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Nice listing of the putative carbon intensity of biobased chemicals.

It's become increasingly clear to me in recent years that all efforts to address climate change have failed miserably, as we can see by looking at the Mauna Loa carbon dioxide data, at least until the Republicans either destroy the carbon dioxide observatory outright or begin to fudge the data, neither of which will have any bearing whatsoever on the truth itself, other than to obscure it.

Thus, among the many burdens we have placed on all future generations is the likely need they will have, in order to stabilize the climate, for the need to actually remove carbon dioxide - our waste, not theirs necessarily - directly from the atmosphere.

This is an almost impossibly difficult engineering task, although there are many scientists who refuse to give up hope that it is an engineering challenge that can be met. (One of my personal favorites is Christopher Jones's group at Georgia Tech.)

I question it, but I believe that if it is possible at all, biobased chemicals, which theoretically could sequester carbon in an economically viable way inasmuch as the carbon would not be sequestered in the oft imagined waste dumps, but as products, useful products, in particular polymers.

As I catch up on some reading, I came accross an interesting paper in the relatively new, but rich, journal, ACS Sustainable Chemistry and Engineering which gives a very nice table of the carbon intensity of a broad range of biobased chemicals from a number of biological feedstocks.

The paper in question is this: Meta-Analysis of Life Cycle Energy and Greenhouse Gas Emissions for Priority Biobased Chemicals (ACS Sustainable Chem. Eng. 2016, 4, 6443−6454). While the parent paper may be behind a firewall, the "Supplementary Information" which actually contains the data tables on the carbon cost (or benefit) of biobased fuels is not and can be accessed by the general public.

Supporting Information, Meta-Analysis of Life Cycle Energy and Greenhouse Gas Emissions for Priority Biobased Chemicals

If one looks at the table, one will see that many of the chemicals actually release more carbon dioxide than they sequester. While this may seem to make the situation hopeless, it actually need not always be so, since these calculated values assume certain process parameters.

In many cases one of the inputs for processing is heat and currently heat is often provided by the use of dangerous fossil fuels. It is possible however for this heat to be obtained in other ways, notably with the use of high temperature nuclear reactors of types being evaluated all over the world by nuclear engineers. This may offer an avenue to making some of those processes (most notably those involving reformation) that are marginally carbon positive, carbon negative.

Some excerpts of the full paper's text:

Biofuels and biobased chemicals have received significant interest as a potential low-carbon and environmentally sustainable alternative to conventional fossil-based fuels and petrochemicals. As defined by the US Secretary of Agriculture in the Farm and Rural Investment Act of 2002, biobased products are commercial or industrial products that are composed of biological products, renewable agricultural and forestry materials, or intermediate feedstocks, in whole or insignificant parts.1 The annual production of biobased chemicals(excluding fuels) is estimated to be 50 million tons,2 dominated by biobased polymers (55%), oleo chemicals (20%), and fermentation products (18%).3 Commercialization of biobased chemicals is still nascent, and their penetration rate in the global market will be strongly dependent on the development of biorefineries.4 The US Department of Agriculture (USDA)estimates that the global chemicals industry is projected to grow 3−6% annually through 2025, with the biobased chemicals share of that market rising from 2% in 2006 to22% or more by 2025.5

50 million tons is a trivial amount, given that we now irreversibly dump more than 30 billion tons of carbon dioxide into our favorite waste dump, the atmosphere now, and - while we wait like Godot for the solar and wind miracle that never comes - the dumping is rising in volume, not falling. Still, one hopes that we can make progress.

Some other text, later in the paper:

In this study, we reviewed published results for life cycle GHG emissions and energy use for 34 priority biobased chemicals, including those identified by DOE, compared against their fossil-based counterparts. Prior meta-analyses of bioenergy systems showed that there are several factors controlling environmental benefits from GHG emission and energy use, from biomass carbon cycle and soil carbon change to selection of appropriate fossil reference systems, homogeneity of input parameters, and coproduct handling schemes.25,26 The present meta-analysis is conducted for biobased chemicals, focusing on collection and interpretation of existing LCA results with statistical analysis. It does not attempt a harmonization of various cases but rather aims to identify trends across the many feedstocks and processing routes that have been considered, while examining the statistical effects of modeling factors such as coproduct allocation. The main goals of this work are to evaluate a potential renewable chemical standard, to identify gaps in the assessment literature and to synthesize the state of knowledge for net energy and life cycle GHG emissions assessment of biobased chemicals.

Another paper along these lines in the same issue of the same journal that strikes me as interesting is this one: Reductive Catalytic Fractionation of Corn Stover Lignin (ACS Sustainable Chem. Eng. 2016, 4, 6940−6950)

Here's a graphic from the paper's abstract:

The cellulosic ethanol business has failed commercially, and the plants built to make it commercially viable have all failed. These were fermentation systems, inherently batch processes, batch processes, particularly water based batch processes are seldom successful to make commodity chemicals.

