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Sat Aug 17, 2019, 12:41 PM

China's Hydrofluorocarbon Emissions for 2011−2017

Last edited Sat Aug 17, 2019, 04:32 PM - Edit history (1)

The paper I'll discuss in this post is this one: China’s Hydrofluorocarbon Emissions for 2011–2017 Inferred from Atmospheric Measurements (Bo Yao,† Xuekun Fang,*,‡ Martin K. Vollmer,§ Stefan Reimann,§ Liqu Chen,† Shuangxi Fang,† and Ronald G. Prinn,‡ Environ. Sci. Technol. Lett. 2019, 6, 479−486)

A long time ago, I had a relatively brief interlude of living, after high school, as a beach bum in Hermosa Beach, California, which was - this is how old I am - quite affordable on the salary of a factory laborer, which was the job I held at the time. Of course, in order to a beach bum, to afford to rent a place at the beach, one had to have a roommate, and I did, a wonderful person my age who despite several descents into serious alcoholism, remained a lifelong friend, until he died.

He died from melanoma. Fun and the sun. We had good times there in Hermosa Beach. California. In those days there was no helmet law in California, and he used to cruise around Hermosa Beach shirtless and helmetless.

(As Shakespeare put it, He... "...would have died hereafter." )

I actually had quite a few friends who died from melanoma.

My roommate, who was among other things, highly intelligent but nevertheless worked the same kind of dead end jobs as I did, had quite a wonderful sense of humor. One of the expressions of that humor was to wake up on Saturday mornings, switch on our tiny black and white television and while drinking coffee and chain smoking cigarettes watching Japanese monster movies from the 1950s, Godzilla, Gamera and all that stuff, and doing wonderful mimicry of the lines therein.

The monsters in these movies were all mutants, as I recall, generally resulting as a side effect of nuclear testing. The movies were either hilarious, at least the way my roommate interpreted them, or they were childish and silly, but one supposes that the underlying theme, as the monsters routinely trashed power lines, was that there were some, um, problems, associated with uncontrolled wildly applied technologies introduced without much forethought.

Who would have thought that?

I wasn't a big fan of actually watching the monster movies myself but of course, I was exposed to them by osmosis. One feature I recall of them was that they usually involved a consortium of scientists gathered in the room, assembled by the Japanese government and civil authorities, and led by a senior scientist who knew everything there was to know about radiation induced monsters. The scientists would declare a strategy for dealing with the monster - sometimes it involved a statement that the authorities must get an atomic bomb from the Americans - and the authorities would accept and do whatever the scientists said, because they were scientists.

I told you the movies were silly.

While I was beach bumming, serious work was going on about 80 km away at the University of California at Irvine, by Mario Molina a post doc, to study the atmospheric chemistry of chlorofluorocarbons, the CFC's, which were widely utilized refrigerants.

Mario Molina won the Nobel Prize for this work. By the way, Mario Molina is the first Mexican scientist to win the Nobel Prize. He immigrated to the United States which is where, as an immigrant, he did work that um, saved many lives that otherwise would have been lost to, um, melanoma, one of the still intractable fatal cancers.

The choice to use CFC's for refrigerators and air conditioners was because the scientists who discovered them thought they were wonderful compounds, because they had high heats of vaporization and because they were inert. This was a great discovery, or at least was thought to be a great discovery until Mario Molina, Mexican Immigrant to the United States, discovered that they weren't inert; they were substances that catalyzed the destruction of the ozone layer that protects the earth and all living things from radiation, solar radiation. Although the CFC's are catalysts, like all catalysts, they are consumed ultimately. In this case they are consumed, long term, by radiation, and end up decaying, albeit with a fairly long half life, into hydrochloric & hydrofluoric acid and carbon dioxide.

Donald Trump, by the way, is not intellectually qualified to mow Mario Molina's lawn, by the way, or pick oranges from Molina's orange trees, if Mario Molina has orange trees. Donald Trump is way too stupid and ignorant to work for Mario Molina in any capacity.

Because of Mario Molina's discovery, the world's first major environmental treaty, the Montreal Protocol, was ratified by the major governments of the world in 1987, when the racist moron Ronald Reagan was President of the United States and showing the effects of the Alzheimer's disease that would ultimately kill him. I personally believed that the United States would move away from allowing racist intellectually impaired and morally impaired from running its government from the White House.

I was clueless. The racist moron in the White House, a low quality doltish and clownish Mussolini knock off, makes Ronald Reagan look far less odious. Making Ronald Reagan look less odious in a remarkable achievement, probably the only achievement that bone spur Mussolini will ever have.

