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NNadir

NNadir's Journal
NNadir's Journal
May 1, 2018

Wow. This is different. CNN actually notices there might be an ethical problem with your Tesla.

Is there such a thing as an ethical electric car?

Dirty Energy

As long as we're all "green" in the United States - our electric cars, our solar cells, our wind turbines - well - as long as we're "green" who gives a rat's ass about poor people, child slavery, any of that unpleasant stuff?

We're "green..."

Or maybe not. Despite all of us who have broken our arms patting ourselves on the back for being "green," last week we were at 411.68 ppm of the dangerous fossil fuel waste CO2 in the atmosphere, as opposed to 387.45 ten years ago.

I wonder how much of the two trillion bucks we just spent in the last ten years on "green" wind turbines and "green" solar cells went to educate the third world children who work our metal mines.

A lot, ya think?

I'm sure Elon Musk is all over it, since he's a goddamned hero, as I hear every time is holy name is mentioned.

We may be amused about public lying by the orange nightmare, but we're less interested in how we lie to ourselves. And that my friends, is a problem.

Have a nice "hump day" tomorrow.
April 28, 2018

I just stumbled into a very old paper by "Lord Rayleigh" contemplating water boiling in a pot.

John William Strutt, the 3rd Baron Rayleigh, commonly known as "Lord Rayleigh," was the winner of the 1904 Nobel Prize for his discovery of the gas Argon, which is now a very important gas with tremendous industrial application. (It is about 1% of air, by mass, but since it is non-reactive and colorless, no one before Rayleigh realized it was there. His discovery was actually incredible and relied on appreciation of very small differences in highly precise measurements of the density of nitrogen.)

"Lord Rayleigh" also discovered why the sky is blue, an effect to this day known as "Rayleigh scattering."

Recently I have been considering, in connection with understanding the physics of liquid plutonium, the physics of bubbles, a subject about which I know very little, when I came across a paper in one of my favorite journals. The paper is this one: New Modeling Strategies Evaluate Bubble Growth in Systems of Finite Extent: Energy and Environment Implications (Chatzis et al, Ind. Eng. Chem. Res., 2018, 57 (16), pp 5680–5689)

While this paper was partially about a subject I rather despise but still study (since one must know the enemy), the chemistry and physics of dangerous fossil fuels, I was inspired to go to the references and encountered a paper from the early 20th century, one by Lord Rayleigh.

Lord Rayleigh, O. M. F. R. S., VIII. On the Pressure Developed in a Liquid During the Collapse of a Spherical Cavity. London Edinb. Dubl. Philos. Mag. 1917, 34, 94– 98, DOI: 10.1080/14786440808635681

I quote:

WHEN reading O. Reynolds's description of the sounds emitted by water in a kettle as it comes to the boil, and their explanation as duo to the partial or complete collapse of bubbles as they rise through cooler water, I proposed to myself a further consideration of the problem thus presented; but I had not gone far when I learned from Sir C. Parsons that he also was interested in the same question in connexion with cavitation behind screw-propellers, and that at his instigation Mr. S. Cook, on the basis of an investigation by Besant, had calculated the pressure developed when the collapse is suddenly arrested by impact against a rigid concentric obstacle. During the collapse the fluid is regarded as incompressible. In the present note I have given a simpler derivation of Besant's results, and have extended the calculation to find the pressure in the interior of the fluid during the collapse. It appears that before the cavity is closed these pressures may rise very high in the fluid near the inner boundary.


How beautiful is that?!!!

One of the world's greatest scientists stopping, at the height of his fame, to wonder about what happens to bubbles when water boils.

Of course that's probably very much connected with why he was a great scientist, because even bubbles and the sounds they made interested him.

This struck me as very wonderful, and I thought I'd write it down.

I hope you're having a pleasant weekend. This little find has made mine.
April 27, 2018

These shibboleths are additional cases of selective attention, and frankly they're nonsense.

Let's look at the artificial criteria set for nuclear energy, which is that at no point in the next 1,000 or next million years depending on the rhetoric of the people who hate it without knowing anything at all about it, the industry prove that no one will be harmed by it.

This is a standard that no form of energy - were any other form of energy subject to it - can meet.

In a rational and morally reasonable world, the external costs of energy need to be included in the price, but they are not. Fossil fuels and biomass are allowed to kill tens of millions of lives - roughly 70 million every ten years - without being required to pay a penny of medical costs, never mind the costs of lost productivity is not charged either to the users or the producers of dangerous fossil fuel. It's charged to all future generations.

The leaking wells, the mountains whose tops have been removed, the mercury pollution, the completely ignored radioactive pollution from gas hydraulic fragmentation work (fracking) or the destruction of the planetary atmosphere, damage that will remain essentially forever.

"Renewable energy" is not at all actually "renewable," nor is the criteria for "pricing coming down" at all honest.