But the process here is thermal, and thus quite different, far more amenable to continuous flow.

The stover, irrespective of the failure of the cellulose to ethanol processes, is still carbon captured from the air. Perhaps it's not wise to throw the baby out with the bathwater.

The chemicals shown here in the graphic are hydrogenated ("saturated), but the intermediates (shown in the full text but not shown here) are unsaturated, meaning that they are potential precursors to polymers. What is interesting about these putative polymers (which are not discussed in the paper) is that they are highly functionalized and could in theory be utilized to make resins like commercially important peptide synthesis resins, but more importantly, I think, a whole host of functionalized resins designed to remove dilute and sometimes toxic (or commercially desired) elements from very dilute streams, for example mercury from coal plants now found in all the world's water supplies, or lead, from coal and other sources.

I'd like to think there's still some hope for the future, even in times that seem hopeless.

Esoteric but interesting, I think.

Enjoy the remainder of the weekend.

Went to a Phil Murphy 4 Governor Event; Quite a Turnout.

Somehow, about a year or so ago, I found myself on Phil Murphy's mailing list, before he announced he was running for Governor.

I asked myself, who the hell is Phil Murphy, and why is he crowding my inbox.

It was all "Christie sucks" stuff, and I said, "I know, Christie sucks, but, um, who's Phil Murphy?"

A recent email invited me to an event near where I live. It was at a West Windsor Athletic Club, owned by a Chinese American immigrant; the mayor of West Windsor is a very popular Chinese American immigrant; 76% of West Windsor voted for Ms. Clinton.

He came with Bernie Sanders son, Levy Sanders. (For the record, I don't actually like Bernie Sanders.)

Anyway. There were about 300 people there, maybe a few more, standing room only.

Phil Murphy spoke and he's quite an engaging guy; despite all the Sanders praise, I rather liked him, well informed, clearly bright, enthusiastic and as he made clear, despite his (Goldman Sachs generated) wealth, he came up from a lower middle class family. Like me, his father didn't finish high school.

Criticisms: The staff had people write out questions in advance so that they could go through them and make sure they were all "soft ball" - questions which would allow him to make responses that the audience, 100% democratic, would all approve.

I had the privilege of chatting with three other people outside, one of whom, like me was a scientist, who as it happens is working on solar energy projects. (I do not approve of solar energy.) I was gratified though that this scientist agreed with me that nuclear energy is a critical tool that we must have to fight climate change. We both felt Phil soft balled it; wind and solar...wind and solar...blah...blah...blah.

All four of us though liked Phil, including a nice woman who immigrated from a foreign country, Kansas, who agreed, as the four of us did, that New Jersey is the best state in the Union and that Phil Murphy might prove a wise choice to lead the state.

(I have to check out the other candidates though.)

Turnouts have been pretty good at his events.

One note of optimism:

It seems that since the election of the orange nightmare, political events are becoming more important for everyone, and attendance is rising. Three hundred people at a political event early in the gubernatorial process is impressive. This I think is because many of us around the country recognize that turning our country over to right wing traitors who care not a whit about America but only there own power - including the leadership of our awful congress - has made us recognize that our country could, indeed, be destroyed. We are looking for leaders.

Phil Murphy I think, although I have some reservations, could be an fine leader for New Jersey. Even if he's hanging out with the Sanders crowd - probably to deflect from the Goldman Sachs history which he shared with Corzine - my impression is that he's more like Hillary Clinton inasmuch as he's bright, and he cares.

I'm seriously considering a primary vote for him.

Phil Murphy for Governor.

Barack and Hillary Should Put America on "Do not answer."

I don't know if this has been here before, but I rather enjoyed it.

If I Were Barack Obama or Hillary Clinton, I’d Put America Under ‘Do Not Answer’

When I saw the image of former President Barack Obama in flip-flops, shorts and a backward cap, along with his wife, former first lady Michelle Obama, in the shortest of shorts, walking across the beach, I was relieved for them. They served this country well for eight years—even when millions of its citizens blatantly disrespected them for no other reason than that the hue of their skin made them antithetical to the virtues of their America. So much so that Obama’s successor is the most unqualified president in U.S. history; a man who is small by every measure who won, largely, because he sold his supporters the notion that he could restore the nation to the lily-white land of yore...

... Now that the sky has cracked and pieces have begun to fall, political journalists along with average citizens have been calling on former President Obama to speak up. So he did, 10 days after leaving office—which, in some respect, felt hasty—to disavow the travel ban targeted to immigrants from primarily Muslim nations.

The statement was appreciated, but make no mistake: Obama may speak out when it suits him as promised following the election, but he owes this country nothing. Not while on vacation. Not after eight years of service to a sizably ungrateful nation. Not less than a month after leaving office...