The Montreal Protocol was the last time, by the way, that international governments behaved as nobly as the fictional Japanese civil authorities dealing with Gamera; they actually listened to the scientists.

Of course, the CFC manufacturers definitely engaged, briefly as I recall, although I was relatively uneducated at the time, in the cigarette company inspired denial game at the time, the same strategy now widely and far more successfully utilized by the dangerous fossil fuel companies to prevent the destruction, on a far greater scale than CFC’s, of the planetary atmosphere. Eventually though, the CFC companies realized that they could make a ton of money by replacing CFC's with the recently discovered HFC's, which are similar to the CFC's but lack chlorine atoms.

So eventually the CFC corporations signed on ultimately to the Montreal Protocol, and yes, they made a ton of money by doing so. Win-win, I guess.

All of the world's modern refrigerators, all of the air conditioners we burn dangerous fossil fuels to run to shield ourselves from climate change, all the refrigerants in our swell Tesla cars that we hype to shield ourselves from our own moral poverty with respect to climate change utilize HFC's rather than CFCs.

The HFC's share the property that made CFC's useful, relatively high heats of vaporization and a phase diagram that has a liquid/vapor line near ambient temperatures, relative chemical inertness, but like CFC's, they share a physical property that makes them less benign than people are willing to believe, which is that they are potent greenhouse gases. And as is the case with CFC's, they have long atmospheric half lives; some of them have half-lives of thousands of years, and global warming potentials which are, in some cases, tens of thousands of times larger than that of carbon dioxide.

We all like to think we are "green" here in the United States, and like to wag our fingers at China, where many of the materials for our "green" technology are manufactured and/or (at least until recently) our toxic stuff is "recycled," the latter practice resulting in the health consequences for Chinese children who have high levels of carcinogenic PBDE and related flame retardants in their blood plasma and other tissues. We import "green" Chinese stuff and export our dirty polluting industrial practices (which by the way make money) and declare ourselves "green."

We are as clueless as a stupid kid who might have thought that the United States would never once again allow a racist intellectually impaired person with missing morals, such as Ronald Reagan was, again to occupy the White House.

Never underestimate ignorance, because ignorance kills, and as we are seeing, world wide, with the rise of ignorant protofascist or openly fascist "leaders," ignorance can be very popular.

This brings me to the paper to which I linked at the outset of this post. From the introductory text:

Hydrofluorocarbons (HFCs) have an only negligible effect on stratospheric ozone loss.1,2 Thus, they have been used to replace ozone-depleting chlorofluorocarbons (CFCs), halons and hydrochlorofluorocarbons (HCFCs), in refrigeration, air conditioning, foam blowing, and other applications since the 1990s. This is in compliance with the Montreal Protocol that was agreed on in 1987 for the control of the consumption and production of ozone-depleting substances (ODSs).1 However, most HFCs are potent greenhouse gases with high global warming potentials (GWPs).1 The Kigali Amendment to the Montreal Protocol was agreed upon in 2016 and sets up schedules for limiting HFC production and consumption in both developed and developing countries. Previous studies showed that atmospheric mole fractions of HFCs have increased globally between 2012 and 2016 by an average of 1.6 ppt year−1 for HFC-32 (CH2F2), 2.1 ppt year−1 for HFC-125 (CHF2CF3), 5.6 ppt year−1 for HFC-134a (CH2FCF3), and 1.5 ppt year−1 for HFC-143a (CH3CF3), and these rates are faster than average increases reported for 2008−2012.1,3

Along with the phase-out process of CFCs and HCFCs in compliance with the Montreal Protocol, HFCs have become widely used as replacements in China and other parts of the world since the 1990s. For example, in new mobile air conditioners in China, HFC-134a has replaced CFC-12 (CCl2F2) as a refrigerant since around 2000.4 More recently, HFCs have become widely used to replace HCFCs, whose production and consumption were frozen in 2013 and will be phased out by 2030. For example, HCFC-22 (CHClF2), which was the predominant refrigerant used in the room air conditioning sector, is currently being replaced by R-410A (a blend of HFC-32 and HFC-125).5,6 Apart from the Kigali Amendment to the Montreal Protocol with a freeze on production and consumption of HFCs in 2024, no additional regulations on HFCs [excluding HFC-23 (CHF3)] are currently being enforced in China.

There is a lot of interesting stuff in the paper, all kinds of cool equations but the graphics therein give a feel for the results.

