about it completely wrong. With this article a major validated and verified tool in the very solving of this important problem, which Ms. Rutledge should support, is being attacked with accusations which do not stand at all to rigorous and educated scientific scrutiny, and with conclusions that all scientists involved with this study do not agree with.

In my professional opinion, as PhD chemist who has published in the electronic cigarette field in peer-reviewed journals, and has valued, trusted and rigorous collaborations with Enthalpy on these very matters, this story needs to be either drastically rewritten to reflect the actual science, or else removed entirely, including from other outlets that are now spreading this ignorant and pointless attack. Either way, a public apology should be given by Ms. Rutledge, if not the Milwaukee Journal Sentinel.

Ms. Rutledge, if you really want to help this important cause and promote truly accurate testing, which is critical if we ever hope to solve this, do the right thing here. Rewrite this story, or have it taken down.
 
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AndriaD

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Comments are closed for the article. So here are my opinions.

First off, I do not fault a journalist for trying to communicate a known important problem in vaping. This problem is potentially very serious, and people do need to know about DA and AP. If I did not believe that I would not have been part of the team that first published this a year ago. Nor do I at all fault Dr. Reid of Marquette for taking an honest crack at testing for these compounds. I applaud his efforts, and I hope he can bring another validated method online in this big effort to make vaping as safe as possible. But there are some very profound problems with many details of this article out of the Milwaukee Journal Sentinel by Raquel Rutledge.

From the article:
"Marquette and Enthalpy said their analyses passed their quality control measures and that they stand by their results.

The discrepancy highlights differences in testing methodology and desired levels of detection. Marquette's approach used a more sensitive technique that scientists say can detect lower levels, down to parts per billion. The Journal Sentinel consulted with three independent experts who said the university's method was superior.

The problem is, it is also more time-consuming and costly.
"

No, this is NOT the problem, and the author has been informed of this, because Enthalpy has contacted her and tried to explain the science. A lower LOD (Limit of detection) or LOQ (limit of quantification) is certainly preferred, but ONLY if the method assay is validated against other methods, and the lab has a lot of experience doing this particular test. Diketones are notoriously difficult to get accurate levels of, and it can take a lot of time and effort to get trustworthy data, especially when there are other flavor compounds present, as in an e-liquid. WAY more time and cost than is implied that Marquette went through for their 5 samples, which are the only samples that they have tested for DA and AP, as in ever. The difference between an LOD of 1 ppm or 0.5 ppm is NOT significant, and certainly does not define a "superior" method, especially if the following information is taken into account.

The Marquette lab (Dr. Scott Reid) used GC-MS with a derivative method (converts DA and AP to specific nitrogen compounds that are then analyzed). This is fine, but they had NEVER done this assay before, and it is not a validated method. Meaning they never did any other known valid method for checking their numbers. Nor did they use an internal standard to measure against which is common practice for qualitative GC-MS assays. They also ran the samples on a GC-MS column shared by others in the department, with the original stock column, instead of using a dedicated instrument, like that which is used at Enthalpy Analytical.

Marquette asked the Journal Sentinel to have Enthalpy to verify their results, not the other way around. Enthalpy has years of experience with their methods, which are validated, and have run these tests 1000s of times. Not only this, but Enthalpy verified their own results with two methods: GC-MS and derivative HPLC, and those two methods got matching results between them for each sample given that per ml and per gram can differ by up to 30% depending on sample density. Enthalpy Analytcial’s methods are validated, accredited, and they run these assays over 500 times a month. Dr. Reid has run a total of 5 samples ever, all for this article, and with a method not validated for e-liquid samples, but instead is recommended for the analysis of diketones in beer. I have not spoken with him myself, but I am told by Gene Gillman (Director of Enthalpy Analytical) that Dr. Reid is a very nice and reasonable man, and he is not happy with how this story ended up, and certainly does not agree that his method is "superior", no matter what the unspecified "experts" said in the article. Enthalpy is currently working with Dr. Reid to understand the differences between the methods. This is how science is done!