The first statement is true because the elements utilized in this technology can easily be depleted and in fact, their mining his highly fossil fuel dependent. I recently posted a set of graphics from a recent paper in the primary scientific literature showing this fact, because there are more and more scientists who are questioning this cockamamie scheme to destroy the planet.

Some life cycle graphics on so called "rare earth elements," i.e. the lanthanides.

Predictably this post had no response because the ingrained mythology with these "nuclear is expensive," "renewables are cheap" shit one never stops hearing consists now entirely of people sticking cotton in their ears and chanting - without a shred of thought - these same delusional slogans. But the result is clear enough. Without high density liquid fuels and extractants the useless and very expensive wind industry would collapse entirely like a turbine in Diller.

?crop=1.00xw:1.00xh;0,0&resize=900

But it's not the fact that wind turbines seldom work for more than 20-25 years, as I've pointed out with many appeals to the Danish Database of its more than 6000 turbines that are incapable of producing as much energy as one large nuclear plant can produce in a single building, never mind that Denmark has already decommissioned more than 3000 of these disgusting hulks of wasted metal, the coal used to refine that metal, the gas and coal to make the misused concrete and marine and land based diesel fueled ships and trucks.

This database is here: Danish Energy Agency Master Register of Wind Turbines

I've analyzed this database at various points in various blogs, here's text from a post I offered on another website:

If one downloads the Excel file available in the link for reference 29 one can show that the Danes, as of the end of March 2015, have built and operated 8,002 wind turbines of all sizes. Of these, 2727, or 34.1% of them have been decommissioned. Of those that were decommissioned, the mean lifetime was 16.94 years (16 years and 310 days). Twenty-one of the decommissioned wind turbines operated less than two years, two never operated at all, and 103 operated for less than 10 years. Among decommissioned turbines, the one that lasted the longest did so for 34 years and 210 days. Among all 2727 decommissioned wind turbines, 6 lasted more than 30 years.

Of the 5,275 turbines still operating there are 13 that lasted longer than 34 years and 210 days, the longest, having operated (as of March 31, 2015) for 36 years and 303 days. The mean age of operating Danish wind turbines is 15.25 years, 15 years and 92 days.

In March of 2015, the entire Danish wind industry produced 1,137,405,953 kWh (or 1.13 TWh) of electricity, which is the equivalent of 4.0967 petajoules (0.0041 exajoules). Thus for the 31 days of March 2015, the average continuous power output of the 5,275 operating wind turbines was 1529 MW. Since the rated (peak) capacity of the wind turbines operating in March of 2015 was 4096 MW, it follows that the capacity utilization of wind turbines in Denmark was 31.2%. These figures should make it clear that two average sized nuclear power plants, which would not have required thousands of trucks and cranes to travel all over Denmark trashing the landscape nor barges in the parts North Sea that the Danes have not yet trashed with oil and gas rigs as well as wind turbines, could have easily out produced all of the Danish wind turbines. Further there is no reason, other than appeals to stupidity and selective attention on the part of vociferous anti-nukes crying over a few atoms of tritium or some other such nonsense, that two hypothetical nuclear reactors could not be designed to last 60 or even 80 years. Even further, the nuclear power plants would not need redundant infrastructure to back them up.


Sustaining the Wind, Part I

The last sentence in the reproduced text brings me to the big, giant, obviously fraudulent lie that one hears over and over and over and over: "Renewable prices are falling."

If I buy a car that runs only 30% of the time that gets 40 miles per gallon when it does, but also require another car that runs the other 70% of the time, and both cars cost the same and both cars need insurance, maintenance, etc, am I being honest or am I being a freaking liar if I point to the one that gets 40 miles per gallon, isolate its cost from others and announce loudly that "driving is cheap!"?

Or am paying selective attention if I ignore the cost of the other car that I must have if I want to drive at will, particularly if I have little control or insight when the "cheap" car will be available to run?

Without access to dangerous natural gas and or coal, the renewable industry is useless. Moreover both systems are redundant and it dishonest and entirely misleading to cite the cost of one without acknowledging the cost of the other.

The inherent requirement for redundancy is wasted resources, and wasted money. I note that if I stick a neodymium iron boride magnet on a wind turbine, and another in a gas plant, the return on the external costs of manufacturing the magnet per MWh for the gas plant goes up, not down.

Moreover the external costs of each, destruction to the environment and to human and ecosystem health, accrues to the other.

Finally, it can be shown by appeal to the fact that a power plant boiler fueled by dangerous fossil fuels cannot, by definition be an adiabatic system, i.e. that it must exchange heat with the environment to work at all, it follows that shutting a gas or coal or oil powered plant actually requires that energy be wasted. If I have a pot of boiling water on my burner, and I turn it off for an hour, come back and decide I need boiling water and turn the burner back on, the water will not boil instantly. I will waste gas heating it to the boiling point all over. Even 1st graders know that. How is that so called "renewable energy" advocates never think of that issue? Is it related to the fact that they're not big on "thinking?"