...Similarly, on the day of the Women’s March on Washington and subsequent days after, quite a few called on former Democratic presidential candidate Hillary Clinton to also engage and help the resistance. Typically, after an election, the losing presidential candidate goes off and finds some business. While we are undeniably living in unique and increasingly dire circumstances, not only do I question the push for Clinton to more aggressively speak out against the antics of this amateurish administration, but I also worry about its ineffectiveness this early.

If she were to level stronger statements against Tropicana Jong-il, all that would do is invite comment from a man who can’t seem to escape campaign mode for the kind of needless public feuds he’s known for courting...

...Last August, Clinton spelled out in no uncertain terms the dangers of electing an orange clown who surrounded himself with men modeled after the Ku Klux Klan and Nazis. In each and every single debate, she pointed out that her political opponent was a con man who would be a puppet of a Russian authoritarian obsessed with shirtless selfies and unlawfully seizing neighboring land. Clinton was not my ideal candidate, but had she won 70,000 more votes in three states with laws designed to make it much more difficult for people who look like me to vote, there would be less talk about what a disastrous campaign she ran. Then again, it would have been yet another instance of black people picking up the slack for white people.

Many of the very people who have pushed Obama and Clinton to speak out more are the same people who didn’t initially want to talk to their white relatives about what it means to support a man who has an extensive history of bigotry...

Pretty powerful stuff; I refer you to the full text at the link.

The Net Carbon Dioxide Penalty Associated With Large Scale Energy Storage Systems.

A paper published in the most recent issue of Environmental Science and Technology, the premier scientific journal on environmental science published by the American Chemical Society discusses the environmental cost of large scale energy storage systems, in particular, batteries.

The link to the paper is here: Emissions and Economics of Behind-the-Meter Electricity Storage (Environ. Sci. Technol., 2017, 51 (3), pp 1094–1101)

For many people - those without access to university library systems or subscriptions - the full text will be behind a firewall, but the abstract gives a decent summary of what's inside the full paper:

Here, we characterize the economic payoff and regional emission consequences of BTM storage without colocated generation under different tariff conditions, battery characteristics, and ownership scenarios using metered loads for several hundred commercial and industrial customers. Net emissions are calculated as increased system emissions from charging minus avoided emissions from discharging. Net CO2 emissions range from 75 to 270 kg/MWh of delivered energy depending on location and ownership perspective, though in New York, these emissions can be reduced with careful tariff design.

The nice graphic also accessible from the abstract alone, shows the broader case.

Some excerpts from the text of the full paper:

Stationary electrochemical (battery) storage has seen significant improvements in cost in the past decade and is a promising way to perform many electric-grid functions.1,2 Battery storage is being installed both on the utility side of the customer meter at the transmission and distribution level (“grid-scale”), and “behind-the-meter” (BTM) for individual facilities. Grid-scale storage can be used to delay infrastructure upgrades, perform wholesale market transactions including energy price arbitrage and frequency regulation, and absorb over generation by distributed generation resources, among other services. BTM batteries can reduce retail electricity costs by shifting the timing of utility purchases while also performing grid-scale services via aggregation or proper tariff structures. BTM storage is being adopted in areas that have high retail electricity prices and generous battery subsidies…

…Policy makers are now implementing rules and subsidies that encourage large scale deployments of electric storage. California has set a storage procurement target of 1.3GW by 20204 and provided an incentive of $1300/kW.5 New York City has an incentive of $2100/kW.6 At the federal level, FERC Order 7557 instructed grid operators to compensate fast-responding resources like storage for their speed and accuracy in frequency regulation markets. The emissions consequences of deploying a storage technology depends in part on how it is operated; in turn, the operating policies depend on who owns the storage. Previous research has focused on grid-scale storage. Investor owned grid-scale batteries will be operated to maximize profit from wholesale market transactions, resulting in homogeneous battery behavior across a grid region. A number of studies have shown that grid-scale storage will increase total power system emissions under the grid’s current fuel mix when operated for energy arbitrage,8−12 …

The text includes also a description of the limits owing to the physics of batteries:

...The simulated battery faces three main types of physical and market constraints.

1. Battery state of charge (SOC): Expressed as a fraction of total energy capacity, SOC is restricted to 20−100%, with a penalty function above 90%, to prevent increased degradation from high and low voltages. These restrictions are also found on electric vehicle batteries.28

2. Total capacity: The capacity used to charge and discharge the battery and held for ancillary services cannot be greater than the capacity of the battery.

3. Frequency regulation capacity: We assume that the frequency regulation signal is energy neutral (no net charging or discharging), similar to the dynamic regulation signal implemented in the PJM Interconnection(PJM).29 However, during any given time period, the battery will gain and lose charge as it follows the regulation signal. Therefore, we place a constraint on capacity used for frequency regulation to ensure Solicits are not violated. One year of regulation signal from PJM30 was used to estimate the amount of charging and discharging possible during a single period..

