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Rate of mass loss from the Greenland Ice Sheet will exceed Holocene values this century.

The paper I'll discuss in this post is this one: Rate of mass loss from the Greenland Ice Sheet will exceed Holocene values this century (Jason P. Briner, Joshua K. Cuzzone, Jessica A. Badgeley, Nicolás E. Young, Eric J. Steig, Mathieu Morlighem, Nicole-Jeanne Schlegel, Gregory J. Hakim, Joerg M. Schaefer, Jesse V. Johnson, Alia J. Lesnek, Elizabeth K. Thomas, Estelle Allan, Ole Bennike, Allison A. Cluett, Beata Csatho, Anne de Vernal, Jacob Downs, Eric Larour & Sophie Nowicki, Nature volume 586, pages 70–74 (2020))

So called "renewable energy" hasn't saved the world; it isn't saving the world; it won't save the world. I have nothing more to say about the literally pyrrhic apparent triumph of the antinukes than what it says on the AAAS t-shirt distributed this year says: Facts are facts.

Since this paper which is a modeling paper, suggests, by fitting the model to the best historical data on the Greenland Ice Sheet what the future of the ice sheet will be, given that we have deliberately chosen not to do anything effective about climate change:

The abstract of the paper is available at the link.

For convenience, an excerpt:

The Greenland Ice Sheet (GIS) is losing mass at a high rate1. Given the short-term nature of the observational record, it is difficult to assess the historical importance of this mass-loss trend. Unlike records of greenhouse gas concentrations and global temperature, in which observations have been merged with palaeoclimate datasets, there are no comparably long records for rates of GIS mass change. Here we reveal unprecedented mass loss from the GIS this century, by placing contemporary and future rates of GIS mass loss within the context of the natural variability over the past 12,000 years. We force a high-resolution ice-sheet model with an ensemble of climate histories constrained by ice-core data2.

They suggest the data to which they fit their model represents a loss of ice amounting to around 6,000 billion tons of ice per century, 6 trillion tons during the Holocene, which is the current post glacial era in which civilization arose. Using their model, they predict that Greenland will lose between 8,000 billion tons to 35,000 billion tons in the 21st century, greatly exceeding any value recorded in the last 12,000 years.

For those lacking access to the full paper, I'll offer a few excerpts and graphics. From the paper's introduction:

The GIS lies within the rapidly warming Arctic, and its contribution to sea-level rise has recently accelerated1. The increased rate of GIS mass loss since the 1990s is substantial, but the lack of data on long-term GIS mass change makes it difficult to evaluate this short-term phenomenon within the context of natural variability5,7. Efforts to quantify rates of ice-mass loss through time have relied on historical climate data and image analysis, contemporary airborne and satellite observations, and numerical ice-sheet simulations5,8,9. Combined, these approaches reveal that the GIS was roughly in neutral mass balance during the nineteenth century, experienced variable mass loss in the twentieth century, and has undergone a substantial increase in mass loss in the past 20 years1,5,10. The future of GIS mass change is uncertain, but projected warming combined with feedbacks in the coupled ice-sheet–climate system will lead to continued losses9,11,12. Given plausible future climate scenarios, the GIS may be entirely gone in as few as 1,000 years13...

A few excerpts from additional sections:

The GIS’s past...

...Geological observations of GIS change are most abundant during the Holocene14. For this reason, the Holocene has been targeted as a timeframe for simulating GIS history15,16,17,18,19,20. Model simulations so far have been used to assess spatiotemporal patterns of GIS retreat and to constrain its minimum size. Simulated changes in ice volume are largely the product of climatic forcing; palaeo-mass balance is typically modelled using one of the ice-core δ18O time series from central Greenland, which is converted to temperature and precipitation, and scaled across the ice sheet15. Some approaches improve model performance with geological constraints, but climate forcing is still scaled from limited ice-core data, sometimes using prescribed Holocene temperature histories to improve model–data fit16,17. One recent study19 used data averaged from three ice-core sites to adjust palaeotemperatures from a transient climate model, and scaled precipitation from one ice-core accumulation record. All these estimates of mass-loss rates during the Holocene provide important context for projected GIS mass loss, but they have not been extended into the future, making quantitative comparisons uncertain...

GIS modelling

We place today’s rates of ice loss into the context of the Holocene and the future using a consistent framework, by simulating rates of GIS mass change from 12,000 years ago to AD 2100. We use the high-resolution Ice Sheet and Sea-level system Model (ISSM), which resolves topography as finely as 2 km (refs. 21,22,23). Our simulations are forced with a palaeoclimate reanalysis product for Greenland temperature and precipitation over the past 20,000 years2. This reanalysis was derived using data assimilation of Arctic ice-core records (oxygen isotopes of ice, and snow accumulation) with a transient climate model (Methods). We account for uncertainty in the temperature and precipitation reconstructions by creating an ensemble of nine individual ISSM simulations that have varying temperature and precipitation forcings2 (Methods). Sensitivity tests using a simplified model in the same domain24 suggest that the range in plausible palaeoclimate forcing, which we use, has a larger influence on simulated rates of ice-mass change than do model parameters such as basal drag, surface-mass-balance parameters and initial state. We compare our simulated GIS extent against mapped and dated changes in the position of the GIS margin3,4...

Some pictures from the text:

Fig. 1: Domain for the ice-sheet model and moraine record of past GIS change in SW Greenland:

The caption:

a, Map of the present-day GIS, showing commonly used domains (as labelled) and our model domain (outlined in red). NO, north; NE, northeast; NW, northwest; CW, central–west; SE, southeast; SW, southwest. b, WSW Greenland (boxed in a), showing widely traceable moraine sequences3. JI, Jakobshavn Isbræ; KNS, Kangiata Nunaata Sermia. c, Cosmogenic–nuclide exposure-age chronologies of all moraines between the ocean and the GIS4 (boxed in b); 1σ age uncertainties are listed; moraine lines are dashed where uncertain. Base-map topography from BedMachine37.

Fig. 2: Increased and variable GIS mass loss during the Holocene.