Is that wise for what is already a trivial form of energy, so called "renewable energy?"

In this country, the United States, we built more than 100 nuclear reactors in less than 25 years while providing some of the cheapest electricity on earth. Why are we here to announce that what has already happened is impossible? Could it be that we listened to people with very, very, very, very poor minds, assholes like the anti-nuke Amory Lovins, Helen Caldicott, Joe Romm, Harvey Wasserman, bourgoeis shit for brains people who worked like arsonists complaining about forest fires as they worked to destroy the manufacturing infrastructure, the intellectual infrastructure, the engineering schools of the only truly new form of energy discovered in the last 100 years, a form of energy discovered and developed by some of the finest minds the world has ever known?

Can it be that picayune selective attention, emphasizing Fukushima over 7 million air pollution deaths every damn year has caused a reign of stupidity that is destroying the future?

How come we can't do what we've already done? What's the reason? Any idea?

Right now, that "cheap renewable energy" has lead to the countries in Europe having the highest electricity rates being, Denmark (where electricity is almost double the price in France) and Germany. The Danes can't drill for oil and gas in the North Sea fast enough, and the Germans have no plan to stop digging (and importing) coal.

Eurostat Energy Prices

Finally, we squandered more than 2 trillion dollars on wind and gas in the last ten years, with the result that this hyped crap doesn't even produce 10 of the 576 exajoules of energy we use each year on this planet.

This information is here, in the UNEP Frankfurt School Report, issued each year: GLOBAL TRENDS IN RENEWABLE ENERGY INVESTMENT 2017

and here:

IEA 2017 World Energy Outlook, Table 2.2 page 79 (I have converted MTOE in the original table to the SI unit exajoules in this text.)

The so called "renewable energy" industry is not at all cheap because it soaks money for almost no result. It hasn't worked to solve environmental problems, it isn't working to do so, and it won't work to do so.

The whole damn so called "renewable energy" enterprise is a huge international effort for people to lie to themselves, and to destroy the future.

There was, after all, a reason that humanity largely abandoned so called "renewable energy" in the 19th century, when the population was less than 1/7th of what it is now. The reason is that then - even more than today - most human beings lived short miserable lives in dire poverty.

And that's what we're offering our children and their children and their children and their great-great-great grandchildren, short miserable lives of dire poverty albeit, unlike the unfortunate bulk of the world population in the 19th century, lives in a severely degraded environment.

They will look at those rotting wind turbines on land and in the sea, be drinking water with the leaky toxins of land filled solar cells, perhaps billion of them, and think of us with hatred and contempt. From my perspective they will be totally justified.

History will not forgive us, nor should it.

Thanks for asking. Have a nice evening.


April 23, 2018

In a sensible world, this plutonium would be highly valued.

Metallic plutonium, of which all warheads are composed, albeit as a gallium alloy used to stabilize the delta phase, has unique properties, the most important of which is its very low melting point.

Its metallic forms a binary eutectic with iron, and a well characterized ternary eutectic with cobalt and cerium.

More intriguing is its eutectic with neptunium, suggesting that weapons grade could almost instantaneously rendered entirely unsuitable for nuclear weapons by applying the "Kessler Solution".

By the use of the neptunium/plutonium eutectic, it would be relatively straight forward to completely and totally phase out nuclear weapons.

These properties - the properties of plutonium eutectics - were explored in a marvelous reactor type that ran at Los Alamos for about two years in a very small reactor operating at about 1 MW of power in the early 1960s, before stupid journalists began holding forth on subjects about which they know nothing. The reactor could be easily contained in a small garage.

Because the phase system of plutonium includes the insolubility of the fission products strontium and cesium. This means that the use of liquid plutonium fuels allows for spontaneous separation - without appeal to any kind of chemical reprocessing - of fission products from fuel. Since cesium boils at a relatively low temperature, this means that a continuous separation via distillation is possible, allowing for the recovery of pure radiocesium for use to irradiate pollutants such as the alkyl halides, in particular those that are extremely intractable, PCBs and PFOS.

Liquid plutonium has the highest known value of eta, the neutron yield per fission, meaning it is quite simply, the world's best breeding fuel. It has a breeding ratio of 1.5, unprecedented, suggesting a doubling time of 7 years.

breeder was discussed in ref. (29). The general configuration assumed is an array of reactor modules, containing a sufficient number of modules to produce 500-1500 MW(e) (perhaps 10-30 modules). A specific and realistic description of a molten plutonium fuelled capsule core, using current best estimates for limiting factors, yields a doubling time of 7 years, breeding ratio of 1-5, and specific power of 1 MW/kg Pu.


(Whitman, Fast Breeder Reactors, Proceedings of the London Conference on Fast Breeder Reactors, Pergamon Press 1966 pg 286.)

At a specific power of 1MW/kg of liquid plutonium this means that the 54 metric tons that the idiot reporter thinks of in terms of "nuclear explosions" even though he clearly has no idea how nuclear weapons work, is sufficient to produce about 54000 megawatts of power.