The paper conclusively makes what should be an obvious outcome, but somehow isn't. Large scale energy systems waste energy, and therefore, since the overwhelming majority of energy on this planet is provided by dangerous fossil fuels, increases emissions.

It is said that Albert Einstein once remarked that the laws of thermodynamics are the only laws of science that he thought would never be over turned.

The first law is the law of energy/mass conservation and can be stated as dU[sub]universe[/sub] = 0 where the energy, U, includes but is not limited to the energy associated with mass. If we ignore the energy trapped as mass (which is accessible only with nuclear reactions) this law is a simple statement of the fact that energy is conserved, it can never be lost although it can change form, notably, and most importantly to forms that cannot be converted to useful work, usually, in a practical sense, low grade heat.

The second law, the one that "efficiency will save us" types generally like to ignore, can be stated as dS > 0. This means that the entropy of the universe, disorder, which may be expressed mathematically as a number of states available to a system, is always increasing. This law states that any energy conversion from one form to another will lose exergy, the ability to convert it into useful work, almost always in the form of heat (although in practice this loss can be as radiation).

The third law, which is somewhat esoteric, and not really relevant to the environmental crisis before us is that dS -> 0 as T -> 0.

There is also a zeroth law, which is important in an environmental when one shuts down a coal plant or gas plant because the wind is blowing or the sun is shining for what may be a short period. This law states that any two systems experiencing a temperature gradient - different temperatures - will eventually reach the same temperature. One therefore needs to waste energy to restart the coal or gas (or diesel) plant if one has shut it down.

Many people assume that energy storage will somehow be an important cog in reducing carbon dioxide emissions, since they like to fantasize that someday, somehow, that so called "renewable energy," in particular, wind and solar energy will become significant forms of energy, even though they have never been a significant form of energy, are not a significant form of energy, and will never become a significant form of energy no matter how much money is thrown at them.

Nevertheless, as the internal costs - the costs paid for the manufacture, delivery and operation - of batteries fall, even as the external costs - the costs to the environment, human and ecosystem health, and the future are not falling at all, and are possibly, owing to the toxicological and resource depletion issues associated with their manufacture and use, are rising.

Large scale commercial battery systems are now known, even if their overall capacity is not really huge, and the materials required for their manufacture make them unsustainable over long periods of time.

The second law of thermodynamics dictates that the use of batteries will always waste energy. Most people can see this experimentally themselves when they feel a computer battery, or any kind of rechargeable battery, during the charging process. It always feels warm to the touch. This is waste heat, the energy, or more properly the exergy lost.

Consider a nuclear reactor. A nuclear reactor takes potential energy expressed as mass and converts it to heat. In a fission reactor, this heat is generated on an atomic/molecular scale by the very high speed of the fission products of uranium, neptunium, plutonium, americium or curium when an atom of one of these elements is split by a neutron. The nuclear energy which is potential energy associated with the fact that whichever of the aforementioned atoms will weigh slightly more than the sum of the fission products (and neutrons) released in the fission event is converted to thermal energy. A small fraction of the energy is carried away by neutrons which induce more fissions, or collide with reactor components or coolants to produce heat. Some of the energy is also released as radiation, and some of it is lost immediately as neutrinos, which do not react with matter in a way that makes the energy recoverable. (Neutrinos represent about 5% of the energy lost in a nuclear fission reactor). Now the energy is in the form of heat, and the heat is converted to mechanical energy by using it to boil a working fluid - almost always water - to drive a turbine as vapor. In order for this to happen, the opposite side of the turbine must always be cooler than the hot side; this conversion is the energy lost as heat in the cooling towers. In addition some of the heat will be lost to the materials of which the boiler is constructed, and other heat leaks, including the turbine housing, steam lines, etc. The turbine converts the mechanical energy to electrical energy by use of a generator. The armature of the generator loses small amounts of energy to friction with the air in which it moves, more is lost by eddy diffusion currents in the materials as well as electrical resistance and the slow (but real) degradation of the materials in the magnets. The electricity is then shipped - where energy is lost to resistance in the wires - and finally used in the system where it is required, a computer, a refrigerator, electric heaters, etc.

If however we choose to store the energy in a battery, we need to convert electrical energy to chemical energy, which is always an inefficient process which releases resistive heat. Now to the above changes to forms of energy we need to add two more, the conversion of electrical energy, including a shift of alternating current to direct current – itself an energy losing proposition – and the conversion of direct current to chemical energy (in the battery), the storage of this chemical energy which is subject to (generally small) losses owing to diffusive effects, and the reconversion of chemical energy to electrical energy as direct current, followed by conversion of the direct current (via an inverter) to alternating current to supply the grid, with transmission losses occurring on both sides, the charging and discharging of the battery.

If the power is used to charge an electric car, the situation is even worse.

In the nuclear case, no carbon dioxide penalty is observed, but for the standard grid electricity supplies in most of the world, France excepted, a carbon penalty for this profligate waste of energy is observed, since regrettably most of the world's energy systems do not rely on nuclear energy; the overwhelming bulk of the electricity generated on earth relies on burning fossil fuels.