The caption:

a, Simulated cumulative change in WSW GIS ice mass from 12,000 years ago to AD 1850, for nine model simulations (Methods). b, Simulated position of the WSW GIS margin in the Holocene, for the transect shown in Fig. 1c. Black circles represent independent observations of ice-margin position based on mapped and dated moraines (with one-standard-deviation age uncertainty); the red circle is the present-day GIS margin. c, Bar plot showing the mean rate of ice-mass loss from 12,500 to 7,000 years ago; vertical lines and shading show moraine age and one-standard-deviation uncertainty for every moraine between Baffin Bay and the present-day ice margin4; asterisks mark the five centuries with the highest rates of mass loss.

In figure 3, notice the vertical line on the extreme right of the large graphic. This would be an excellent time to tell me all about how many "Watts" of solar cells are installed in California. Please avoid, since we live in the age of the celebration of the lie, using units of energy, GigaJoules - which matter - in favor of units of peak power - which mean zero at midnight in California.

The annual weekly minimum for carbon dioxide concentrations as measured at Mauna Loa was likely reached last week. The data hasn't been posted, but as I follow these data points weekly, I expect it will come in at about 411.0 ppm +/- 0.2 ppm. In 2010, the annual minimum was reached in the week beginning September 26, 2010. At that time, the concentration of the dangerous fossil fuel waste carbon dioxide in the planetary atmosphere was 386.77 ppm. Read the caption and choose your dot on the vertical line that represents the 21st century, the age of "renewable energy will save us" aka, in my mind, the age of the lie.

Fig. 3: Exceptional rates of ice-mass loss in the twenty-first century, relative to the Holocene.

The caption:

The mean rate of ice-mass change each century, from 12,500 years ago to AD 2100, is shown by the black line. The light grey bars indicate the ice-mass change in each of the nine simulations. For the 1900s, simulated rates are shown in dark grey. For the 2000s, rates of ice-mass change for various RCP2.6 and RCP8.5 simulations are shown as blue and red circles (see legend in inset). The histogram on the right incorporates all (n = 1,125) Holocene rates of ice-mass change. The inset shows simulated rates of ice-mass change in annual timesteps from AD 1850 to AD 2100.

Fig. 4: Substantial change in surface elevation of the GIS over the twenty-first century.

The caption:

a–c, Simulated change in surface elevation of WSW GIS (metres per century; colour scale) for the centuries in the Holocene with the highest mass-loss rate (a, c) and during the cold event 8,200 years ago (b), from model experiment 9. d–f, Simulated change in surface elevation (metres per century; colour scale) over the twenty-first century under the MIROC RCP2.6 (e) and RCP8.5 (f) scenarios, compared to the twentieth century (d). g, Comparison of the mass-loss rate for WSW GIS (right axis, red) and for the entire GIS (left axis, black), from AD 1972 to AD 2018, based on observations5 (r2 = 0.82, where r is the correlation coefficient). h, Comparison of the mass-loss rate for WSW GIS (right axis, red) and for the entire GIS (left axis, black), from AD 2015 to AD 2100, from our simulation using the MIROC RCP8.5 climate forcing (r^(2) = 0.97).

Some additional text from the paper:

The substantial increase in rates of GIS mass loss in the past two decades is exceptional in the context of estimates of mass loss in the historic interval5,8,9,35. If the rates of mass loss observed over the past two decades were to remain constant for the rest of the twenty-first century, the total rate of mass loss over the twenty-first-century would be around 6,100 Gt per century for WSW Greenland5. This value is within the low end of our simulated range of mass-loss rates during the early Holocene. However, 6,100 Gt per century may vastly underestimate the rate of mass loss for the twenty-first century, because climate is projected to become increasingly unfavourable for maintaining even the current levels of GIS mass balance6. Our simulations of twenty-first-century WSW GIS mass loss, using an identical model and model set-up, address the limitation of extrapolating observed rates of mass loss and yield century-average mass-loss rates of 8,800–10,600 Gt per century for RCP2.6 scenarios and 14,000–35,900 Gt per century for RCP8.5 scenarios (Methods, Fig. 3).

As of 2018, the humanity was consuming 599.34 exajoules of primary energy per year. 81% of that energy came from dangerous fossil fuels, as opposed to 80% of 420.19 exajoules that were being consumed in the year 2000. Things are getting worse, not better.

Every year, quantities of carbon dioxide added to the atmosphere as dangerous fosssil fuel waste amounts to more than 35 billion metric tons. Land use changes, including those involved in providing so called "renewable energy" - for example the destruction of the Pantanal for ethanol farms - add about another ten billion tons.

To provide about 600 exajoules of primary energy each year, would require, assuming 190 MeV/fission, ignoring neutrinos, completely fissioning about 7.5 thousand tons of plutonium each year. The density of plutonium, in at least one allotrope, is about 19.9 g/ml, depending on the isotopic vector. The size of a cube containing 7.5 thousand tons of plutonium - which could never be assembled as such owing to criticality constraints - is less than 8 meters on a side.

I am often informed by people that "nobody knows what to do with (so called) 'nuclear waste.'" In saying this, it is very clear that these people have never in their wildest imagination ever considered what to do with hundreds of billions of tons of dangerous fossil fuel waste, which is choking the planet literally to death. Of course, their considerations are weak, because the best evidence is that these people can't be bothered to open a scientific paper or a science book on the subject of any kind of waste. Somehow people expect me to be impressed by rote statements reflecting, to my mind, a total lack of attention or at least a very lazy selective attention to statements from equally lazy and equally misinformed people, often journalists or "activists" of a type that have never passed a college level physical science course. Ignorance, we know, runs in circles, scientific and engineering ignorance as well as political ignorance.

I have been opening science books and reading scientific papers for the bulk of my adult life. A huge percentage of them are about waste and so called "waste." Perhaps, I'm the "nobody" about whom these people speak, since I know perfectly well what to do with so called "nuclear waste." It contains, I'm convinced, enough plutonium (as well as americium and neptunium) to save the Greenland Ice Sheet, and in fact, the world.

Tears in Rain.

I wish you a safe and pleasant weekend.

