3M’s Decade of PFAS Analytical Malaise, 1984-1993
Photo by Carl Bohacek©
Please LINK to this article in my substack [Kris Hansen’s PFAS Journal]. You can subscribe (for free) and receive new content directly to your email; or read the text here. Non-Comprehensive Peer-Reviewed Literature Appended below.
3M’s Decade of PFAS Analytical Malaise, 1984-1993
Forbidden Knowledge at 3M, Part II
In 1983, the New York Times published “Fighting Back: Lewis W Lehr [3M’s CEO]; At 3M A Tough Stance Against a Tough Environmental Bill.” [LINK] The article summarizes 3M’s then-CEO’s opposition to Minnesota’s new “Superfund” legislation, a bill that aimed to hold industry accountable for its industrial waste and provided for “the cleanup of problem disposal sites and compensation for victims.” According to Lehr, the environmental protection legislation placed “an unfair liability burden on 3M" and was a demonstration of Minnesota’s “adverse business climate.”
Lehr was aware of 3M’s PFAS issues at the time he was CEO pushing back against the Superfund bill [LINK, App R & S]. It’s easy to imagine that 3M culture, under Lehr, who the NYT characterized as “highly critical - both publicly and privately - of MN’s political leaders” over the Superfund bill, was not one that embraced accountability for issues of environmental contamination. Perhaps Lehr’s attitude and the culture it created contributed to 3M’s Decade of PFAS Analytical Malaise, 1984-1993.
Part II, 1984-1993: Adding LCMS to OFA + F/NMR + gas chromatography (GC)
The 1980’s brought about a revolution in analytical chemistry with the advent of liquid chromatography-mass spectrometry (LCMS)*. As technological advances were developed and shared, foundational knowledge grew; the power and applicability of LCMS blossomed.
LCMS was a revolution in analytical chemistry because it was a new way to introduce some compounds into a powerful detector called a mass spectrometer. In particular, especially in the 1980s, LCMS transformed the analysis of compounds that were non-volatile and/or thermally labile…compounds that were challenging to analyze using existing analytical tools.
Without going too far into the geeky details, there are several characteristics of PFOS that made it an excellent fit for some types of LCMS: it is soluble in water, it exists as a charged species in water, it’s not super big (as molecules go) and, as we well know, PFOS is very stable. [Jumping ahead in our timeline by many years, just for orientation, the method that I developed for determination of PFOS in human blood in 1997 [LINK] was an LCMS method].
Analytical Developments OUTSIDE 3M 1984-1993: Because 3M chose not to share information they had about PFOS being a major component of the organic fluorine in the general population, no one working outside of 3M was developing methods for environmental characterization of PFOS and thus no one published on it.
Analytically, if not politically, 3M’s objective in the 1980s should have been additional confirmation (beyond that provided by OFA, F/NMR and GC) that PFOS was a component of the organic fluorine found in the blood of the non-occupationally exposed population. Despite what the company may imply, to do so, it was NOT necessary for 3M to have a method that was developed entirely in-house at 3M, capable of high-thru put, highly quantitatively accurate, automatable, or extremely sensitive (e.g. to 1 ppb). A semi-quantitative analytical technique complimentary to 3M’s existing PFOS tool box would have sufficed.
To determine whether PFOS COULD have been detected during this decade of LCMS development, assess the peer-reviewed literature between 1984-1993, looking at published data on LCMS analysis of molecules structurally similar to PFOS in matrices similar to blood (PFOS in blood proxies!)
On my website blog (for the geeks) is a NON-COMPREHENSIVE summary of relevant peer-reviewed research reported between 1982 and 1993 demonstrating LCMS capabilities for low-level detectability of relatively low molecular weight, water soluble, ionizable compounds (PFOS proxies). This survey of the peer-reviewed literature demonstrates the utility and versatility of LCMS that developed between the early 1980s to the early-1990s and includes methods for low-level characterization of (for example) drugs, metabolites, pesticides, surfactants and dyes in biological or environmental matrices.
While a literature analysis cant provide 100% certainty that PFOS could have been detected at the same level as these proxy molecules (perhaps another reason 3M kept secret even the NOTION that PFOS was a component of the organic fluorine in blood), as an educated assessment, in the hands of an LCMS expert the goal of PFOS confirmation in blood could have been met in this decade and long before I did so in 1997.
Analytical developments INSIDE 3M, 1984-1993: As LCMS was developing as a power tool in the field of analytical chemistry OUTSIDE 3M, inside 3M, publicly available documents indicate that the technical leadership for PFOS and PFOA analytical method development shifted from Dr. Hagen (GC expert), Dr. Newmark (F/NMR expert) and Dr. Belisle (OAF expert) to the man who would become my boss in 1996, Mr. Jim Johnson.
