Groundwater Contamination by PFAS from Military Firefighting Training to Persist for Centuries.

[NNadir]

I have very little time on my hands this weekend, but I thought I'd just note this paper I came across as I work to catch up on the literature:

Centurial Persistence of Forever Chemicals at Military Fire Training Sites Bridger J. Ruyle, Colin P. Thackray, Craig M. Butt, Denis R. LeBlanc, Andrea K. Tokranov, Chad D. Vecitis, and Elsie M. Sunderland Environmental Science & Technology 2023 57 (21), 8096-8106.

Some text from the introduction:

Severe contamination of freshwater resources at diverse locations globally has been caused by fire training and firefighting using aqueous film-forming foams (AFFF) that contain 1–5% by weight per- and polyfluoroalkyl substances (PFAS). (1) Drinking water hotspots for one PFAS, perfluorooctane sulfonate (PFOS), have been detected near hundreds of United States (U.S.) military bases that repeatedly used AFFF. (2) Suppressed immune function and other adverse health effects have been associated with exposures to PFOS at concentrations less than 1 ng L–1, which is more than 10 billion times lower than concentrations found in AFFF. (3,4) Polyfluoroalkyl precursors that transform into PFOS and other terminal PFAS of regulatory concern make up the majority of PFAS in AFFF. (1,5,6) For example, AFFF manufactured by 3M prior to 2001 (3M AFFF) contained hundreds of precursors that accounted for >50% of the total PFAS. (5?7) However, most precursors are not routinely monitored, and all are currently unregulated. Thus, additional information on the physicochemical properties, environmental behavior, and persistence of precursors is urgently needed.

Commercial standards are available for less than 10 out of the hundreds of precursors previously detected in AFFF. (7?10) This means a toolbox of analytical methods (Table S1) is needed to fully account for all of the PFAS in AFFF and present at AFFF-contaminated sites. In prior work, we reconstructed the mass budget for PFAS in AFFF and impacted surface waters, and developed a method for calculating the relative proportions of PFAS produced by 3M and other manufacturing processes in environmental samples. (6,11) This method relies on a combined analytical and statistical method that applies the total oxidizable precursor assay (TOP) followed by Bayesian inference (BI). TOP+BI quantifies precursors grouped by their perfluorinated chain length (Cn) and manufacturing origin (electrochemical fluorination/3M versus fluorotelomerization/FT) from the change in perfluoroalkyl carboxylates (PFCA) before and after TOP based on the oxidation patterns of these precursor groups...

...The main objectives of this study were to quantify: (1) the flux of PFAS from the vadose zone into groundwater and (2) the contributions of precursor transformation to groundwater contamination at an AFFF-contaminated military base on Cape Cod, Massachusetts (Joint Base Cape Cod: JBCC). We used multidecadal groundwater time series data in combination with a vadose zone survey conducted by the U.S. military to constrain a numerical model for precursor transport and transformation at the site. Results provide the first estimates of precursor physicochemical properties (sediment–water and air–water interface partitioning) and biotransformation rates grouped by chain length. We project modeling results forward in time to estimate the expected timescales of contamination in the absence of remediation efforts...

A figure from the paper:



The caption:

Figure 1. Prevalence and magnitude of 3M AFFF contamination at military bases across the continental U.S. (a) Location of 327 military fire training areas with known AFFF use, including the field site for this study (JBCC, red star). (20) (b) Maximum concentrations of PFOS measured in groundwater at AFFF-contaminated military sites across the country. (21) Gray shading in (b) shows the minimum, mean, and maximum PFOS concentrations at JBCC measured in well S425-0063 indicated in (c). (c) Site map of the fire training area at JBCC. The elevation of the groundwater table in meters is indicated by the contour lines. The land surface elevation of the fire training area is 32 meters above sea level, and the depth to groundwater is ?17 meters.

Another figure, related to the expected lifetime of these contaminants:

Figure 6. Contemporary and projected future PFAS reservoirs beneath the fire training area. (a–d) Direct measurements as blue circles for groundwater (GW) and green squares for the vadose zone, and modeled reservoirs as lines (expected mean) and shaded regions (IQR) from the first use of the site to the present. (e–h) Projected distribution of PFAS in the vadose zone and groundwater following the use of 3M AFFF. The gray-shaded regions indicate the temporal range of sampling window in this study. The black dashed line indicates the year when concentrations in groundwater are expected to fall below the Massachusetts state-level MCL.

Some conclusions from the paper:

The U.S. military is the largest global user of AFFF. (50) Military sites contaminated by AFFF manufactured by 3M are distinguishable by high PFOS concentrations in groundwater and downgradient drinking water sources (Figure 1a,b). (2,21) PFOS is absent from contemporary foams and its production was phased out by 3M (the main global manufacturer) around 2002, indicating residual contamination is a legacy problem. (5,6,8) Based on reported groundwater PFOS concentrations at military bases across the U.S., we estimate that 3M AFFF was used by at least two-thirds of the 327 presently identified PFAS-contaminated military sites. (21)
This study highlights the potential for elevated PFAS exposures downstream from AFFF source zones to persist for centuries. Since chemical transport is comparatively rapid on Cape Cod, other AFFF sites may experience even longer periods of elevated PFAS exposures. The combined effect of surface activity and sorption of PFAS to solids means most releases at AFFF-contaminated sites are retained in the vadose zone. This implies that remediation of the vadose zone is needed to prevent long-term contamination. Otherwise, groundwater contamination would need to be captured and treated for centuries to limit deleterious downstream exposures...