Occasionally, after decades of failure, we still hear a lot of silly cheering about hydrogen “energy.” Hydrogen is not energy, since it does not occur in free form in the natural environment except in extremely dilute concentrations which are of no practical use. Hydrogen is just another energy storage system, subject to all the thermodynamic laws described above. The situation for hydrogen for a purely thermodynamic sense is even worse, although, truth be told, there are thermochemical (high temperature) water splitting processes that can improve the thermodynamics of hydrogen use somewhat, but no matter what, manufacturing hydrogen gas will always waste energy.

The point of the paper, which should be obvious to anyone with a knowledge of the physical sciences is that energy storage, wastes energy, and therefore increases emissions.

The fantasy that underlies the opposite impression is the fantasy that solar and wind energy will someday become significant and even dominant forms of energy. This has not happened. It is not happening. It will not happen. The massive investment world wide in so called "renewable energy" has not lead to a decrease in the use of fossil fuels. The reverse is true. We are now burning more fossil fuels than at any point in history, and the accelerating rate of the accumulation of the dangerous fossil fuel waste in the earth's favorite waste dump, its atmosphere, demonstrates this fact conclusively and irrefutably.

The reality is that careful examination of scientific principles can explode popular myths, and a little science can help if the goal is really to save the environment, as opposed to wallowing in dogma.

Have a nice day today.

Interesting paper on the problem of electronic waste associated with cars.

I'm not a big fan of the car CULTure, something that runs through many things I've written here and elsewhere.

One of the fantasies that runs through first world wishful thinking types is that some day everyone will be driving swell electric cars, powered by wind and solar energy and that the car CULTure will become sustainable.

It hasn't. It isn't. It won't be.

One of the reasons it won't - and this reason also applies to why so called "renewable energy" isn't actually "renewable" - concerns the issue of critical materials, relatively rare elements which for which only limited supplies are possible without huge environmental costs.

(If this sounds like the "peak oil" fad that was under discussion some years ago, and seems discredited now, it actually is. The failure to run out oil before we ran out space to put it's chief waste, carbon dioxide, is not actually as benign as some people may think. The increase in oil production owes to ratcheting up the already unbearable environmental cost of petroleum (and gas) mining.

Cars are a disaster; it doesn't matter whether their electric cars, gasoline cars, diesel cars, or gas turbine cars. They have not been, are not, and never will be sustainable, and the cultural assumption that their use is essential a crime against all future generations.

An interesting paper appears in the current issue of Environmental Science and Technology, one of the world's premier scientific journals relating to environmental issues.

Here's a link to the paper: Stocks, Flows, and Distribution of Critical Metals in Embedded Electronics in Passenger Vehicles (Environ. Sci. Technol., 2017, 51 (3), pp 1129–1139).

Some excerpts from the introduction:

Recent concerns regarding the availability of raw materials for future technologies have motivated material criticality assessments.(1-4) According to Graedel et.al, 2015(4) rare earth elements (REE) are particularly critical considering the risk associated with the global supply being dominated by one country, while the criticality of precious metals (PMs) such as Ag, Au and Pd is regarded to economic importance, environmental implications and substitutability, respectively.

One of the major applications of critical metals (CMs) is in electrical and electronic equipment (EEE),(1, 4) which is at the same time increasingly embedded in other products, notably automobiles.(5-9) Currently, embedded automotive electronics account on average for 30% of the total car cost (this percentage is expected to increase to 50% in 2030)(8) and already 15–25% of the global neodymium–iron-boron (NdFeB) permanent magnet production is used for automotive electronic applications.(7) It can therefore be expected that the amounts of CMs in end-of-life vehicles (ELVs) increase dramatically in the coming years.

Recycling emerges as a key strategy to ensure future access to CMs.(1) However, current treatment of ELVs favors the recycling of bulk metals like iron, aluminum and copper while most CMs end up in the automobile shredder residue (ASR) from which they are currently not recycled.(10)

...not currently recycled...

One of the fun things one hears when one points out that things like wind turbines and solar cells require critical materials is a kind of glib hand waving comment, "they could be recycled."

But they aren't recycled now. This represents, like the entire "renewables will save us" conceit, a rather selfish claim that future generations will do what we don't do ourselves. This, of course, comes at a time when the current generation is doing everything in its power to see that all future generations are left with almost no resources, a destabilized atmosphere, and a toxic mess.

Here is a nice graphic from the paper, talking about what kinds of critical materials are found in various types of cars:

Recycling of critical materials has a profound energy, thermodyanmic, and thus environmental cost.

It's an interesting read. It may be behind a firewall, but one can generally access it in a good university library.

Just a brief note.

Have a nice day tomorrow.

ACS and 150 Science Organizations Call On the White House to Rescind Exceutive Order...