Unlike the scientists referenced in my literature review, Mr. Johnson was not a technical leader in the field of LCMS. He wasn’t an analytical chemistry leader within 3M. In fact, Johnson wasnt even an analytical chemist. When Johnson joined the PFAS characterization effort at 3M, his title was Senior Biochemical Pharmacologist working in the Drug Metabolism Group [LINK], [LINK] #1279. When LCMS experts were expanding the limits of analytical chemistry, Johnson was dosing and characterizing the pharmacokinetics of radiolabeled PFAS in rats [LINK]. With this in mind, it’s not surprising that I found little evidence of analytical method development at 3M between 1984-1993. However, when analytical updates are presented to the FC Steering Committee during this time, they are provided by Johnson [e.g. #2725], a biochemical pharmacologist.
Given the magnitude of the risk associated with widespread public contamination of a 3M chemical known to be persistent, bioaccumulative and toxic to mammals and fish [e.g. LINK, #2573, LINK, AppAA], confirming and characterizing that risk should have been paramount for the corporation. Best and Brightest, All Hands on Deck, Full Court Press, etc. And yet 3M entrusted development of the next generation of PFOS analytical methods to a pharmacologist.
Where INSIDE 3M and OUTSIDE 3M should have come together but…didnt: I came across a series of 1983 internal memos from within Philip Morris Company (yes, the tobacco company), asking permission to retain Dr. Jack Henion (professor at Cornell), as a technical expert in the “blossoming field” of LCMS. The requests note the potential of LCMS as an analytical tool, especially for the analysis of non-volatile compounds in complex solutions (both characteristics of PFOS in blood) [LINK]; one memo specifically states that LCMS “provides a needed complement to well-established” methods [LINK]. Another indicates that Henion had already signed a secrecy agreement with Philip Morris [LINK]. Retaining an expert in the field was what scientists at Philip Morris were pursuing to maximize the utility of a new analytical tool to solve their big questions in 1983.
Like Philip Morris, 3M also retained Henion. However, based on publicly available documents, 3M’s partnership with Henion did not start until AFTER 1993. Despite the criticality of the PFOS risk to public health, it took 3M an additional 10+ years to secure a relationship with an external LCMS expert to contribute to the characterization of PFOS in blood. (That’s not the only thing odd about 3M's partnership with Henion. We will dig into THAT weirdness in Part III).
There were several outside research groups that had established considerable expertise in analyzing molecules like PFOS between 1984 and 1993 (not just Henion). But, as far as we can tell, during 3M’s Decade of PFAS Analytical Malaise, the company did not approach any of them to further confirm PFOS in the blood of the general population.
Once again, 3M chose inaction over action, ignorance over knowledge.
If I had the chance to question 3M leadership, I’d ask: did 3M hire any LCMS experts between 1983-1993 and request their help in confirming the identity of the major component of the organic fluorine present in non-occupationally exposed human blood?
Why not?
No later than 1992, 3M (Johnson) did finally acquire an LCMS [#2725]. However, there is no publicly available record indicating any effort by Johnson or anyone within 3M, to confirm that PFOS was present in the blood of the general population. Dale Bacon, leader of 3M’s Environmental Lab (Johnson’s boss and the guy who would become my boss after Johnson abruptly left the company following my discovery) admitted under oath that he was aware in the 1980s that PFOS was present in the blood of the general population [LINK]. Again, there is no available evidence that Bacon or anyone in 3M’s leadership team pushed for additional confirmation work.
And then there’s Document #1408.
I find #1408 to be one of the most provocative publicly available documents. It’s dated November 18, 1993 in the index on the MN AG’s site. No author is attributed to #1408, but based on tone and content, I’d bet a lot that it was written by my first boss at 3M: Jim Johnson.
I think this doc strikes me so hard because I created something similar when I was in the midst of my PFAS “discoveries” in 1997-1999. My own version of #1408 was, like Johnson’s, a somewhat tormented list of what I did know, what I didnt know, and what worried me most about what I didnt know. (To be fair, my “lists” were typically reports and I put my name on them). Topically, my list wasnt the same as Johnson’s but the tone is familiar. I remember feeling satisfaction in confidently asserting what we had definitely figured out and real agitation listing what we still did not know. The disquiet I read in Johnson’s musings tended towards questions around the toxicity and pharmacokinetics of PFOS while my own anxiety was about understanding the root cause of human- and environmental- exposure. (I havent been able to locate many of my reports in publicly available records).
Take a look at #1408 when you have the time. Remind yourself that it was written in 1993, 7 years before 3M admitted publicly their chemical (a likely carcinogen) was in your blood and the blood of your baby. See where YOUR emotions go when you read that statement of fact halfway down the first page: “We have found PFOS in human sera (Plant workers and blood bank)” followed by all the disturbing questions and anxious musings about potential health effects associated with PFOS exposure. Read through Johnson’s questions about how PFOS could affect human health, especially vulnerable populations, and consider how few of those questions 3M invested in answering.