Remediation might involve solid phase extraction, however disposal of the extractants without destruction of the adsorbed contaminants simply moves pollution from one place to another, this at a material and energy cost.

In my view, the only low impact means of sustainably cleaning up this mess accumulated over the late 20th century would be with ionizing radiation.

Have a nice weekend.

[Historic NY]

1. The scary thought is how long this was going on and into water supplies undetected.

We have a site here in the Hudson Valley at an air guard facility.

[NeoGreen]

2. If your only tool...

...is a hammer,

Define, "low impact."

[NNadir]

3. It's not worth defining anything to anyone clearly lacking any scientific abilities.

I know the species well here, and I'm familiar with the type; they've been prattling on here for years, through the more than 50 ppm increase in dangerous fossil fuel waste in the planetary atmosphere (about which they couldn't care less).

Radioactivity is an essential tool, and the rhetoric of antinukes is exactly equivalent to the rhetoric of antivaxxers, although truth be told, antinukes have killed vastly more people with the application of their ignorance than antivaxxers did with theirs.

The death toll of antinukism is about 19,000 people per day, recorded only as air pollution, not even counting climate change and the death toll associated with a burning planet, which left the air in the Northeast of this continent nearly unbreathable. Covid on its worst day never killed 19,000 people, and air pollution has been around much longer than Covid and is still around.

It's a holocaust per year.

And of course, this summer, while bourgeois antinukes lay around the swimming pools picking lint out of their navels trying to figure out if any atoms from Fukushima have showed up in their rather pixilated brains, oodles of people will die all around the world from extreme heat without a peep from these barely literate malcontents.

Do I make myself clear?

No?

I couldn't care less.

I'd love to congratulate all the world's antinukes on their success in setting the planet on fire.

[NeoGreen]

4. If you truly believe that...

...

...the only low impact means of sustainably cleaning up this mess accumulated over the late 20th century would be with ionizing radiation.

You should present it.

This organization would love to give you a forum to present this hypothesis:

https://www.awma.org/

As a matter of fact, they have a conference dedicated to the problem of PFAS in the environment:

https://www.awma.org/pfas

Next one is in late January 2024 in NC, just a short train ride from anywhere on the east coast.

Plenty of time to prepare a presentation, you do it on DU all the time.

I would look forward to reading it and the reviews/comments.

[NNadir]

5. I have posted many references to the radiolytic decomposition of PFAS...

..in my journal here.

It's a topic I discuss relatively regularly as I am intimately aware of environmental issues and give a shit about them.

I have often included graphics showing the free radical degradation mechanism of the carbon flowing bond, with a bond energy in the far UV range.

It's unsurprising to me that people who hold science in contempt and whose disinterest in environmental issues, which they hold far below their uneducated parochial paranoia about, say, Fukushima, have not bothered to read anything either from me or from anyone else concerning this topic.

I already knew of course that just don't give a rat's ass about the environment.

[NeoGreen]

6. Any honest scientist who cares about the environment and...

...has a hypothesis as profound as the one you presented in the OP above, would jump at the chance to present it to a forum dedicated to the problem.

If you truly believe it, you would present it for peer review.

Not hide it in some blog.

You are sitting on the only sustainable low impact means to address PFAS, and you think posting it in a blog is good enough?

Wow.

Madame Curie would be proud.

[NNadir]

7. It's not my job to educate fools.

Last edited Sat Jun 10, 2023, 10:58 PM - Edit history (1)

To the extent I participate in education here, my journal here speaks for itself. Once again for the benefit of anyone who has any difficulty with reading, I have discussed the radiolytic destruction of PFAS on many occasions here, citing the primary scientific literature.

If one is too busy carrying on insipidly about Fukushima to read about anything else, that's hardly my problem.

In about 5 minutes I'm going to hear a lecture by a two time Nobel Laureate. I don't have much time to talk to clowns.

[NNadir]

8. On reflection, not that I credit anything antinukes say about science or scientists, I'll...

...provide a link to some earlier posts on this topic that whiny antinukes may have missed while they spent their days trying to find out if radiation killed anyone at Fukushima, even if they didn't give a shit about the 19,000 people who died from seawater.

(Since they don't give a fuck about climate change, antinukes have no interest in the safety of coastal cities, even though in their tortured imagination the thought that someday, somewhere, somehow someone may actually die of radiation in the event, given them cause to crank up their fossil fueled computers and scream across the internet about it.)

It's just as amusing as hell to see an antinuke express any interest in science. In general they focus on soothsaying, this in a purely mystical sense.