Nature: What a Joe Biden presidency would mean for five key science issues.

The following appears in the "News" section of the major scientific journal Nature:

What a Joe Biden presidency would mean for five key science issues (Amy Maxmen, Nidhi Subbaraman, Jeff Tollefson, Giuliana Viglione & Alexandra Witze, Nature News October 1, 2020.)

I believe the article is open sourced and anyone can read it.

Some Excerpts:

Election Day in the United States is a little more than a month away, and scientists are watching the outcome of the presidential race closely. President Donald Trump’s handling of the coronavirus pandemic, actions to downplay climate change and perpetuation of misinformation have horrified many scientists. “We face a national crisis unlike any we have witnessed,” says a statement of concern about the state of democracy in the country, drafted by US scientists and signed by more than 3,400 supporters in response to Trump’s leadership...

...But what does Biden, a six-term senator from Delaware who served as vice-president under former president Barack Obama, stand for science-wise? Nature interviewed current advisers to Biden, advisers who served during Obama’s presidency and policy analysts about actions the former vice-president might take in five key science areas if he’s elected. (The Biden campaign did not respond to questions from Nature.)

Pandemic response

If Biden wins the election on 3 November, he will inherit not only a country in the throes of a pandemic that’s destroyed lives and livelihoods — but also one in which public opinion is deeply divided over the true extent of the coronavirus outbreak and the measures taken to abate it. Despite public-health agencies counting more than 200,000 COVID-19 deaths in the country, some Trump supporters feel that the impact of the virus has been exaggerated in an effort to control the populace.

Why the United States is having a coronavirus data crisis

Biden would also inherit a haphazard pandemic response, researchers say. “The problem with our whole response is that we’ve been changing the response since day one,” says Georges Benjamin, the executive director of the American Public Health Association in Washington DC...

... Coming in with a strong response plan and the ability to adapt to an evolving situation will be crucial for steadying both the outbreak and the US economy, he adds.

Biden’s pandemic plans — which his team has been preparing since March, say sources close to the campaign — promise to ramp up the country’s test-and-trace programmes; address racial and ethnic disparities in COVID-19 infection rates and outcomes; and rebuild pandemic-readiness programmes cut by the Trump administration.

Still, it will take time to bring the pandemic under control in the United States, says Kavita Patel, a physician who advises on health policy for Harris but is not currently advising the campaign. Biden’s staff members, she says, “need to hit the ground running” in order to turn the US response around...

...If elected, Biden has committed to supporting the World Health Organization (WHO), which Trump began to withdraw the United States from in July. As well as providing badly needed funds to the WHO to fight the coronavirus, polio and other diseases globally, reinstating the United States’ commitment to the organization would pave the way for joining its international COVAX facility, which aims to accelerate the search for and manufacture of coronavirus vaccines...

Climate change

...The coronavirus pandemic isn’t the only divisive issue that Biden would face if elected — he would also be confronting climate change. Trump has moved to pull the United States out of the 2015 Paris climate treaty, rolled back a suite of regulations intended to reduce greenhouse-gas regulations and called global warming a hoax.

In contrast, Biden is now campaigning on the most aggressive climate platform ever advanced by a US presidential nominee in the general election. Addressing the demands of an increasingly vocal liberal base, his US$2-trillion plan calls for massive investments in clean-energy research and development and low-carbon infrastructure, such as public transit and energy-efficient buildings. It also calls for the United States to generate 100% clean electricity by 2035 and to produce “net-zero emissions” by 2050. The question facing Biden and his team, if they win in November, is how to make it happen...

I will state, for the record, that I regard the rote political position of our party, my party - that so called "renewable energy" will save the world - to be dangerously wrong headed, since so called "renewable energy" has been failing miserably at addressing climate change for several decades: The situation is getting worse not better, but I do believe that science - which is a human activity and begins with theory, some of which are biased - does demand experimental proof, and the failure of the anti-nuclear "renewable energy will save us" experiment has unmistakable results, and one does see growing recognition of this.

But no matter, since Biden can think and Trump cannot, he will at least take the issue seriously and hopefully bring young fresh minds into the discussion.

Research priorities

...As well as tackling the pandemic and climate change, a President Biden would have the opportunity to develop other science priorities for his administration. This process typically includes tapping experts to coordinate science policy and establishing research focuses for the White House. (The actual job of doling out science funding is left to Congress.)

These advisers will be crucial because although Biden and Harris generally support science and its role in crafting public policy, neither has worked extensively on science issues. When he served in the Senate, Biden’s focus was more on foreign affairs and the judiciary, and Harris has a background in criminal justice, including her former position as California’s attorney general.

NASA soars and others plummet in Trump’s budget proposal

If Biden is elected, he should choose a science adviser as quickly as possible to start developing and implementing whatever research priorities do emerge, says Michael Lubell, a physicist and science-policy expert at the City College of New York. That position is currently held by meteorologist Kelvin Droegemeier — who did not start until nearly two years into Trump’s presidency...

...Biden’s most obvious research interest has been in cancer science, particularly following the death of his 46-year-old son Beau in 2015 to brain cancer. As vice-president, Biden headed a government ‘cancer moonshot’ initiative that kicked off in 2016, the last year of Obama’s presidency. It aimed to speed up the rate of progress against the disease by coordinating with companies and researchers to share data and results. The initiative later morphed into a non-profit group, which Biden suspended last year after deciding to run for president.

“Biden will want to make sure that any momentum from that effort that began in 2016 has not waned," says Jon Retzlaff, vice-president for science policy and government affairs at the American Association for Cancer Research. He also notes that Harris’s mother, Shyamala Gopalan, a major influence on the vice-presidential candidate, was a leading breast-cancer researcher who died of cancer...

Space exploration

Under Trump, NASA has pursued an ambitious strategy — named Artemis, after Apollo’s twin sister — to put US astronauts on the Moon four years from now. Space exploration is one of the few areas where the Trump administration has put in significant effort to develop science policy.How Biden, if elected, might alter the course set out by Trump is another unknown. As vice-president, Biden was not deeply involved in space-policy issues — unlike Pence, who has actively worked on Trump’s space initiatives.