In order to produce this power level, each second 671 milligrams would need to fission.

In January of 2018, according to the EIA, the consumption of electricity (accessed 4/23/18) was 373,213 thousand MWh, which translates to an average continuous power of 502000 MW.

Thus the surplus plutonium is enough produce more than 10% of US electricity. Moreover, since it has a high breeding ratio and a short doubling time none of it need be consumed; after 7 years it would be sufficient (particularly in a "breed and burn" reactor that is designed to not be refueled over periods of decades) to provide more than 100000 MW, after 14 years, 200,000 MW.

The EIA figures for January 2018 show that 64,455,000 tons of coal were burned to generate electricity in January 2018, which is up 1.8% over January of 2017, or 24 tons per second.

In order to save some of the 19,000 lives lost from air pollution every damn day, 365 days a year, 366 in leap years, we would need to completely eliminate this 24 tons a second of coal, not that we have any stupid journalists anywhere on this planet who give a shit about the 7 million people who die each year from air pollution while they prattle on ignorantly about putative "nuclear explosions.

As for "thousands of nuclear explosions" this is a remark from a scientifically illiterate shithead journalist who doesn't know shit from shinola about plutonium and doesn't apparently know what a fucking "disaster" is. A disaster is those 7 million people, not the 54 metric tons of plutonium. A "disaster" is not something that resides in his imagination to the exclusion of everything else. A disaster is what's happening.

As for "slips of the hand" one of those occurred in 1946 and killed Louis Slotin. It didn't cause a "nuclear explosion." Of the 8 people in the room, 3 lived for more than 40 years after the accident, several died in accidents, and one seems to have died from a radiation related cancer.

I know more about plutonium than the reporter at Reuters will ever know, especially since he's clearly starting somewhere close to zero.

We live in times that exalt stupidity, fear and ignorance. Journalists are a big part of the problem.

In recent years I've come to know many young men and women, people in their late teens and early twenties who are nowhere near as stupid as we are. In fact, it's been my pleasure to know many who are clearly brilliant, unbelievably so.

The plutonium described here was prepared by a race of people in a race to assure they would be known as the most absurd generation ever to have lived. These young people are vastly smarter than that generation was.

We are leaving these young people with a planet with depleted resources and a severely degraded environment, but at least, being much smarter than we are, at least they will have this plutonium and plenty of available and already mined depleted uranium in order to make more of it.

Regrettably, this, it seems to me, to be their last best hope. Thank God they have it, even if we're way to unintelligent to have understood it ourselves.

April 22, 2018

Some life cycle graphics on so called "rare earth elements," i.e. the lanthanides.

Source: Behind the Scenes of Clean Energy: The Environmental Footprint of Rare Earth Products (Zhao et alACS Sustainable Chem. Eng., 2018, 6 (3), pp 3311–3320)

No comment from me, just some pictures, all referring to the preparation of 1 kg of the various indicated materials:





Table 1. Life Cycle Impacts of 1 kg REO Common to Bayan Obo Mines and Ion-Adsorption Clays





Table 2. Life Cycle Impacts of 1 kg Phosphor





Table 3. Life Cycle Impacts of 1 kg NdFeB Magnets Produced by Two Facilities Using Two REE Sources





Have a nice evening.

April 22, 2018

Recovery of Phosphate from Human Waste.

Many large areas of the planet have been sacrificed for so called "renewable energy," including places like Glen Canyon sacrificed by an "environmentalist" named David Brower from the Sierra club in a kind of cynical trade he had no moral right to make, something to somewhat dubious credit he regretted, not that the Canyon was ever restored, anymore than the Colorado River Delta's destroyed habitat was ever restored.

(The current Sierra Club is no better: Right now they are engaged in a completely destructive attempt to sacrifice huge swathes of the continental shelf off the coast of New Jersey for idiotic unsustainable wind turbines that will be leaky navigation hazards 20 years after they're built as well a huge environmental insult to the benthic ecosystem, not that these airheads give a shit about science. Apparently the illiterate adviser to the government here from the Sierra club hates nuclear energy and is willing to send thousands of ships to sea loaded with coal based steel and coal derived concrete, because, he says, of a few uranium Navajo miners he heard about from the 1950's. What an asshole...all the wind turbines in Denmark, more than 5000 of them, can't produce as much energy as one of the two Salem Creek nuclear power plants does in one single building.)

Among the most egregious destroyed ecosystems sacrificed on the altar of so called "renewable energy" - in this case owing to run off from the agricultural land in Iowa devoted to "renewable" ethanol for cars - is the delta of North America's largest river, the Mississippi.

Hypoxia in the northern Gulf of Mexico: Does the science support the Plan to Reduce, Mitigate, and Control Hypoxia?