•Letter to U.S. President Donald Trump

President Donald J. Trump
The White House
United States of America

Dear President Trump:

The January 27, 2017, White House Executive Order on visas and immigration has profound implications for diplomatic, humanitarian, and national security interests, in part because of the negative impact on U.S. science and engineering capacity.

The 151 undersigned organizations – representing a broad spectrum of professional scientific, engineering and education societies, national associations, and universities – are deeply concerned that this Executive Order will have a negative impact on the ability of scientists and engineers in industry and academia to enter, or leave from and return to, the United States. This will reduce U.S. science and engineering output to the detriment of America and Americans.

Scientific progress depends on openness, transparency, and the free flow of ideas and people, and these principles have helped the United States attract and richly benefit from international scientific talent. From the Apollo Program and exploring the far reaches of the universe, to advancing biomedical research for curing diseases and harnessing science to build a thriving high-tech sector, the United States is considered a leader in science, education and innovation. In order to remain the world leader in advancing scientific knowledge and innovations, the U.S. science and technology enterprise must continue to capitalize on the international and multi-cultural environment within which it operates...

What's going on his tiny little brain as he runs his tiny little fingers through his confusing hair?

"Scientists, we don't need no stinking scientists..."

I'm personally definitely seeing this as my son enters college, with all the universities clearly wondering, "what's going to happen to us..."

What indeed?

An interesting inversion in the distribution of lanthanides, (RRE) in Kentucky coal ash.

In my position as a student and an advocate of nuclear energy I get to hear a lot of, um, what has come to be known as "alternate facts" although I still prefer the word "lie" to "alternate fact."

One of my least favorite "alternate facts" about nuclear energy is very popular in spite of being, um, delusional, is the one that goes "Nobody knows what to do with nuclear waste," even though I and lots of other people whose work I've read and studied know very well what to do with so called "nuclear waste." Lots of people know what to do with fission products and actinides, and it's not their fault that their critics are completely ignorant of their work and are just doing a Kelly Conway and "making stuff up." The treatment of used nuclear fuel has been the subject of study for more than half a century by some of the finest minds one can find.

I would submit that the first step in understanding "what to do with" so called "nuclear waste," is to recognize that nothing which is useful, in many cases, extremely useful can be considered "waste." For example, one of the world's great environmental problems among many great environmental problems, concerns halocarbons, chlorocarbons (including chlorofluorocarbons to be sure) which are a problem because of their long half lives and stability on a human lifetime scale, and worse, fluorocarbons, not just atmospheric varieties but also water born and living tissue born perfluorocarbons like PFOS and PFOA (respectively, perfluorooctanoyl sulfonate and perfluorooctanoic acid) and their analogues and degradants.

I would submit, if you look into it, that there is nothing that can break a carbon fluorine bond quite like gamma radiation, and an excellent source of gamma radiation is fission products.

But I'm not here presently only to complain about anti-nuke ignorance and stupidity, but to note some issues with a form of waste that, unlike used nuclear fuel which is remarkable only inasmuch as it hasn't killed anyone, to remark on a recent publication about a real form of waste with which nobody knows how to deal, coal waste.

Fossil fuels, especially coal, are responsible for the seven million deaths that take place each year from air pollution, and where air pollution deaths are concerned, coal's contribution is largely a function of particulates, which are often carbon particles that have reactive species like dibenzofurans, dibenzodioxins and a bunch of other nasty stuff.

But another function of the death and destruction and health impact of coal waste concerns the ash and fly ash, which often includes powerfully toxic volatile elements, the most famous of which is the neurotoxic element mercury, but also includes other toxic elements like arsenic and selenium.

The accumulation of coal ash is a very, very serious problem, involving billions of tons of waste, that leads to events like the Martin County coal slurry disaster which destroyed hundreds of miles of rivers, contaminated the water supply of 27,000 people and resulted in a fine of $5,600 levied by the wife of the asinine thug who now runs our Senate, rubber face gorgon himself, Mitch McConnell.

(If you look, you might begin to harbor suspicions about the role that coal based mercury plays in inducing insanity by comparing the map of the States carried by Trump with distribution of national coal plants. I'm not saying it's cause and effect, but it is an interesting speculation, now that mass insanity in the United States is on display for all the world to see.)

Anyway. Is coal waste really "waste?" I think it is, but that doesn't mean it's entirely useless. For instance, W. Alex Gabbard at ORNL in a rather famous article in the Oak Ridge National Laboratory Review pointed out that some forms of coal ash actually contain more energy content in the uranium present in the ash than was present in the original fuel.

This brings me to the lanthanides, which are often called the "rare earth elements" "REE" even though many of them are not really rare at all, although some are.