President Donald Trump views the Artemis II space capsule
Trump views a space capsule that's part of NASA's Artemis programme, which aims to put astronauts on the Moon by 2024.Credit: Bill Ingalls/NASA/Planet Pix/ZUMA Wire

He did, however, express enthusiasm for space in May, when NASA sent two astronauts to the International Space Station on a privately built spacecraft for the first time. In response, Biden posted his congratulations on the website Medium — and noted that he was vice-president when this ‘commercial crew’ programme began in 2009.

NASA might not dramatically change its course under a President Biden, experts say. The Democrats’ official platform says the party is “committed to continuing space exploration and discovery”, including “NASA’s work to return Americans to the Moon and go beyond to Mars”...

Personally, I am a big supporter of robotic instruments in space, human space travel, not so much...but that's just me...

International research collaborations

Scientists widely feel that Trump’s isolationist stance has eroded the position of the United States as a global leader in major scientific collaborations and dimmed its allure as a destination for foreign students and researchers. Biden’s foreign-policy and immigration plans could mend some frayed ties, but science-policy experts warn that the road to recovery will be longer than a single four-year presidential term.

Well before the 2016 election, Trump’s nationalist campaign rhetoric, with vivid promises to build a wall along the US–Mexico border, spooked foreign scientists. And weeks after his presidential inauguration, a ‘travel ban’ executive order targeted at seven Muslim-majority countries stranded international students at airports, sparked protests and sent shock waves through the US research community. “When you don't have certainty over what the future immigration laws of the host country are going to be, you're going to think twice before deciding to uproot yourself and move to another country to pursue your PhD,” says Ali Nouri, a molecular biologist and president of the Federation of American Scientists...

Amid this crackdown, US scientists are concerned about racial profiling against Chinese scientists, and some scientists in China are wary of travelling to the United States for conferences or partnering on projects with US scientists. US funding agencies have denied that the increased scrutiny has caused collaborations to suffer and insist that the US government’s interest is in select cases of unethical or illegal behavior.

Having an ignorant racist for a President is clearly extremely dangerous in science - as well as many other areas - because science is in fact international and we disconnect from the world at our peril.

Biden is sure to be a huge improvement, a vast improvement, in fact an improvement on an almost infinite scale, since essentially he'll be starting from zero or less than zero.


I felt that the Obama administration was, overall, the best administration for science in my adult life, particularly in the first term.

President Biden and Vice President Harris will have huge issues to address, many of them involving science and engineering issues, and if nothing else, we can be sure that without a President Biden and Vice President Harris, science will suffer greatly, as it is doing now, at the expense of hundreds of thousands (actually millions) of lives.

Un Cadeau des Dieux

My wife got laid off from her University job today.

We kind of knew the University was on its last legs; as many private universities are.

Small private liberal arts focused universities are dying rapidly. Her university is still alive, but going down fast in the days of Covid.

Years ago, for the one and only time, I got fired, and I ran into an acquaintance, and told her I'd just lost my job, and she said, "That's great! This is a tremendous opportunity!"

I was polite about it, and didn't say the "Fuck you Lady!" that was going through my head.

But she was right. I left a wing of the industry which was dying - API manufacturing - because of Indian and Chinese competition, and went into another side where I learned so much more than I ever knew. Getting fired was just great for me. My life would have sucked if it didn't happen.

We are NOT watching the debates tonight. It's not like it matters; we're all Biden all they way for all the time and have no interest in watching that old senile drooling, drug addict in the White House try to take down someone who knows something he will never know; what it is to be decent, intelligent, and worthy of ones life.

Tonight we'll be watching Blade Runner 2049, celebrating that we are still alive, and yes, drinking a bit.

Life is beautiful and then you die.

Tears in rain.

Palestinian refugee receives Spanish citizenship after discovering Jewish Sephardic roots

As a U.K.-based academic who was born in Dubai to a Palestinian father and Lebanese mother, Heba Nabil Iskandarani had plenty of potential national identities.

What she lacked, however, was a passport.

A 26-year-old lecturer in architecture at Birmingham City University, Iskandarani has been stateless for most of her life, possessing only a Lebanese travel document that defines her as a Palestinian refugee.

But after discovering that her Palestinian father had Jewish roots going back to Spain, Iskandarani was able to claim Spanish citizenship thanks to a 2015 law that promised to naturalize anyone whose Jewish ancestors fled the Spanish Inquisition.

In an interview with the Jewish Telegraphic Agency, Iskandarani attributed her quest for citizenship as rooted in both an emotional search for an identity and as a practical remedy to the bureaucratic complications that resulted from her lack of national citizenship.

“This deep addiction for belonging made me look deeper into my family history,” Iskandarani wrote in a Sept. 12 Facebook post. “I wanted to find a solution to break the cycle of shame, the feeling of being less than all. I needed an identity a country to fall back too [sic]...”

Palestinian refugee receives Spanish citizenship after discovering Jewish Sephardic roots

Daily new Covid cases in New Jersey have jumped from September 12 to September 25,...

...from 297 cases per day, to 750 cases per day.

Not good...

My wife keeps talking about things like Christmas and next summer.

I'm not entirely sure I'm going to live that long. I'm clearly high risk, fat, old, borderline diabetic, with type A blood and male.

I think we get our ballots the first week in October. I'm filling out mine immediately and bringing it down to the County Board of Elections. I do hope to see that piece of shit dragged out of the White House if necessary, but failing that, I want to do my part to make it happen.

Screening Study of Different Amine-Based Solutions as Sorbents for Direct CO2 Capture from Air

The paper I'll discuss in this post is this one: Screening Study of Different Amine-Based Solutions as Sorbents for Direct CO2 Capture from Air (Francesco Barzagli, Claudia Giorgi, Fabrizio Mani, and Maurizio Peruzzini ACS Sustainable Chemistry & Engineering 2020 8 (37), 14013-14021).

Let me start this commentary by repeating myself: We will be damned for all time in history for leaving future generations the task of picking through our garbage dumps to survive. We will not be forgiven and we should not be forgiven.