However not all of the destruction of the Mississippi delta and similarly surface bodies, both fresh and saline, threatened by nitrate and phosphate driven hypoxia, "eutrophication," is tied to agricultural runoff either for putative "renewable automobile fuel" or for food. Some of it derives from run-off from cities and large towns and is tied to wastewater treatment.

Fecal matter is rich in phosphorous, and many wastewater treatment systems are not equipped to remove very much of it, and it ends up in rivers, lakes, creeks, ponds, bays and seas where it taxes the ecosystems.

Phosphorous remains an essential element for maintaining the "green revolution" of the 1950's - specifically the agricultural revolution that allows us to feed a large, if stressed, human population, now exceeding seven billion people.

It is thus with interest that I came across a paper in the scientific literature today written by scientists at Cal Tech that offers an interesting approach to addressing this problem, by electrolyzing waste water: Phosphate Recovery from Human Waste via the Formation of Hydroxyapatite during Electrochemical Wastewater Treatment (Hoffman et al, ACS Sustainable Chem. Eng., 2018, 6 (3), pp 3135–3142).

From the opening text:

Discharge of phosphorus-containing wastewater to surface waters can cause algal blooms, leading to growth of toxic cyanobacteria, hypoxia, and disruption of food webs.(1,2) At the same time, phosphorus is a limited resource with an average price that has nearly tripled between 2005 and 2015,(3) making the recovery of phosphorus from waste crucial.(4) Toilet and domestic wastewater are an important source of phosphorus, as up to 22% of the world’s consumption of phosphorus could be recovered from human urine and feces.(5,6) Recovery of phosphorus from toilet wastewater or septic systems could therefore reduce phosphorus pollution as well as reduce dependency on imported mineral phosphate in countries where access to affordable fertilizers is limited.(7)

Enhanced biological phosphorus removal (EBPR) may provide effective phosphorus recovery in centralized wastewater treatment processes,(8) but in rural communities, small onsite sanitation systems (e.g., septic tanks, latrines, or cesspools) make this technology challenging without engineered processes to maintain the correct microbial population.(9) Phosphorus recovery in rural communities can be accomplished via forced precipitation as struvite (NH4MgPO4·6H2O) or hydroxyapatite (Ca5(PO4)3OH), but these strategies typically require separation of urine and feces, addition of chemicals, or use of sacrificial electrodes that further complicates and increases the cost of existing wastewater treatment strategies.(10?12)

Electrochemical systems have previously been suggested for phosphorus removal from wastewater. Electrochemical coagulation of phosphate from synthetic wastewater has been achieved using sacrificial aluminum or iron anodes,(13,14) as well as magnesium anodes, which allowed for struvite recovery from ammonium-containing solutions.(15) However, this type of electrode is depleted by oxidation and needs to be replaced on a regular basis...


The authors have developed a new series of electrodes (albeit electrodes containing the rare elements tantalum (a conflict metal) and iridium, although the main material seems to be the wonder material titanium dioxide (rutile), one of the more common minerals on earth.

During a process utilizing these electrodes the authors report the precipitation of a phosphate mineral, hydroxyapatite, after describing their goals thusly:

The purpose of this study was to evaluate the potential for phosphate removal from human wastewater during electrochemical treatment using the same combined anode–cathode system previously shown to provide efficient wastewater treatment.(20,23,24) Phosphate-containing precipitates were identified and phosphate removal efficiencies were measured in authentic and synthetic toilet wastewater. Experiments in synthetic wastewater allowed quantification of the effects of ion composition, buffering capacity, current density, and electrode surface area to volume ratio on phosphate removal kinetics and equilibria.


They use synthetic and real toilet water in their experiments, and recover calcium, phosphate and the eutrophic participant ammonium as well. A graphic from one set of experiments:



The caption:

Figure 1. Mg2+, Ca2+, PO43–T, and ammonia (NH4+ + NH3) percent removal during electrochemical treatment (3.3 V; 50 A) of toilet wastewater ([Cl–] = 80 mM) in pilot-scale reactor. Initial ion concentrations are indicated in the legend.


They do considerable analysis of their phosphate material, x-ray crystallography, all that good stuff, and then produce more results relevant here with real toilet water:



The caption:

Figure 3. Percent PO43–T, Ca2+, and Mg2+ remaining during potentiostatic electrochemical treatment (3.6 V; ?18 mA cm–2) of genuine toilet wastewater (filled markers) and synthetic wastewater (empty markers) with similar ionic compositions. [PO43–]T,0 ? 0.5 mM; [Ca2+]0 ? 1.3 mM; [Mg2+]0 ? 1.3 mM. Error bars represent ± one standard deviation of three replicates.


The authors find a limitation, the concentration of calcium needs to be relatively high to obtain nearly complete precipitation of the phosphate, although they note that urine usually contains significant calcium.

Here is a theory vs. experimentt graph of recovery of phosphate:



The caption:

Figure 4. Measured vs predicted percent total phosphate removal following galvanostatic electrolysis (4 h; 10 mA cm–2). Error bars represent ± standard deviation of three replicates. Experiments are referenced by letter and are described in Table S1.