The authors, from Chinese, Swiss and American (MIT) institutions, engage in "bottom up" - figures obtained from industrial reports - and "top down" - observations of atmospheric concentrations in sampling stations across eastern Asia, to estimate the emissions of these gases.

The caption:

Figure 1. Sampling sites used in this study. The sites are Heyuan (HYN; 23.69°N, 114.60°E), Shangri-La (XGL; 28.01°N, 99.44°E), Jiangjin (JGJ; 29.15°N, 106.15°E), Lin’an (LAN; 30.30°N, 119.73°E), Mount Waliguan (WLG; 36.29°N, 100.90°E), Shangdianzi (SDZ; 40.65°N, 117.12°E), and Longfengshan (LFS; 44.73°N, 127.60°E). The figure and image were made with GeoMapApp ( www.geomapapp.org )/CC BY/CC BY,(32) and the China boundary file is from MeteoInfo
( http://www.meteothink.org/index.html ).

The caption:

Figure 2. Annual emissions of HFCs in China derived from inverse modeling using atmospheric observations at seven sites.

The caption:

Figure 3. Estimates of HFC emissions in China during the period of 2005–2017. The emission estimates are from top-down(8−15) and bottom-up(6,33,34) approaches. The x-axis error bar in the plot represents the span of the target period in the respective study, for example, the 14 months from November 2007 to December 2008 in ref (11) and the 3 years from 2010 to 2012 in ref (14).

The caption:

Figure 4. Proportions of each HFC of the total in China, in terms of mass and CO2-equivalent emissions. An asterisk denotes the combined proportion of HFC-236fa, HFC-245fa, and HFC-365mfc to total HFCs.

The caption:

Figure 5. Global HFC emissions and China’s contributions to the global atmospheric HFC radiative forcing. CO2-equivalent emissions for Annex I countries were derived from UNFCCC.(29) Global total CO2-equivalent emissions were based on emissions derived from observations at remote AGAGE stations.(22,30) Emissions for China were derived from ref (6) for 2005–2010 and from this study for 2011–2017. The “aggregated” error bars shown in China’s HFC CO2-equivalent emissions during the period of 2011–2017 are the sum of the postererior emission uncertainty multiplied by the corressponding GWP value for each HFC. Contributions from China’s HFC emissions to global HFC radiative forcing were calculated using the AGAGE atmospheric measurements ( http://agage.eas.gatech.edu/data_archive/global_mean/ ). In panel b, uncertainties were not estimated because uncertainties were not available for China’s HFC emissions during the period of 2005–2010.(6).

International treaties, as noted in the paper, call for the phase out of HFC's, by the way, by 2024. Good luck with that humanity, while we continue to elect tin horn Mussolini types around the world, celebrants of ignorance.

Future generations will live with this crap we've left in the atmosphere for thousands of years, although technology exists that might accelerate their degradation. One of the best ways, and effectively the only way major way environmentally, to degrade these compounds is to expose them to radiation. Unfortunately many of us have a preternatural and frankly ignorant fear of radiation, and therefore many of claim that radioactive materials are waste and thus refuse, more or less to make them and more importantly to utilize them. Thus the only sink for these fluorinated gases is the stratosphere and ionsphere, where they are relatively depleted owing to the Maxwell Boltzman distribution owing to their high molecular weights with respect to nitrogen and oxygen.

We are as clueless, in this regard, as a stupid kid who might have thought that the United States would never once again allow a racist intellectually impaired person with missing morals, such as Ronald Reagan was, again to occupy the White House. We think it would be a good idea to bury these useful materials.

Go figure.

Fluorine is, of course, the most electronegative of all the elements in the periodic table, which means that it forms very strong bonds with other elements, and when these bonds are covalent, the resulting compounds will be long lived and persistent. Thus we should be very careful with their use. Another serious environmental crisis is concerned with fluorinated organic acids and sulfonic acids, PFOS, PFOA. These compounds are so ubiquitous that I recently came across a paper in analytical chemistry noting that it is almost impossible to obtain a "blank" - a substance in which they are not present - for analytical purposes. This is scary.

These compounds, PFOS and PFOA type compounds, are subject to a small degree to metabolism, which lies behind their toxicity, but like other fluorine compounds are subject to radiolytic degradation, since gamma radiation, x-rays, and UV radiation possess sufficient energy to break the strong chemical bonds responsible for their persistence.