Of course, we already have people picking through landfills to survive, but in my view, the most egregious dump of them all is precisely the one which almost no higher living thing can escape, our atmosphere.

Some years back, there was a moderately prominent energy website on the internet - it apparently operated from 2005 to 2013 -The Oil Drum which was built around the idea advanced by James Kunstler a journalist, once at Rolling Stone, in his book, The Long Emergency, that the world was experiencing "Peak Oil" and that we were all going to die when oil ran out.

(I could offer my standard joke that one cannot get a degree in journalism if one has passed a college level science course, but it appears that Kunstler does not have a degree in journalism; and certainly doesn't have one in a scientific discipline either.)

Personally, although I was certainly known to ridicule Kunstler despite that he was inexplicably popular among many of us on the left - the same people who opposed the two Iraq wars which were about claims of the essential nature of petroleum, also embraced Kunstler's fetishizing that pernicious substance - but I wish he'd been partly right, that oil was running out, if not about everyone dying without it. Regrettably it hasn't run out, even though the destruction we wrought to get at it is increasingly odious.

As of 2018, according to the 2019 Edition of the World Energy Outlook, dangerous petroleum was the largest single source of primary energy on this planet, producing 184.34 exajoules of energy out of 599.34 exajoules. It was the third fastest growing source of energy in the 21st century, after dangerous coal and dangerous natural gas; together they made up 81% of the world energy supply in 2018, as compared to 80% in the year 2000.

Things are getting worse, not better, but thank you Germany for pretending to care, even if pretending to care has been expressed by an embrace of stupidity. You're excused Germany, inasmuch as we live in the age of stupidity, and the stupidity of the German Energy Policy is simply an embrace of our times.

Eventually though, irrespective of the fate of Kunstler's mentality over the short term, the world will run out of oil, at least if we don't drown in its waste. I personally hope it is sooner rather than later.

This said, if we are ever to have any hope of reaching human development goals, which were first succinctly codified in Article 25, section 1 of the largely ignored 1948 Universal Declaration of Human Rights, an industrial society will require sources of carbon for essential chemicals and materials. Even though we live in the pyritic age of stupidity, we also live in the Golden Age of Chemistry, and an obvious source for carbon, the source in fact utilized by living things, is the otherwise dangerous fossil fuel waste carbon dioxide.

This paper is about the much discussed concept of "Direct Air Capture," often abbreviated in the scientific literature as "DAC," of carbon dioxide. This is an energetically expensive proposition, because in a purely thermodynamic sense, one must overcome the Entropy of Mixing, said entropy having contributed to the dubious embrace of dangerous fossil fuels by providing an efficiency kick. Sophisticated arguments have been advanced about why it might work; other sophisticated arguments have been advanced stating why it won't work. I come in on the side of saying it is feasible, not easy, but feasible, but only if no carbon dependent energy source (with the possible exception to a limited extent of bioenergy) is utilized to address overcoming the entropy that we, and all generations before us beginning in the 19th century, have dumped on future generations. From my perspective it is obviously feasible, since plants and algae do it all the time, albeit from the agency of providing a huge surface area via the self replicating function of life.

I personally think that a better industrial choice for capturing carbon dioxide from the air is indirect air capture, utilizing seawater, but that's another topic entirely.

Even I concede however that under limited circumstances, there are circumstances under which direct air capture might be viable, as a side product.

This involves my view of the wisest approach to what I'll call - since it involves a massive electrical circuit, the grid - capacitance, although I'm not a fan of the sometimes discussed idea of massive "super capacitors," designed to store electricity on a grand scale in the same way as it is stored, for example, in cell phones, or TV's in a short term fashion.

Capacitance is a refined word for energy storage. Energy storage is widely discussed as a scheme to make so called "renewable energy" a practical source of energy, by throwing good money after bad: So called "renewable energy" is an expensive failure, and attempts to store it to make its availability fit better into energy demand are misguided because they will certainly fail, just as so called "renewable energy" has failed to address climate change, particularly because what would be required would be the storage of electrical energy for a very long time in many circumstances. The mass requirements of doing so, and the toxicological and carbon associated with accumulating that mass, would surely be incredibly destructive and expensive.

Nevertheless, on an electrical grid, short term capacitance is a necessary feature. Here is the CAISO graphic for electricity demand in California during the recent extreme heat wave, accessed on September 6, 2020 at 3:05 pm Pacific Coast Daylight time:

Note that the distance between the forecasted peak power on that date, 45,168 MW, and the minimum at around 6:45 am on the same date, looks to be, from the graph, about 26,000 MW is roughly 20,000 MW. There are two ways to address this discrepancy, one being to build redundant power plants to cover these exigencies. This is extremely wasteful and therefore environmentally and economically unattractive, and it represents the reason that the highest electricity prices in the OECD are found in Germany and in Denmark. The other is capacitance, but this need not - in my opinion should not - involve the storage of electricity itself either in batteries or in massive super capacitors since this approach will clearly be environmentally odious. A better option would be to store the energy as heat, as in a phase change material, or as compressed air, or perhaps both.

For the purposes of this discussion, I will only discuss compressed air. Compressing air generates heat according to - on the simplest level - Charles Law, although vastly more sophisticated gas laws are obviously well known and widely used. It follows that gases cool when they expand adiabatically, that is, without heat being added. However, if one adds heat, in particular waste heat, one can under the right circumstances increase the exergy derived from the heat, where exergy is the usable energy extracted from the system.

If the air is compressed over a solution containing a carbon capture agent, similar to the amines discussed here, or - more to my personal liking - metal hydroxides, one can remove carbon dioxide from the air as a side product of the effort.

Another possibility is to use air as the working fluid in a Brayton cycle, during which the air is continuously cycled over carbon capture agents. This is certainly possible; all jet engines are Brayton cycle heat engines, and all use air as the working fluid.

If the air is superheated after compression, say to temperatures approaching 1000° or even higher, this will have the effect of combusting the greenhouse gas methane as well as carbon particulate matter, the latter a serious health risk, the former a potent greenhouse gas. If the heat transfer medium is highly radioactive it will have the effect of destroying the ozone depleting greenhouse gas nitrous oxide, residual CFC's, HFC's, sulfur hexaflouride, carbon tetrafluoride.