Here are the results of the two labs:
GASPING21G1-01.png


The units for the data are given as “ug/mL”. I will assume she means “μg/mL”, micrograms per milliliter, since ug is not an actual unit. Did Ms. Rutledge or the Sentinel’s editor not know this? Given the focus on small LOD differences between the two labs, I am troubled by this unit error.

Enthalpy was asked to run for verification 3 samples. They ran and got, using two different methods, reproduced results for Foghorn Randy, Matik Pomegranate, and Radioactive Vapes Grape. The last two were measured as ND (non-detects, zero within the method's LOD), while the Randy had 61.8 μg/mL DA and 207 μg/mL AP, again, results matching between two methods. This is the GOLD STANDARD for such a test: to have results matched between two different validated methods, in this case GC-MS and derivative-HPLC. These results are somewhat different than Marquette's first time ever doing a DA or AP test, and with an unvalidated method, and without an internal standard, let alone a 5-point calibration curve.

But according to Raquel, who is clearly not an analytical chemist, none of that matters at all. Marquette claims a slightly lower LOD, so it is superior, end of story. Forget verification. Forget years of intense and voluminous experience working out dilutions and flavor-matrix problems. Forget published methods for testing DA and AP in e-liquids in peer-reviewed journals. Forget that LOD and LOQ are practically invalid terms if the method is not validated, and you have essentially zero experience running it.

It should also be noted that while Ms. Rutledge seems to be trying to insult Enthalpy as being inferior to Marquette, which is not based in any data whatsoever, and makes zero sense, it was Enthalpy that helped first bring this problem of diketones into the open, and was the first to publish peer-reviewed validated tests to determine their concentrations in e-liquids. They also were the ones that measured DA in cigarette smoke (acknowledged in Pierce, J.S., et al., Crit. Rev. Toxicol., 2014), which is on average about 100x the exposure from vapor from positive-testing e-liquids, something that Raquel evidently does not find important. It should also be noted that there are no data to suggest that levels of DA or AP in e-liquids below 1-5 μg/mL have any negative health impact.

Now, based on the implications of the article, Matik and Radioactive Vapes think they have been selling two DA- and AP-positive e-liquids, when these compounds are almost certainly not present at all.

Now Dr. Reid is in, for an ethical chemist, the very uncomfortable position of having essentially preliminary data of an assay still in development being labeled as superior to an established commercial lab using two validated methods for verification of results, something Dr. Reid himself does not agree with.

Now an established commercial analytical lab that has specialized for years in e-liquids and tobacco products, and has been a long trusted vanguard for accuracy in testing for AEMSA for this very problem, and who was integral to first publishing this DA/AP problem, is being attacked because their validated and verified results do not match that of a lab that has no experience with this assay, using an unvalidated and uncalibrated method. How can this possibly be? What is the purpose of this complete lack of regard for rigorous analytical chemistry?

Now this story is being carried by other outlets with a new title that is meant to slander Enthalpy Analytical, Inc. If these results were part of a manuscript submitted to a scientific journal for publication, and the conclusions Ms. Rutledge has put forth were the conclusions of the paper, it would be rejected upon peer-review based on profoundly faulty logic and a complete lack of understanding of fundamental analytical chemistry, starting with the use of incorrect units.

If Ms. Rutledge wanted the industry to solve this problem, she has gone about it completely wrong. With this article a major validated and verified tool in the very solving of this important problem, which Ms. Rutledge should support, is being attacked with accusations which do not stand at all to rigorous and educated scientific scrutiny, and with conclusions that all scientists involved with this study do not agree with.

In my professional opinion, as PhD chemist who has published in the electronic cigarette field in peer-reviewed journals, and has valued, trusted and rigorous collaborations with Enthalpy on these very matters, this story needs to be either drastically rewritten to reflect the actual science, or else removed entirely, including from other outlets that are now spreading this ignorant and pointless attack. Either way, a public apology should be given by Ms. Rutledge, if not the Milwaukee Journal Sentinel.