Two links specific to the issue of radiolysis of PFAS from posts I've written here are these:

A Nice Scientific Review Article on the Destruction of Persistant Perfluoroorganic Pollutants. (2020)

...and...

Nice Mechanistic Graphic on the Mechanism of Mineralization of PFAS by Irradiation. (2022)

Of course, I don't write posts about every scientific paper I read on any topic; I would be required to write hundreds of posts per week to do so.

Both posts, regrettably, contain links to the primary scientific literature and describe, um, science. While I hardly am likely to "jump at the chance" to discuss science with people whose contempt for it is obvious, and because I know that in any case, any attempt to tell people whose dogma consists of chanting about how nuclear energy is "too dangerous" and hundreds of millions of deaths in this century from air pollution are not a reflection of fossil fuels being "too dangerous" or climate change being "too dangerous," I'm dubious that it will do any good to present these links.

These people who don't give a rat's ass about anything but some radioactive atoms escaping into the environment to join those already there, for instance the potassium on which their insipid and useless lives depends.

I have only requested one piece of information from antinukes, who carry on insipidly about used nuclear fuels that they, in their appalling ignorance, call "nuclear waste."

The question I ask is this one: If so called "nuclear waste" is so dangerous, can you demonstrate that in the 70 year history of its accumulation, that its storage has killed as many people as will die from air pollution in the next six hours, about 4500 people?

They never answer. They change the subject, they mumble insipidly, that get even more puerile than normal, but they never answer the question.

The reference for the 4500 figure, by the way is here, from one of the most prominent scientific medical journals in the world:

Global burden of 87 risk factors in 204 countries and territories, 1990–2019: a systematic analysis for the Global Burden of Disease Study 2019 (Lancet Volume 396, Issue 10258, 17–23 October 2020, Pages 1223-1249).

This study is a huge undertaking and the list of authors from around the world is rather long. These studies are always open sourced; and I invite people who want to carry on about Fukushima to open it and search the word "radiation." It appears once. Radon, a side product brought to the surface by fracking while we all wait for the grand so called "renewable energy" nirvana that did not come, is not here and won't come, appears however: Household radon, from the decay of natural uranium, which has been cycling through the environment ever since oxygen appeared in the Earth's atmosphere.

Here is what it says about air pollution deaths in the 2019 Global Burden of Disease Survey, if one is too busy to open it oneself because one is too busy carrying on about Fukushima:

The top five risks for attributable deaths for females were high SBP (5·25 million [95% UI 4·49–6·00] deaths, or 20·3% [17·5–22·9] of all female deaths in 2019), dietary risks (3·48 million [2·78–4·37] deaths, or 13·5% [10·8–16·7] of all female deaths in 2019), high FPG (3·09 million [2·40–3·98] deaths, or 11·9% [9·4–15·3] of all female deaths in 2019), air pollution (2·92 million [2·53–3·33] deaths or 11·3% [10·0–12·6] of all female deaths in 2019), and high BMI (2·54 million [1·68–3·56] deaths or 9·8% [6·5–13·7] of all female deaths in 2019). For males, the top five risks differed slightly. In 2019, the leading Level 2 risk factor for attributable deaths globally in males was tobacco (smoked, second-hand, and chewing), which accounted for 6·56 million (95% UI 6·02–7·10) deaths (21·4% [20·5–22·3] of all male deaths in 2019), followed by high SBP, which accounted for 5·60 million (4·90–6·29) deaths (18·2% [16·2–20·1] of all male deaths in 2019). The third largest Level 2 risk factor for attributable deaths among males in 2019 was dietary risks (4·47 million [3·65–5·45] deaths, or 14·6% [12·0–17·6] of all male deaths in 2019) followed by air pollution (ambient particulate matter and ambient ozone pollution, accounting for 3·75 million [3·31–4·24] deaths (12·2% [11·0–13·4] of all male deaths in 2019), and then high FPG (3·14 million [2·70–4·34] deaths, or 11·1% [8·9–14·1] of all male deaths in 2019).

Interestingly this comprehensive survey has nothing related to nuclear power, despite all the coal, gas, and oil that has been burned to run websites from dumbass antinukes.

And, of course, it is perfectly understandable why antinukes are unfamiliar with the contents of this paper. They don't read science; they don't care about science; they don't care about humanity; and they don't care about the state of the planet.

They are such appalling people that they feel that anyone of them can arrogantly suggest that a scientist should "jump" at a chance to correct their ignorance.

Personally, as a scientist, I find these pernicious set of people tiresome. For years, I had this set on my ignore list, but in a moment of weakness, I seemed to have removed some of them thinking that they might be amusing, but the death toll related to their propaganda isn't funny. I'm in the process of returning some of these morons to that list.

At this point, my only interest in them is to recall the disgust I feel for how many people have been killed by their loud assertions of ignorant dogma. Again, that number, even without climate change, is on the scale of hundreds of millions of people, about 80 million since Fukushima.

Have a pleasant Sunday afternoon.