Although unlike the hyped up energy charlatan Amory Lovins, I am aware of Jevon's Paradox, I still think that high efficiency is desirable, particularly if we consider human development goals of justice and opportunity and health for all of humanity, not just those of us who live in wealthy countries. A very high temperature Brayton cycle, or a series of them, coupled to a Rankine cycle and perhaps even a Stirling cycle offers a number of opportunities, including the opportunity of providing sensible heat for chemical processing and, in fact, carbon dioxide recovery and reduction into useful products.

From the paper's introduction:

The recent climate conference COP21 (Paris, 2015) underlined the need to take actions by most of the world’s countries to mitigate climate change and keep the global temperature rise well below 2 °C above preindustrial levels.(1) In addition to the reduction of the combustion of fossil fuels and the improvement of the CO2 capture from large-point sources, the so-called carbon capture and sequestration (CCS) technology,(2,3) a strategy that is emerging as crucial for achieving the ambitious Paris’ target, is the development of negative emission technologies (NETs).(4) NETs relate to CO2 removal from the atmosphere through techniques such as the chemical CO2 capture from ambient air, called direct air capture (DAC).(5) DAC is a developing technology with the potential to contrast the dispersed emissions coming from transport and residential heating, which cannot be captured at their sparse sources and represent approximately half of the annual anthropogenic CO2 emissions.(6,7) In the DAC process, large air-absorbent contactors equipped with many fans blow the air to the absorber, where the ultradiluted CO2 (approximately 410 ppm) is selectively removed and the “clean” air is returned to the atmosphere. Afterward, the sorbent is regenerated and the captured CO2 is released for disposal or, more interestingly, for direct utilization, as, for example, in the catalytic methanation.(8) Moreover, DAC systems benefit from their inherent flexibility of placement, and careful location planning can favor the use of renewable energy and can reduce the cost of CO2 transportation from the capture site to the storage or utilization sites.(9) An ideal DAC process should combine a quick and efficient CO2 capture with low-energy inputs for air handling, sorbent regeneration, and CO2 release. Although DAC processes were considered prohibitively expensive until a few years ago, with costs in the range 200–1000 $/ton of CO2 (10 times higher than conventional capture from flue gas), the most recent economic analyses suggest that with the latest improvements (mainly engineering) the DAC technology is approaching commercial viability, with capturing costs that can be reduced to less than 100 $/ton of CO2.(10−12) In particular, several studies demonstrated that an air–liquid cross-flow scheme, which reduces the pressure drop, can dramatically lower the capture cost...(9)

The "approximately 410 ppm" remark is bitterly amusing to anyone who pays attention to carbon dioxide concentrations in the air. I am certainly such a person, as I monitor these levels closely on a weekly basis. I note that it was only a few years ago that scientific papers were talking about "approximately 390 ppm."

Depending on this year's carbon dioxide minimum, which will probably occur this week, measured at Mauna Loa we may never see a level as low as 410 ppm again, so dramatic is our failure to address climate change. In the last 52 weeks, going back to the week beginning of the week of September 29, there have been six where the concentration at Mauna Loa was lower than 410 ppm. That week, represented the annual minimum. We have not, as of this year, seen a value as low as 410 ppm: The last data point, the week beginning September 20, 2020, reported a concentration of 411.27 ppm. If values fall this year to 410 ppm - I doubt they will - it will be the last time in the lifetime of anyone now living that it will do so. (This year's maximum was 417.43 ppm, measured in the week beginning May 24, 2020, during worldwide Covid shutdowns.)

So there's that.

Later the introduction continues:

So far, the main potential technologies involve chemisorbent materials; (6) in particular, many researchers have focused on the development of solid-based sorbent systems, especially immobilized amine/silica sorbents or hollow fiber sorbents.(13−18) Alkaline liquid sorbents have also been taken into consideration for their fast and efficient CO2 capture in continuous (not batch) processes; (6) however, their development has so far been limited due to the high costs of regeneration. Aqueous solutions of sodium and potassium hydroxide have been extensively studied as sorbents for DAC processes for their strong alkalinity and their high reaction rate even with ultradiluted CO2.(19,20) Despite a good capture efficiency, the process is energy intensive: the sorbent regeneration is based on the formation of CaCO3 by adding Ca(OH)2, and the subsequent calcination of CaCO3 to release pure CO2 requires very high temperatures (900 °C), which entail high energy costs, up to 180 kJ/mol CO2.(9,10,19)

With the aim of developing new liquid sorbents for the efficient capture of ultradiluted aerial CO2 with a lower regeneration energy compared to KOH and NaOH solutions, we decided to investigate the performance of several amine-based sorbents in DAC systems. Aqueous amines are well-known (and widely investigated) sorbents for the efficient CO2 capture from large-scale emission points (CO2 12–15% v/v), which can be regenerated at T = 100–120 °C, a temperature well below that required for the CaCO3 calcination.(21,22) Currently, many researchers are working to develop innovative amine-based absorbents able to combine the most efficient CO2 capture with the lowest heat of CO2 desorption,(23−26) an important parameter for assessing the regeneration energy (the opposite of the heat of CO2 absorption, usually lower than 90 kJ/mol CO2 for all of the most studied aqueous amines).(22,27)

For various reasons, I'm not quite sanguine about giving up on alkali metal hydroxides, although - despite it's limited availability - for various reasons I won't discuss presently, I favor cesium or at least rubidium hydroxides. I note that alkali hydroxides can be made into continuous systems by the expedient of drizzling in saturated solutions of group 2 hydroxides, those of calcium, strontium or barium. The authors are nonetheless focused on reducing the regeneration heat and energy required, as they state above, and study various amines.

The amines tested and their structures are shown in a table in the text:

Here is a photograph of their equipment, accompanied by a schematic:

The caption:

Figure 1. Apparatus for the determination of the percentage of CO2 absorbed and its schematic flow diagram. Blue lines refer to air and black lines to the liquid sorbent.