In general, many of the lighter lanthanides, lanthanum itself, cerium, praseodymium, and neodymium, are readily available, although the so called "renewable energy" industry, as well as the electric car industry are putting a certain amount of pressure on their supplies. The heavier lanthanides are somewhat rarer, and notable among the elements of concern are europium, used in phosphors for low energy lighting such as LEDs, and dysprosium, which is a component of very high quality magnets used in things like, um, "renewable" wind turbines. The wind industry has proved useless in addressing climate change, more or less, but would be even more useless without lanthanide based magnets, and dysprosium is very much an element of concern, in particular because the majority of the world's high quality lanthanide ores are enriched with respect to the lighter lanthanides (lanthanum through samarium) and depleted with respect to the heavy lanthanides (gadolinium through lutetium).

It was therefore with some interest that I read the following paper in the primary scientific literature in the current edition of the fun journal Energy and Fuels where you can find all kinds of people playing around with dangerous fossil fuels, biofuels, carbon dioxide and stuff like that.

The paper in question is this one:

Size-Dependent Variations in Fly Ash Trace Element Chemistry: Examples from a Kentucky Power Plant and with Emphasis on Rare Earth Elements (Energy Fuels, 2017, 31 (1), pp 438–447)

It's written by Chinese scientists - the world's most knowledgeable scientists where lanthanide chemistry is concerned are in China - collaborating with scientists in Mitch McConnell's home state. (That can't be pleasant, being a scientist in a state that elected Mitch McConnell.)

One of the major environmental problems with lanthanide processing, which despite the "green" label attached to so called "renewable energy" is separations, and one of the major separations that one seeks is to separate the heavies from the lights.

Apparently coal combustion can do that.

Some excerpts from the paper:

In general, the partitioning of trace elements in coal combustion is a function of the volatility of the elements, with low volatile elements, such as the rare earth elements (REEs, or REY if Y is included), Sc, Hf, Mn, Rb, Th, and Zr, being distributed evenly across bottom ash and fly ash (group 1 after Clarke and Sloss(1) and Meij(2)), intermediate volatility elements, such as Zn and As, which are enriched in fly ash relative to bottom ash (group 2), and the halogens, Hg, Se, and B, among the most volatile elements (group 3). Among other factors, the concentration of an element in fly ash depends first upon the element abundance in the feed coal then upon combustion conditions, the type of fly ash generated (such as the amount of carbon), the particle size and surface area of the fly ash, and the flue gas temperature at the point of ash collection.(1, 3, 4) Further discussion of trace element partitioning can be found in the studies by Martinez-Tarazona and Spears,(5) Vassilev and Vassileva,(6) Senior et al.,(7-9) Yan et al.,(10) Vassilev et al.,(11, 12) Karayigit et al.,(13) Narukawa et al.,(14) Li et al.,(15) Pires and Querol,(16) López-Antón et al.,(17) and Hower et al.,(18-20) among others.

In recent years, REEs in coal and coal combustion products (CCPs) have attracted much attention because (1) the rapidly grown demand for REY as a result of their wide applications as metal catalysts, permanent magnets, light-emitting diodes, batteries, phosphors, and various components for renewable energy equipment,(21-24) (2) the supply crisis of 2010 and the price spike of 2011,(25) which was caused by the export restrictions from China and initiated a treasure hunt by way of exploration for REY deposits all over the world,(26) (3) highly elevated concentrations of REY in some coals and CCPs that are comparable to or even higher than those in conventional economic deposits,(27, 28) and (4) preliminary REY extraction experiments (e.g., studies by Taggart et al.(29) and Rozelle et al.(30)) that showed that CCPs may be technically suitable as REE ores.

Some comments on the volatile elements in coal waste, including the toxic elements arsenic, selenium, lead and uranium, coal waste being a subject about which most people could care less, even thought they can wax stupid for hours about so called "nuclear waste," with used nuclear fuel being comparatively easy to contain since in more than half a century less than 75,000 metric tons of used nuclear fuel have accumulated, whereas billions of tons of coal ash have accumulated or been vaporized:

3.2.1Some Volatile Elements (As, Se, Cr, Co, Ni, Zn, Pb, and U)
The behavior of trace elements in the ash collection system at coal-fired power plants takes on at least three different modes of behavior. Trace elements, such as arsenic, are volatilized in the boiler and then captured by the ESP or baghouse fly ash.(32, 41-43) Figure 3 based on Table 6 in the study by Sakulpitakphon et al. (with one correction that the ESP 10/325–500 mesh ash has 1949 ppm of As and not 1494 ppm as published)(32) shows the distribution of As by the ash collection hopper and by mesh size within each hopper. Not unexpected, the As concentration is higher in the second and third row ESP hoppers than in the economizer and mechanical hoppers, a function of the lower flue gas temperature in the ESP hoppers. With the caveat that every coal and every unit is different and will produce different trace element distributions, this is in line with the increases from <100 ppm of As in the mechanical hoppers to 545, 703, and 1259 ppm in the first through third ESP hoppers in another unit burning eastern Kentucky coal.(42)...