They write:

Based on eqs 1 and 3, high phosphate removal is predicted at high initial calcium concentrations and high initial ratios of calcium to phosphate concentrations (Figure 5). Reliance on high calcium concentrations for efficient phosphate removal is a limitation of this technology. However, urine in toilet wastewater typically contains sufficient calcium to achieve greater than 50% phosphate removal (i.e., ?1 mM following ?10× dilution by flushing).(44)


Equations 1 and 3 are ordinary equilibrium equations one might find in an introductory chemistry course:





They have a nice 3D theoretical prediction graph on the relationship between calcium concentration and phosphate removal:



The caption:

Figure 5. Predicted percent total phosphate removal. Predictions are based on solving the simultaneous eqs 1 and 3 at varying initial total phosphate and calcium concentrations and a cathodic pH of 9.4.


Discussion of toilet water might be inclined to induce giggles, but it is a very serious matter.

As it happens the number of people who [Idie from a lack of toilets or even more primitive waste treatment facilities numbers about 361,000 human beings a year, children under the age of 5.

This amounts to roughly 1000 children a day.

Toilets and the water in them are serious issues, very serious issues.

But in this country, we're not at all into seriousness.

It's a little off topic as I consider the proposed destruction of the coastal benthic zone of New Jersey for a literally quixotic adventure in providing rotting steel at sea for future generations to clean up, but...but...

By contrast to the thousand children people who die each day because of trivializing selective attention, it can be shown by appeal to the scientific literature that over a period of a half a century, the number of excess deaths attributed to uranium mining by Navajos owing to cancer was less than 100.

Still, according to the asshole at the New Jersey Sierra Club, a fetish over the miners justifies destroying the benthic zone of the New Jersey coastal shelf.

The asshole notwithstanding, if we're going to bring electricity to the third world to provide toilets that are safe for the environment, that electricity needs to be nuclear electricity.

If you want to be a real environmentalist, as opposed to an ersatz environmentalist spewing 50 year old slogans about uranium miners, you need to read and think about what you read.

Have a nice Sunday evening.

April 22, 2018

I saw "The Death of Stalin" last night.

Being familiar with the history of this event, and kind of curious about it since I couldn't imagine how someone could rearrange the end of the horror of Stalinism into a comedy I went to see the movie The Death of Stalin last night by myself, as both my wife and my son at home are working like crazy on their intellectual pursuits.

I couldn't imagine I would laugh, but laugh I did. It was hysterically absurd.

Steve Buscemi, playing Khruschev - who in real life was actually a crude and uneducated, if highly intelligent man - steals the show. He plays Khruschev sort of the way he played the Carl Showalter in Fargo, although also adding a level of something quite different.

I have always hated the real life Beria, a rapist, torturer and murderer, and Simon Beale does a pretty good job portraying this awful man, although his physical resemblance is not quite that strong to the real Beria, who had a thin and almost intellectual look, although he was one of history's greatest beasts.

Michael Palin is wonderful as Molotov as well.

If you are interested at all in the tawdry history of Stalinism, as well as possessed of a somewhat offbeat sense of humor, don't miss it.



April 22, 2018

A Minor Problem With Visible Light Up-conversion to UV for Pollutant Destruction: It's a Myth.

Since the mid-20th century, a large amounts of seriously recalcitrant organic pollutants - most often organohalides - have been accumulating, sometimes at dangerous levels, particularly in the tissue of animals high in the food chain, including but not limited to human beings. One can read lots of papers about these molecules in breast milk (and the milk of other species) for example.

The long term persistence of these molecules is related to the strength of the chemical bonds that define them, and these in turn are defined, in quantum mechanical terms by a set of molecular orbitals, most often characterized mathematically as three dimensional wave functions. In quantum mechanics, the transition from one state (represented by its wave function) to another state (represented by a different wave function) requires a certain minimal energy, to wit: It is not possible for a large number of energy packets (quanta of light) to break a bond whose energy transition exceeds the energy associated with its wavelength/frequency.

The energy of light is of course, described by the famous Planck equation, which most people who take science courses encounter in high school, or in the worst case, early in their college careers:



An unfortunate feature of our times, wherever environmental issues are discussed, is sun worship - an enthusiasm for all things "solar" - that may hark back to some ancient religious fervor, I don't know, as I'm not a participant.

Scientists are not magical beings separate from humanity; they are pretty much like everyone else, and as such they can get caught up in popular fads, and run with ideas that prove to be nonsensical. Some years back, stuck in some airport somewhere and bored out of my mind with nothing to read, I came across a delightful little book all about these kinds of adventures in scientists kidding themselves, this one: Yes, We Have No Neutrons: An Eye-Opening Tour through the Twists and Turns of Bad Science. It's all about "Cold Fusion," "IQ testing" "N-rays" etc, etc, etc...

A fun read, take it as you will...