Ms. Rutledge, if you really want to help this important cause and promote truly accurate testing, which is critical if we ever hope to solve this, do the right thing here. Rewrite this story, or have it taken down.

Excellent response. And it is precisely because of this sort of thing that I've opted to exclude any diketones from my ejuice, by DIYing and using flavors which the flavor mfr says have no diketones -- I figure the flavor mfr's have far less reason to lie or fudge results.

It's not that I think diketones are so horribly deadly. It's that, at this point, not enough is *truly known* about their use in vaping, and there are so many different sources saying different things, it seems impossible for a pure layman to know who is right and who is full of it. I cannot trust actual ejuice makers to even know what they're talking about, nevermind having the integrity to tell the truth about it.

My zero-tolerance to diketones may be nothing but paranoia... but I prefer an excess of caution in pretty much everything.

Andria
 
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Jman8

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Comments are closed for the article. So here are my opinions.

<snip>

*Snipped only cause I didn't want to quote the entire thing.

I think it is great that you set the record straight on the science/chemistry from what the Journal Sentinel reported. The details you provided are a great, informative read, and really help with those who seek to refute what the article is purporting, both at the political and scientific level.

From the political angle, it was already a travesty. It is a clear hit piece designed to state: vaping eLiquid is harmful and science proves this. The finer nuances of that political message are matters of debate as I'm sure not even @Kurt and I agree on the nuances. But hopefully we both agree on this as a hit piece that was written to favor the ANTZ position on eLiquids.

From the scientific angle, it is now established (for me) to be a travesty, and as their political angle rests on the science, then in reality, the article is a flop all the way around.

I'm sure part of the intent was to marginalize Enthalpy (or any commercial lab) and to set up university labs as the 'only reliable source for such testing.' How am I so sure of this? Cause I used to work at the Journal Sentinel and am very familiar with its politics, both internally and for sure the editorial staff.

Kurt asked:

What is the purpose of this complete lack of regard for rigorous analytical chemistry?

I've somewhat answered this above, but wish to be more clear. The purpose is to tell the story that ANTZ wish to convey about eLiquids, and to marginalize anyone that is either neutral or showing even slightest favor to the pro-vaping position.

If I go back and review the original thread on the Dr. F. study results from 2 years ago, I wouldn't be surprised to find a comment by me that would now appear in the vein of "I told you so." This is the political angle of what is going on, and your data has (in my strong opinion) fed the frenzy. That you would be marginalized along the way strikes me as par for the course. They don't need you for the political angle. They just need to cite you as, "even scientific types favorable to vaping are noting the dangers that come with vaping eLiquid." After that is noted, your purpose for them is done. Your regard for rigorous analytical chemistry serves zero purpose for them going forward.

So when you write:

First off, I do not fault a journalist for trying to communicate a known important problem in vaping. This problem is potentially very serious, and people do need to know about DA and AP. If I did not believe that I would not have been part of the team that first published this a year ago. Nor do I at all fault Dr. Reid of Marquette for taking an honest crack at testing for these compounds. I applaud his efforts, and I hope he can bring another validated method online in this big effort to make vaping as safe as possible. But there are some very profound problems with many details of this article out of the Milwaukee Journal Sentinel by Raquel Rutledge.

I would like to have you explain the "known important problem in vaping." Cause the Journal Sentinel did this by communicating that 'eLiquid contains harmful chemicals.' So, either you join that chorus and echo that sentiment, or be VERY CLEAR on the fact that you are talking about POTENTIAL issues. Or please be clear here with how many vapers are observed to have contracted known lung issues from this important problem you are citing. Cause without such observations, then you are literally feeding the frenzy. And as one who is struggling to find respect lately for science given its followers and practitioners, I've about had it with going easy on the philosophical and political implications that come from your not so scientific assertions.
 