A last point: Refrigeration devices are merely heat engines run in reverse. In recent years, as I've been studying thermoelectric devices whenever I have time. These devices seem to be an excellent tool to engineer away the risk of events like Fukushima in nuclear power plants, much as we re-engineer aircraft when the causes of crashes are identified. (To get some insight to this procedure, I recommend the excellent engineering program on the Smithsonian Channel Air Disasters.) We don't seek to ban aircraft when they crash, and ban cars when they crash or are responsible for huge environmental destruction, although in the latter case I think we should at least consider a ban. There will never be such a thing as a "green" automobile. The car CULTure is not sustainable and never will be.

Nuclear energy, which is responsible for the accumulation of potentially very useful radioactive materials to which ignorant people refer to as "nuclear waste," is not perfect and it is not risk free, but it need not be either to be vastly superior to everything else. It only needs to be vastly superior to everything else, which it is.

There is a relevant analogy here:

It was a good idea to replace CFC's with HFC's, even if HFC's are not entirely without risk. CFC's were very serious carcinogenic pollutants, as the friends I have who died from melanoma, may have had their fatal cancers induced because of them.

In any case, for the replacement it is possible to run a thermoelectric device in reverse, just as one can run a heat engine in reverse in a refrigerator or in the air conditioner of a swell Tesla electric car. Thermoelectric devices are, happily, a very active area of research, and though their thermodynamic efficiency is still low, they are being improved, and I certainly support all research into them.

Thus solid state refrigerators are not only possible, but a few commercial examples already exist I believe.

Have a pleasant weekend.

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Response to NNadir (Original post)

Sat Aug 17, 2019, 01:31 PM

1. My Dear Mr. Nadir. On two different occasions in the past, when I have commented....

....on one of your postings, you have responded in a manner that could be characterized as condescending. You recently acknowledged in another post that this may be one of your failings. I don't respond to this because I am, like you, generally unbothered by criticism. This most recent posting of yours leads me to forgive any and all personal affronts that have transpired because I truly admire your taking both Donald Trump and Ronald Reagan to task. "Not intellectually qualified to mow Molina's lawn" and "low quality clownish and doltish Mussolini knock-off" are truly poetic expressions of our new reality. I enjoy your postings even though, for a layman, they are impossible to understand completely. When you now consider thermoelectric cooling as inefficient (for now) alternative by which we may reduce HFC's, are you positing something different than the Peltier Effect solid state devices used in some campers and mobile homes?


That said, keep up the good work, doing what you do. I did enjoy your account of your trip to Oak Ridge, a while back.

Spell check doesn't like "thermoelectric".
I'll try "thermo-electric". Nope, still no good.

I can't end this without thanking you for reminding us of the Montreal Protocols and how we used to at least try to improve our situation with some cooperative agreements. I would hope that a new administration would declare a "Marshall Plan for Environmental and Energy Sciences" on day one.

I don't have any skin cancer yet from my beach bum days. Let's hope that our luck holds out.

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Response to EarnestPutz (Reply #1)

Sat Aug 17, 2019, 04:12 PM

2. Thank you. You are absolutely correct. A thermoelectric device run in reverse is a...

...Peltier effect device.

Thank you as well for having a relatively thick skin when my more obnoxious side arises which it does from time to time. I'm glad you were amused by my locutions about the orange idiot and his mis-worshiped predecessor, Reagan and that it makes you more forgiving of my previous excesses.

I do utilize the ignore key here quite a bit for people who I regard as impossibly ignorant - something you clearly aren't - which has helped me to get less upset with some of the absurd things one hears from time to time. I didn't use to do that, since I thought it was my responsibility to confront ignorance, but that was certainly arrogant and naive on my part, to think I could do that.

This said, I plainly confess that can have a problematic personality when even when dealing with people who are relatively open minded, which again, is my personality flaw and has nothing to do with the people I may offend.

The Montreal Protocol was a very hopeful political adventure in our time, one that certainly inspired a great deal of hope for humanity.

We do have nut cases in this most recent generation, that little Trump inspired Nazi asshole who shot up El Paso for example, but overall I'm very impressed with the young people I meet in this recent generation. They impress me. My sons are both better men than I could ever have hoped to be. I do hope that in their times this generation will revive a tradition of international sanity, something clearly coming apart in these times. They will need it if they are to survive what my generation has done to them. My generation, I think, is one of the worst generations to have lived since the time of Genghis Khan perhaps, and in terms of dolorous impact over the long term, maybe even worse that that.