Carbon dioxide captured by amines, including the commercial carbon capture amine, monoethanolamine, is generally in the form of carbamates, structures in which a carbon dioxide is loosely bound to a amine nitrogen.

Some tables of results:

The formation of carbamates tracked by NMR:

The caption:

Figure 2. 13C NMR spectra of aqueous MEA, 2A1B, AMP, and AMPD at the end of the absorption experiment. The numbers indicate the carbon atoms referred to both free and protonated amine fast exchanging in the NMR scale. Asterisks denote the chemical shifts of carbon backbones of amine carbamate. C indicates the carbonyl atoms of amine carbamate, while b/c refers to the signal of fast exchanging bicarbonate/carbonate ions. The intensity of the signals at 163–167 ppm is not in scale.

The authors explore the use of non-aqueous solvents. This table gives results.

In some cases the carbamates react with the alcoholic functions in the nonaqueous solvents having them to produce alkylcarbonates by the proposed mechanism:

The caption:

Figure 4. Scheme of the proposed two-step reaction mechanism for the formation of alkyl carbonate in nonaqueous EMEA solutions, including (A) the initial formation of the carbamate of the amine and (B) its subsequent reaction with an alcohol.

Excerpts from the conclusion:

With the aim of identifying the most crucial chemical peculiarities for the development of new liquid absorbents for DAC processes, we carried out a screening study on the performance of different aqueous alkanolamine solutions, under the same operating conditions: their ability to absorb CO2 from an air stream was correlated with their chemical structure and with the species formed by the absorption reaction, and useful information on the reaction mechanism has been obtained. As a general finding, aqueous unhindered primary amines are the most suitable sorbents for DAC processes, as they are as efficient as aqueous alkali hydroxides but with a potential energy saving due to the lower temperatures required for sorbent regeneration. The formation of a high yield of amine carbamate seems to be the decisive factor for an efficient CO2 capture, but the formation of an appreciable amount of carbonate/bicarbonate because of the strong basicity of some amines (EMEA, BUMEA) can contribute to attain a high percentage of CO2 absorbed. The amines that are unable to form carbamate have provided poor absorption values...

...These findings highlighted the differences of DAC processes compared to conventional CCS processes and, consequently, the best CCS absorbents cannot be the best choice for the DAC process. The obtained results also showed that aqueous amines are more efficient than the same amines in organic diluents. MEA and DGA in EG/PrOH display slightly lower abs% compared to the aqueous solution by virtue of the high percentage of carbamate formed...

This is a fine paper; I like it, although I'm not sure I agree with the idea of amine carbon capture reagents, in particular because in the case of a commercial example MEA, monoethylamine, the stability of the amine proves to be a long term problem. Another is the recognition that the air is hardly clean, and besides the formation of sulfates, there is a considerable amount of nitrogen oxides in the air. A recently discovered problem in the pharmaceutical and, albeit to a lesser extent, the food industries is the formation of highly carcinogenic and genotoxic nitrosoamines. At the scale of air capture - we're talking billions of tons here - this may be problematic for these amines, even if they are designed to be used in closed systems.

I wish you a pleasant and safe Sunday.

Los Angeles, 2019.

I watched the "Final Cut" of Blade Runner today, which begins with the title, "Los Angeles, 2019."

Flying cars, lots of rain...um...um...

Los Angeles looks a little different than expected in 1982, I think.

There are no replicants in Los Angeles, from what I can tell, but I may be missing something.

I especially liked the part where they get kind of "sciency," when Tyrell tells Batty why he can't live. It was less silly than some things you see in science fiction.

It was though, I think, a pretty good movie, if you like that sort of science fiction sort of thing. I'm not, in general, a science fiction fan, but I liked this one.

A Rare-Earth Samarium Oxide Catalyst for Electrocatalytic Nitrogen Reduction to Ammonia

The paper I'll discuss in this post is this one: A Rare-Earth Samarium Oxide Catalyst for Electrocatalytic Nitrogen Reduction to Ammonia (Yonghua Cheng, Haifeng Nan, Qingqing Li, Yaojing Luo, and Ke Chu
ACS Sustainable Chemistry & Engineering 2020 8 (37), 13908-13914).

I often reflect on Stuart Kaufmann's remark, which has stuck in my mind for nearly two decades, in his fabulous book The Origins of Order that life can be considered, "An Eddy in Thermodynamics." I once spent part of an afternoon with Freeman Dyson - one of the best afternoons of my life - and he approved of that description as well.

The nitrogen-nitrogen triple bond is one of the strongest, and thus one of the most thermodynamically stable, bonds there is, 9.79 ev/bond. This means that it is very, very, very difficult to break. Worse, the activation energy of breaking it is also enormous, 3.5 ev/bond. Yet, for life to exist, breaking this bond is essential because of the impossible to understate role of nitrogen in biochemistry, where it plays a huge role in proteomics and nucleic acids, as well as in amino sugars, the role of which is very critical in immunology, the science at the forefront of the world's current crisis.

Before the development of the Haber-Bosch process, which is brilliantly discussed by one of my favorite thinkers, Vaclav Smil, in his wonderful "down to Earth" popular science book, Enriching the Earth, almost all of the fixed nitrogen on Earth was formed via the agency of a molybdenum/iron metalloenzyme, nitrogenase.

Here is the structure of the metal center of nitrogenase:

The caption:

Fig. 2. (A) Schematic representation of the FeMo-cofactor model. Y represents the bridging ligand with relatively light electron density. (B) Stereoview of the FeMo-cofactor and surrounding protein environment

Kim and Rees Science Vol. 257, Issue 5077, pp. 1677-1682 (1992)

I once had the privilege of attending one of Emily Carter's lectures in connection with the publication of this paper:

Prediction of a low-temperature N2 dissociation catalyst exploiting near-IR–to–visible light nanoplasmonics (Martirez and Carter, Science Advances (2017) Vol. 3, no. 12, eaao4710).

I asked her kind of rhetorically, "What is it about molybdenum, anyway?" and she laughed and made a sort of noncommittal remark about orbitals, a subject about which she knows more than I have ever known or ever will know.