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KFarsalinos

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I disagree with the last comment. The only reason we were asked and contacted by the journalists is because we did the study. It is naive (no offense, i am not attacking or insulting anyone) to believe that none else would do the study if it was not for us. The big difference is that if someone else did it, the damage would have been extreme and we would have no saying and no opportunity to at least comment.
Now, of course everything depends on how you respond. I had more than 10 email exchanges with the journalist before she wrote the article. Did you see her quoting me once in the article? No. Why? Because she did not like my responses. Her emails were even worse than the article. She was claiming that DA and AP could cause damage in a single puff and that we should measure puff concentrations (which are huge compared to daily exposure). She also claimed we should use the 15minute exposure limits (that is, calculate the daily exposure based on 25ppb but multiplied with 15minutes exposure rather than use the 5ppb limit and multiply it with 8 hours exposure). Additionally, she knew that derivatization methods (as used by the university lab) are not very accurate, because i told her so (although she never told me about the Enthalpy and Univeristy lab results, i had no idea they had sent samples to labs to be tested).

Of course the article was quite negative. But what would have happened if the study was performed by a US university before we did it? To have an idea, look at the comment published from a university: http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4361011/
The same people were ready to perform our study, but backed off because we published it first. They also made a presentation on this issue during the FDA workshop in March, although they have done no research on it. I was there, and i used 3 minutes of my presentation to severely attack them for their presentation. I was able to do it because i performed the original study. Would i be able to attack them if that was not the case? Obviously not.
 

KFarsalinos

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Nov 16, 2013
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And a last thing. The evidence we have so far supports that diacetyl is a hazard. Better accept it before we have cases of disease in e-cigarette users. Because after that, there will be no e-cigarette. Of course we do not know how much is needed to cause damage. We do not know many other things, eg there is evidence that some amount of diacetyl may react with PG and/or VG and disappear over time. Most liklely not a large amount, but it can happen. In general, we should not forget that vaping is a daily habit, and consumers vape all day. It is not an intermittent or rare exposure.
We better not hide behind our fingers on that. Obviously, anyone is entitled to his/her opinion. But it is ironic to ask for evidence that will never exist, because we cannot ask people to use diacetyl in order to prove that it can cause disease through vaping.
 

Jman8

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And a last thing. The evidence we have so far supports that diacetyl is a hazard.

Diacetyl is a hazard for vapers? Please provide this evidence..

Better accept it before we have cases of disease in e-cigarette users. Because after that, there will be no e-cigarette.

Based on what? Or better yet, how is this not fear mongering?

Of course we do not know how much is needed to cause damage. We do not know many other things, eg there is evidence that some amount of diacetyl may react with PG and/or VG and disappear over time. Most liklely not a large amount, but it can happen. In general, we should not forget that vaping is a daily habit, and consumers vape all day. It is not an intermittent or rare exposure.

Neither is it intermittent or rare exposure for smoking. But here's the part where you get to claim all lung issues from smoking are because of presence of diacetyl.

We better not hide behind our fingers on that. Obviously, anyone is entitled to his/her opinion. But it is ironic to ask for evidence that will never exist, because we cannot ask people to use diacetyl in order to prove that it can cause disease through vaping.

And yet, people have been inhaling diacetyl on a daily basis via smoking/vaping for decades. The research suggests onset of symptoms occurs in 18 months or less. So, we already have plenty of people (millions really) who are using diacetyl in current products, some of which have been around for a hundred years, and the evidence to support your case of hazard, with lots of evidence.... amounts to what? Please share your findings.
 

Bunnykiller

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Seems the publication has several anti-vaping articles.
They even state cinnamon flavor, chocolate, grape, apple, cotton candy and bubble gum flavors may cause:
"symptoms such as tremors, nausea, vomiting, dizziness, headaches, sweating, swelling, rapid heart rate, coughing and irritability."
I bet they would even find issues with my unflavored..........
sounds like a serious nic overdose ;)
 
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