To me, #1408 reads like a catharsis, perhaps written on a day when, for Johnson, the strategy of ignorance was not enough to bear the burden of knowledge.
Please refer to my previous post for a refresher on the relevant history for PFOS analysis and agnotology within 3M (1975-1983), Part I.
*Note: I used the acronym LCMS to refer, generally to the technique inclusive of any form of ionization (e.g. thermospray, electrospray, ion spray, particle beam) and any form of mass spec (e.g. quadrapole, tandem quadrapole, ion trap).
As referenced in substack post: NON-COMPREHENSIVE Peer-Reviewed Literature Review, 1982-1993, for
LCMS relevant to the analysis of perfluorooctane sulfonate PFOS
Andries P. Bruins, Lars O. G. Weidolf, Jack D. Henion, and William L. Budde; Analytical Chemistry 1987 59 (22), 2647-2652
Ballard, J.M. and Betowski, L.D. (1986), Org. Mass Spectrom., 21: 575-588.
Bruins, A. P., Covey, T. R., & Henion, J. D. (1987) Analytical Chemistry, 59(22), 2642–2646
C. R. Blakley and M. L. Vestal; Anal. Chem. 1083, 55, 750-754, 1983
Cooks, R., Busch, K., & Glish, G. (1983). Science, 222(4621), 273–291.doi:10.1126/science.6353576
Covey, T. R., Bruins, A. P., & Henion, J. D. (1988). Organic Mass Spectrometry, 23(3), 178–186
Covey, T. R., Lee, E. D., Bruins, A. P., & Henion, J. D. (1986). Analytical Chemistry, 58(14), 1451A–1461A.
DN Heller, FJ Schneck; Biological Mass Spectrometry, 1993; Volume22, Issue 3; 1993, pp 184-193
Draper, W.M., Brown, F.R., Bethem, R. and Miille, M.J. (1989). Biol. Mass Spectrom., 18: 767-774
E. C. Huang, J.J. Conboy, T. Wachs, and J.D. Henion, Anal. Chem., 1990, 62. 713A-725A
Eckers, C., Henion, J. D., Maylin, G. A., Skrabalak, D. S., Vessman, J., Tivert, A. M., & Greenfield, J. C. (1983). International Journal of Mass Spectrometry and Ion Physics, 46, 205–208
Eckers, C., Skrabalak, D. S., & Henion, J. (1982); Clinical Chemistry, 28(9), 1882–1886
F. Ventura, J. Caixach, A. Figueras, J. Espalder, D. Fraisse, J. Rivera; Water Research, Volume 23, Issue 9, 1989, Pages 1191-1203
Flory, D.A., McLean, M.M., Vestal, M.L., Betowski, L.D. and Gaskell, S.J. (1987), Rapid Commun. Mass Spectrom., 1: 48-50.
G.H. Hsu, T.R. Covey, and J.D. Henion, J. Liq. Chromatogr., 1987, 10, 3033-3045
Huang, E.C., Henion, J.D. ; J Am Soc Mass Spectrom 1, 158–165 (1990)
Hung-Yu Lin, R.D. Voyksner; Anal. Chem. 1993, 65, 451-456;
J. J. Conboy, J.D. Henion, MW Martin, JA Zweigenbaum; Anal. Chem. 1990, 62, 8, 800–807
Jack Henion, Tim Wachs, and Alex Mordehai, J. Pharm. and Biomed. Anal., 1993, 11, 1049-1061.
Pleasance, S., Kelly, J., LeBlanc, M. D., Quilliam, M. A., Boyd, R. K., Kitts, D. D., … North, D. H. (1992). Biological Mass Spectrometry, 21(12), 675–687
R.D. Voyksner, J.R. Hass, M.M. Bursey; Analytical Letters, 15(A1), 1-12, 1982
Robert Voyksner, Carol Haney; Anal. Chem. 1985, 57, 6, 991–996
Schneider, E., Levsen, K., Dähling, P. et al. Analysis of surfactants by newer mass spectrometric techniques. Z. Anal. Chem. 316, 488–492 (1983)
Voyksner, R.D., Bursey, J.T., Hines, J.W. and Pellizzari, E.D. (1984), Biomed. Mass Spectrom., 11: 616-621.
Voyksner, R.D., Smith, C.S. and Knox, P.C. (1990), Biomed. Environ. Mass Spectrom., 19: 523-534.
W. Muck and J. D. Henion, Biomed. and Environ. Mass Spectrom., 1990, 19, 37-51
Watson, D., Taylor, G.W. and Murray, S. (1985), Biomed. Mass Spectrom., 12: 610-615