By the way, bad science does not always involve bad scientists. Highly intelligent and highly competent people can often mislead themselves terribly. Martin Fleischmann of "Cold Fusion" fame was throughout his career highly regarded as an electrochemist, the author of more than 250 scientific papers, which is why when he erroneously reported "cold fusion" he was taken - initially at least - seriously.

To return to the point of recalcitrant pollutants, it should be pretty clear that since they often appear in surface waters - the Hudson River has long been polluted with polychlorobiphenyls (PCBs) - solar energy doesn't do a very good job at decomposing them. If it did, they would tend to disappear, at least on sunny days in summer.

They, um, don't.

This is because visible light, although it is sufficiently energetic to break some chemical bonds - notably the hydrogen-oxygen bond in water, which is, of course, how photosynthesis works - is insufficiently energetic to break the (aromatic) carbon chlorine bond in a PCB.

At a minimum, higher frequency radiation is required to break these bonds, at a minimum short wavelength ultraviolet radiation, although x-rays and gamma rays are even better. Now even though humanity is working hard at destroying the ozone layer which absorbs and degrades UV radiation, it's a good thing that we can't have "solar remediation" of PCB's, since energy at the wavelength that destroys them would also destroy many of the molecules in our flesh; a fact that is connected with the ever rising rates of melanoma, a largely still incurable cancer that is involved in primitive or more sophisticated sun worship.

However the culture of enthusiasm of all things solar so much as it appears in science has lead many people to speculate that it is possible to "upconvert" visible wavelengths of light into UV light which is known to work, particularly in the presence of titanium dioxide catalysts to degrade recalcitrant pollutants.

I am hardly an expert in the theory of this stuff, by the way. In fact the first time I heard of it is in the paper from the primary scientific literature written by scientists at Yale and Clemson, that I will now discuss, which claims, that the whole affair is, in fact, a myth: The Myth of Visible Light Photocatalysis Using Lanthanide Upconversion Materials. (Cates et al, Environ. Sci. Technol., 2018, 52 (5), pp 2973–2980)

From the introduction, which covers the very real basics about titanium dioxide catalysts and the mechanism of their actions, and a brief summary of the controversy:

Heterogeneous photocatalysis has maintained a strong foothold in water treatment technology research since the explosion of studies involving TiO2 began in the 1990s. Among the many uses of semiconductor photocatalysts proposed by academia in the environmental fields, advanced oxidation is the most common; therein, production of hydroxyl radicals by catalyst suspensions in photoreactors is seen as a “chemical free” alternative to H2O2 and O3-based unit processes for destruction of recalcitrant water contaminants.1,2 While the most effective photocatalytic materials have band gap energies (Eg) that demand UV-range excitation wavelengths, many groups have pursued catalysts that are activated instead by lower-energy visible light.3?6 These efforts are motivated by the prospect of replacing energy-intensive UV lamp reactors with solar reactors, though the operational practicality of this concept has been debated.7 The primary route to visible light activation of semiconductors is through the use of materials with sufficiently low Eg or intraband states to absorb such light and promote valence electrons into the conduction band. Inherently, however, a lower Eg generally implies weaker redox potential of the resulting conduction band electrons (e? cb), valence band holes (h+ vb), or both.8


Here's a picture of the proposed mechanism that people reporting "upconversion" claim:



The caption:

Figure 1. Mechanism of visible-to-UV upconversion sensitized photocatalysis disputed herein. Green circle, UC phosphor particle; white circles, semiconductor photocatalyst particles.


In the paper the authors describe the synthesis of some of these putative upconversion catalysts and their characterization and the proposed mechanism under which they work.

The authors discuss the mechanism of upconversion, which by the way is according to them, as I understand it, a known phenomenon, but one which has very limited intensity:




The caption:

Figure 2. (A) Mechanisms of visible-to-UVC conversion by YSO: Pr3+.(16,17) (B) Primary mechanism of visible-to-UV conversion by Er3+-doped phosphors.(35) (C) Upconversion emission spectra of phosphors under 488 nm laser excitation (140 mW); inset shows YAG:Er3+ and undoped YAG spectra with adjusted axes. The peaks seen at >430 nm are due to leakage of the excitation light from the monochromator.


Anyway, they make the catalysts and then test them against a series of well known persistent organic pollutants, dyes used in the preparation of clothing.



Figure 4. (A) Decoloration of MB by phosphor-TiO2 composites under 488 nm laser irradiation. (B) MB decoloration by composites and controls under white LED irradiation. (C) Degradation of various dyes by composite materials under white LED irradiation for 240 min; solid and striped bars depict Ln3+-doped and undoped phosphor materials, respectively. (D) Degradation of phenol under white LED irradiation. Error bars denote standard deviations of experiments performed in triplicate.


They compare these unimpressive results with actual direct irradiation of "MB" methylene blue with UV radiation not resulting from "upconversion:"



Figure 5. Effect of isopropanol •OH scavenging on photocatalytic degradation of MB by YSO: Pr3+/TiO2 composite particles under W-LED (visible) and UVA irradiation. Error bars indicate standard deviations of triplicate experiments.