I am, by the way, convinced that the best way to replace the dependence of the world on dangerous natural gas - and in some places even coal - for the production of ammonia, which is said to consume about 2% of the world energy supply, does not involve photochemical bond activation, or, for that matter, the electrochemistry under discussion in this paper on Samarium. I think the Haber-Bosch Process is acceptable if the heat energy required comes from process intensification of the thermal downgrade of thermochemical hydrogen production using nuclear energy as the primary energy source.

As I often remark, electricity is a thermodynamically degraded form of energy, and it is only acceptable to use it for chemical processes in the case where it is waste electricity.

Dealing with the environmental - in particular atmospheric - consequences of the Haber-Bosch process, on which the world's food supply depends, is another issue entirely.

From the introduction:

Ammonia (NH3), as a pivotal nitrogen building block and a carbon-free hydrogen fuel carrier, is widely applied in the agricultural, clinical, environmental, and biomedical fields, along with many other fields.(1) Electrochemical dinitrogen reduction via nitrogen reduction reaction (NRR) provides a promising route for green NH3 synthesis.(2) Nonetheless, developing efficient electrocatalysts to boost the NRR and impede the hydrogen evolution reaction (HER) is highly imperative. To this end, extensive efforts, both theoretical and experimental, have been dedicated to exploring effective NRR catalysts, involving precious metals,(3−5) nonprecious compounds,(6−20) and metal-free materials.(21−23)

Lanthanide rare-earth compounds have gained a noticeable popularity in various applications of batteries, sensors, catalysis, and supercapacitors,(24) owing to their unique electron configurations, high surface chemical activity, and robust structure. Recent studies have identified CeO2,(25−27) DyF,(28) and La2O3(29) as promising rare-earth NRR catalysts. As a typical lanthanide oxide, Sm2O3 has recently attracted considerable interest in photocatalysis and electrocatalysis. For instance, Sm2O3 could act as an effective catalyst for the oxidative coupling of methane with high activity, selectivity, and durability.(30) Wang et al. prove that Sm2O3 can catalyze oxygen reduction actively and selectively and with high stability.(31)
Here, we first demonstrate Sm2O3 to be an effective and stable NRR electrocatalyst. Theoretical computations uncover that Sm2O3 can facilitate the NRR and hinder the HER. On the basis of the theoretical results, we synthesized Sm2O3 nanoparticles (NPs) which delivered an appealing NRR performance as well as robust stability.

The authors here did similar computational work to that reported by Carter, but went a step further into the experimental realm:

Density functional theory (DFT) computations are first performed to authenticate the NRR feasibility of Sm2O3. The dominant (222) facet is considered for building the Sm2O3 model. As shown in Figure 1a, the Sm2O3 (222) comprises abundant surface-exposed Sm atoms with a positive charge of +1.01 |e|, which provides the catalytic opportunity for polarizing and activating the negatively charged N2 molecules.(32) Initially, upon N2 adsorption (Figure 1b), the *N2 prefers an end-on adsorption configuration and gains −0.02 |e| from an active Sm atom, resulting in an N–N bond elongation of 1.12 Å. Remarkably, for *N2 → *NNH (Figure 1c), two N atoms in *NNH gain a large amount of charge (−0.57 |e|), and the N–N bond is dramatically elongated to 1.215 Å, indicating that Sm atoms enable the effective N2 protonation to catalyze the NRR.

Some pictures from the text:

The caption:

Figure 1. (a) Schematic of NRR on Sm2O3 (222). (b, c) Optimized models of (b) *N2 and (c) *NNH on active Sm atom: N1 and N2 represent the distal-N and nearest-N, respectively. (d) PDOS of *NNH on Sm atom. (e) Free energy profiles of reaction pathway on Sm2O3 (222) at zero and applied energy of −0.92 V (inset: free energies of various species on Sm2O3 (222).

The caption:

Figure 2. Characterizations of Sm2O3 NPs: (a) XRD, (b) unit cell of Sm2O3, (c) TEM, (d) HRTEM, (e) SAED, (f) lattice measurement, (g) atomic configuration of Sm2O3 (222) facet (side view), (h) XPS Sm 3d spectra, and (i) O 1s spectra.

The caption:

Figure 3. (a) LSV curves of Sm2O3 NPs. (b) Time-dependent current density curves of Sm2O3 NPs for 2 h at various potentials and (c) corresponding UV–vis absorption data of resultant electrolytes and (d) obtained NH3 yields and FEs. (e) UV–vis spectra of the electrolytes after 2 h of electrolysis on Sm2O3 NPs at various potentials. (f) NH3 yields of Sm2O3 NPs, Sm2O3/RGO, and bare RGO at −0.6 V.

The caption:

Figure 4. (a) UV–vis absorption spectra of the electrolytes after 2 h of electrolysis over Sm2O3 NPs at −0.6 V at different conditions. (b) 1H NMR measurement. (c) Cycling test. (d) Chronoamperometry test for 20 h.

From the succinct conclusion of the paper:

In summary, the combined computational and experimental results validate Sm2O3 to be a high-performance rare-earth electrocatalyst for the NRR. Theoretical calculations unveil that the active Sm centers could favorably boost the NRR and impede the HER. The prepared Sm2O3 NPs show an appealing NRR activity along with high stability. This work may provide a new pathway for the rational design of rare-earth catalysts for electroreduction of N2 to NH3.

Again, I basically am less than supportive, despite the fine science demonstrated in this paper, to electrochemical reduction of ammonia, except in the case where there is waste electricity.

However, it is environmentally and economically wise to avoid waste electricity, and the idea of storing it in batteries is about as environmentally odious as one can get in my opinion.

Continuous processes are always desirable, as opposed to batch or interrupted processes, in an environmental and economic senses - because these senses depend on thermodynamics.

This fact - facts matter - is why so called "renewable energy" will continue to fail to address environmental issues while simultaneously failing to address the ethical issues associated with human development goals.

I trust you will have a pleasant and safe weekend.

At the Purchaser's Option...

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