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Response to NNadir (Reply #2)

Sat Aug 17, 2019, 06:20 PM

3. Thank you again for your thoughtful commentary. You've praised your son before and....

Last edited Sat Aug 17, 2019, 10:16 PM - Edit history (1)

....now add more praise for his generation. I'll second that as I admire my two adult daughters and their friends. In almost every way they are better people than my baby boom contemporaries. They are less materialistic, treat others better and work to make our future better, to name just a few things to admire. We can be proud and hopeful because of them.

That said, things are so bad today that invoking Ghenhis Khan somehow doesn't sound like hyperbole. Thanks again.
I confused CFC's with HFC's, didn't I?

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Response to EarnestPutz (Reply #3)

Sun Aug 18, 2019, 10:33 AM

4. Thank you again. No, you did not confuse HFC's with CFC's.

The latter were phased out by the Montreal Protocol, the former were the replacements. Since the replacements required manufacturers having fluorination capability to manufacture them, the same manufacturers who made CFC's, it was something of an easier sell to industry.

CFC's, even though banned, continue to be emitted by historical refrigeration units as they degrade. However overall they're declining in the atmosphere.

Recently it was discovered that there was rogue manufacture of them in China.

Since the HFC's are persistent, and because they are potent greenhouse gases, there are plans to phase them out as well. It appears that they are more soluble in water than the CFC's were, if I recall correctly from my general reading.

Replacement of these with Peltier devices would be a good approach, but we should keep in mind that they are currently at much lower thermodynamic efficiency than reverse heat engines, at least currently. Thus the replacement would require increases in energy consumption. This might therefore have the undesired effect of further accelerating climate change, since no serious effort has been made to make clean electricity, the effort to do so being subsumed by a nonsensical approach that did not, is not, and will not work, solar and wind energy.

In theory, if not in practice, we could accelerate their degradation, both residual and rogue CFC's and HFC's by exposing them to ground level radiation, which would have the added benefit of degrading ground level ozone, which in the troposphere, where almost all of us live, ozone is a serious air pollutant.

Because of their high molecular weight, CFC's and HFC's are much more concentrated at low altitude than at high altitude, which is a good thing, since this slowed the destruction of the ozone layer that protects the Earth from UV.

Regrettably, however, most used nuclear fuels are stored isolated from the atmosphere, in canisters under helium. Ideally, in my view, they would be removed from the canisters, reprocessed, with the strong gamma emitter system of Cs-137/Ba-137m utilized to synthesize insoluble cesium titanates. Titanates are wonderful catalysts for the mineralization, the complete destruction, of alkyl fluorides, the set of compounds to which both CFC's and HFC's. The radiation would provide the energy.

Radioactive cesium titanates might also prove useful for the destruction of PFOS and PFOA in severely contaminated ground waters, such as those observed in parts of Michigan and, I believe, Minnesota.

We do not have as much used nuclear fuel on this planet to make this practice a total solution to the problem, although it might help some. Cesium-137 is subject to Bateman equilibrium, which means at a given power level, it eventually approaches a point, asymptotically where it is decaying at exactly the same rate as it is being formed. It takes many centuries to approach this equilibrium point, but each year that passes, smaller and smaller amounts accumulate, and eventually the accumulations reach gram quantities per year, industrially insignificant.

But again, we're not even close to doing this, since most people - and it's supremely ignorant - regard used nuclear fuels as "nuclear waste," and not the valuable material it actually is. Used nuclear fuels are evaluated by the general public, fed by nonsense from scientifically illiterate and sensationalist journalists, with fear and ignorance.

The investment in fear and ignorance are serious, and in fact dangerous and deadly, psychological cultural practices.

I am very pleased that you observe in your daughters and their friends, the same qualities I see in my sons and their friends. Usually a great generation follows a disastrous generation, and one hopes history will repeat. From what I see, there is good evidence that it will

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Response to NNadir (Reply #4)

Sun Aug 18, 2019, 01:44 PM

5. Amazing. The idea that used nuclear fuel could be used to help reduce....

....harmful green house gases is, to me, just an amazing concept. I'd encourage you to write more about this in the hope that more people join in the climate change and nuclear power conversations with a different perspective.
I live downwind of the Hanford Nuclear Reservation in Washington State where we have spent billions on designing and building a vitrification plant to turn nuclear waste into "glass" that can be stored for millennia. The high end estimates for this project run out to the year 2102 with costs of $677 billion dollars.
I'd be interested in your thoughts about these and other forms of nuclear "waste" and opportunities for utilization rather than disposal.

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