In their discussion the authors write:

Above we have shown that UV UC is not responsible for enhanced dye degradation rates by phosphor/TiO2 composite materials; however, our experiments did indicate that the presence of the YAG:Er3+, YSO : Pr3+, or undoped host enhanced dye degradation rates by phosphor/TiO2 composite materials; however, our experiments did indicate that the presence of the YAG : Er3+, YSO : Pr3+, or undoped host components may result in statistically significant MB degradation enhancements compared to TiO2 alone. This is enhancement is only observed when the system is excited within the MB absorption range, and it does not require absorption by the Ln3+/dielectric component. Control experiments using simple, unfused mixtures of phosphor and TiO2 particles resulted in no enhancement (SI Figure S7), thus clearly indicating that the presence of epitaxial YSO/YAG? TiO2 interface is required for the catalytic effect.


They offer some reasons for why they think that many of the papers on this subject are not reproducible or valid:

In our opinion, the overwhelming majoring of UC-PC literature exhibits three critical experimental flaws: first, the syntheses and quality of the UC materials are highly questionable, typically using low purity stock chemicals and showing XRD patterns that indicate phase impurities (e.g., see ref 21, Figure 1a and b therein). It is well-known that optical propertiesespecially in UC materialsare highly affected by certain transition metal impurities, necessitating the use of 99.99% purity or greater stock chemicals.50 Second, in order to conclude that UC is responsible for the catalytic enhancements, the use of the nonactivated phosphor host material (e.g., undoped YAP or YAG) in control experiments is required in order to confirm that opticaland not chemicaleffects are responsible. Only the study by Feng et al. included such a control, finding that their YAG:Er3+ sample enhanced MB degradation to a greater extent than YAG under white fluorescent lamp excitation (?12% vs ?8% degradation after 2 h), though both performed better than TiO2-only (?5% degradation).10

Finally, UC-PC authors rarely include UC emission spectra of the materials in their publications, which is certainly a minimum requirement for demonstrating UC capability prior to applying this phenomena to environmental technology. Studies unrelated to photocatalysis have shown visible-to-UV conversion by the same aforementioned Er3+-doped systems, though they used single crystals under pulse laser excitation with sophisticated detection systems.35?37,51 Furthermore, the UC spectrum of YSO: Pr3+ provided by Wu et al., as well as one in a more recent YSO: Pr3+ UC-PC paper, were measured with fluorescence spectrometers equipped with a xenon lamps.22,52 Based on our experience in characterizing YSO: Pr3+, cyan or blue laser excitation in excess of 50 mW and phase-sensitive detection are required to resolve the visible-to-UV anti-Stokes emission spectrum.13,26 Their spectra instead appear to be normal Stokes emission that resulted from unintentional UV excitation of the sample by second order diffraction from the source monochromator in the absence of appropriate long-pass filters. This same instrumental blunder has been implicated in false reports of UC by carbon quantum dots,53 and illustrates the importance of avoiding accidental UV excitation when attempting to measure upconverted visible light.


Too bad. One kind of wishes it worked. We could just dump titanium oxide doped with lanthanides in the Hudson River and be done with it, but we won't done with it.

Right now the PCB contaminated riverbed of the Hudson River is being dredged, but the real problem is that this is just moving a pollutant from one place to another: There is no safe place to dispose of the dredged soils really.

Speaking of another "solar will save us" degradation, the degradation of the planetary atmosphere, the vast "solar revolution" has been notoriously ineffective on that score as well. The Mauna Loa observatory seemed to be off line for a few days - I thought Trump and Pruitt had defunded it in my less than inappropriate paranoia, but it came back on line. The reported concentration on April 21, 2018 was 411.14 ppm which is, to my knowledge, the highest value ever measured there.

Be that as it may, we seem to be falling asleep worshiping the sun.

Metaphors aside, don't do it yourself. Melanoma is a tough disease: I lost two good friends to it.

Have a pleasant Sunday.










April 21, 2018

I have a good friend whose name is Michael Cohen.

Wonderful guy, very intelligent, very liberal, a good and supportive friend, but I haven't been in touch with him for a few years.

I called him up this week to make fun of him and his name.

Those of us who have common names that are shared with famous people take a certain amount of crap about it. I've had it my whole life, and it was nice to kid him about it.

Of course, as I know full well, people making jokes about you sharing a name with a famous person always think they're being original and funny and of course, you've heard those jokes 10,000 times, and I'm sure he's going through that, but having been a victim myself, I just couldn't restrain myself.

I try to have a good nature about it, and so did he.

At least the person(s) with whom I share a name aren't going to prison for helping a racist criminal into the White House.

If this state of affairs is a tragedy for our country and the world, a small silver lining for me was to connect with an old friend with whom I needed to be in touch.

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