....Other volatile elements, such as Se(18, 44) and Hg,(19, 32, 41, 42) exhibit more complex behavioral patterns. Mercury concentrations in fly ash, for example, are a function of not only the Hg (and Cl) concentration in the feed coal but also (1) the flue gas T at the point of collection, (2) the amount of carbon in the fly ash, and (3) the form of carbon...

...With respect to the U concentration in the same suite of sized fly ashes, it generally shows a similar negligible variation pattern as the REE, as mentioned below. Hower et al.(20) noted a particle-size-dependent trend toward higher U in finer sizes in both the mechanical fly ash and in the second row ESP fly ash. Because the mechanical fly ash is coarser than the ESP ash, the variation in the U concentration in the ash sizes influences the overall U concentration...

And now to the interesting point:

The REEs do not show significant variation between rows of ash collection systems. With re-examination of the Ce data from the Mardon and Hower study,(42) no definitive trend in Ce variation was observed between the rows. The LREE/HREE, however, decreases from the economizer and mechanical rows to the third ESP row. Considering the fly ashes in this study, while the Ce content generally does not vary significantly between rows or between particle sizes within the individual hoppers, for the <200 mesh ashes, LREE/HREE decreases with a decrease in the particle size.

The decrease in LREE/HREE from 7.15 in the economizer hopper to 4.74 in the ESP hopper is a function of the relative LREE/HREE of the size fractions within each fly ash. The 100–500 mesh economizer ash fractions, accounting for over 78% of the ash, range from 6.93 to 7.79 LREE/HREE. In contrast, the <500 mesh fly ash, with a light LREE/HREE signature, comprises 96% of the ESP fly ash.

This graph below shows the distribution of lanthanides in particles of various sizes:

In every case, the graphs show distributions that look quite different than those found in worked ores including the most economically important today, those in China.

Of course, these coal ash particles are not really "ores" since they are still dilute when compared to mineral sources of the elements. While it might be economic at some point to extract the uranium, if only because the extremely high energy to mass ratio associated with uranium which is responsible for its environmental superiority to all other forms of energy, this is probably not the case with things like wind turbines, which have an extremely low energy to mass ratio, which accounts in part for their poor performance in arresting climate change.

Have a nice weekend.

How Lithium Batteries Catch Fire.

From Chemical & Engineering News. Periodic Graphics

French Tesla Model S Fire Was Caused by Using a Human Rather Than a Robot.


As part of its ‘Electric Road Trip’ tour for the summer, Tesla stopped in Biarritz, France to promote Model S and Model X over the weekend.

During a test drive in a Model S 90D, the vehicle suddenly made a loud noise and sent a visual alert on the dashboard stating that there was a problem with “charging”. The Tesla employee giving the test drive made the driver park the car on the side of the road and all three (the driver, the Tesla employee and another passenger) exited the vehicle.

The Tesla Model S caught on fire only a moment later (pictured above), according to witnesses.

The story is still developing. We are talking to members of the Tesla Motors Club in France and reaching out to Tesla.

Firefighters arrived quickly on the scene to control the fire, but the vehicle was completely destroyed. The result was reportedly similar to the remains of the Model S that caught fire while Supercharging in Norway earlier this year.

The update for the article was this:

Update 09/09/2016: Tesla says Model S fire in France was due to ‘electrical connection improperly tightened’ by a human instead of robots

God damned humans! Can't let them do anything!

C&E News: US Science Community Reacts to the Trump Administration.

Scientists and science advocates are among millions expressing concern over U.S. President Donald J. Trump’s first days in office.

Some moves by the Administration will affect chemists, especially those working at federal agencies. News reports about orders that allegedly restrict communication of federal science as well as a presidential directive that halts hiring of scientists and others drew reactions ranging from concern to outrage.

The biggest backlash was to widespread media reports that many agencies, such as EPA, NIH, and the Department of Agriculture, were ordered to halt communication, including distribution of scientific results...

...The American Association for the Advancement of Science pointed out that the reported moves to restrict communication would violate agency policies meant to protect scientific communication. “Many federal agencies have existing scientific integrity policies that prohibit political interference in the public dissemination of scientific findings,” says AAAS CEO Rush Holt, a former member of the U.S. House of Representatives.

Scientists were up in arms on Twitter, Facebook, and other social media about the Administration’s reported actions. A proposed demonstration called the March for Science attracted over 150,000 Facebook followers in its first two days. No date has yet been set for the event, which is to take place in Washington, D.C., and across the U.S. On social media, some compared the proposed demonstration to 2013 pro-science marches in Canada that were prompted by a muzzling of government scientists under conservative former prime minister Stephen Harper.

U.S. science community reacts to Trump Administration

Imagine that, scientists as demonstrators.

It recalls the old Kliban cartoon, in a way:

Except this time it isn't funny. And in reality, we in the scientific community are not really all just nerds. We are very much human beings, and our culture doesn't take fraud that well, and this fool in the White House is 100% that, fraud.
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