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Gender: Male
Current location: New Jersey
Member since: 2002
Number of posts: 27,981

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I feel like some old engine...

...that lost it's driving wheel.

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In the last 3 years, 21 million people died from air pollution. This figure is clearly...

...available in the scientific literature, a literature with which the deplorables in the anti-nuke industry avoid familiarity, since it's pretty clear that they only not only fail to know any science whatsoever, but actually despise science in general, and math in particular.

A comparative risk assessment of burden of disease and injury attributable to 67 risk factors and risk factor clusters in 21 regions, 1990–2010: a systematic analysis for the Global Burden of Disease Study 2010 (Lancet 2012, 380, 2224–60: For air pollution mortality figures see Table 3, page 2238 and the text on page 2240.)

The air pollution death rate is roughly 800 deaths per hour, every hour, 8766 hours per year, every year, ten years per decade.

And the response from the deplorables in the anti-nuke industry. Innuendo, and more innuendo.

There's something Trumpian about this. Last night the orange asshole carried on about emails, with Ms. Clinton pointing out firmly - and completely honestly - that no secure information was ever breached, and that there is no evidence whatsoever that anyone was harmed by this faux Trumpian defined "disaster."

How is the innuendo here different? Well, for one thing, the deplorable carrying on by anti-nukes, stretching over decades of fear and ignorance resulted in far fewer lives having been saved from death by air pollution than the 1.8 million lives that were saved because of the use of nuclear energy, as noted again, in a highly cited and widely read publication in one of the world's premier scientific journals written by one of the world's most respected climate scientists:

Prevented Mortality and Greenhouse Gas Emissions from Historical and Projected Nuclear Power

(Pushker A. Kharecha* and James E. Hansen NASA Goddard Institute for Space Studies and Columbia University Earth Institute, 2880 Broadway, New York, New York 10025, United States Environ. Sci. Technol., 2013, 47 (9), pp 4889–4895)

(Trump, by contrast, hasn't killed anyone yet, not at least to our knowledge, and it seems that the American people will prevent him from doing so by kicking his useless ass in the coming election.)

But the real tragedy associated with the deplorable anti-nuke selective attention - by which they couldn't give a fuck about tens of millions of air pollution deaths even as they carry on about software that has harmed no one - is that they helped promote an approach to the environment that failed and failed miserably.

2016 is now being recorded as a year of unprecedented new accumulations of the dangerous fossil fuel waste carbon dioxide in the planetary atmosphere. The deplorables in the anti-nuke industry convinced the world to invest quantities measuring in the trillions of dollars on so called "renewable energy," chiefly the solar and wind industry. Combined these two industries, despite this huge expenditure - which might have been more wisely spent on thousands of more useful things - don't produce 5 of the 570 exajoules of primary energy that humanity generates and consumes each year.

As a result, the fastest growing source of energy on this planet is a dangerous fossil fuel, natural gas, without which, by the way, the so called "renewable energy" scam would be even more useless.

In the last ten years while two trillion dollars was being squandered on this unsustainable garbage - which is not actually "renewable" since it relies on the mining of vast quantities of toxic and increasingly rare elements - the rate of increase of the increase in dangerous fossil fuels - the second derivative for those who, unlike anti-nukes, know math - has reached new levels never seen before. 2016 is likely to be the second year in a row that the increase is more than 3.00 ppm, despite never having reached such a rate in recorded history.

So called "renewable energy" didn't work; it isn't working; and it won't work.

Heckuva job deplorables. Heckuva job.

Have a nice week.

Meanwhile Humanity for Hillary Goes Positive...

...Just got to love these beautiful young people coming together to dance to celebrate our diversity and our candidate:


And on their website, they have this powerful endorsement by Makail Baryshnikov:

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It all makes me positive, makes me feel why we should love our candidate.

Reflections on this year's CO2 minimum at the Mauna Loa observatory.

This will be my 20,000th post on this site; maybe I shouldn't have bothered with the internet all all.

Whatever. As Macbeth remarked, "What is done cannot be undone."

The Mauna Loa Observatory each week releases a data point comparing carbon dioxide concentrations in a recent week with the same week of a previous year and the value of the week ten years before.

Each year, carbon dioxide concentrations almost always reach a minimum for the year as a whole in the well into September or early October. In 2015, this point was September 27, at 397.20 ppm; in 2014, it was on September 21, at 395.31 ppm; in 2013, it was on September 8, at 392.06 ppm; for 2012, it was September 16 at 390.73 ppm; for 2011, it was on September 18, at 389.08 ppm.

For September 27, 2016 - the likely minimum this year - the value was 400.72 ppm

The average value for the increases, as compared to the previous year of these weekly data points recorded at Mauna Loa since their inception in 1975 for all data points, - not just those at minimums - is 1.77 ppm. Of those points recorded in the 20th century, the average was 1.54 ppm. For points recorded in the 21st century, the average increase over the previous year is 2.10 ppm.

For 2014, the average was 2.09 ppm, for 2015 - which proved to be the worst year ever recorded, 3.05 ppm over 2014 - the weekly average increases were 2.26 ppm.

For 2016, the average thus far is 3.52 ppm.

The worst 30 such increases recorded of the 2122 such data points, 15 have been recorded in 2016, including the two worst ever recorded, 5.04 ppm on July 31 of this year, and 4.78 on June 12.

All of our efforts to address climate change have failed.

I have taken some flack over the 14 years I've been writing here for my support for nuclear energy. Everything I have ever written on the topic here and elsewhere may have been a complete waste of time - I spent too much of it calling out, in harsh terms, the complete idiots who despise nuclear energy because they get their information from cartoons and uneducated thugs rather than from science and engineering texts. It was a different approach from the polite attempts to be reasonable, like say those of the great scientist who once headed the Atomic Energy Commission, Glenn Seaborg.

It seems likely everything I have ever said or did about energy has failed; but so did everything that Glenn Seaborg said or did about nuclear energy has also failed.

And we are another kind of minimum, the time when we are doing the minimum to address the crisis before all future generations.

The world is investing heavily is so called "renewable energy." Like my less than important efforts on behalf of nuclear energy, and the work of many highly educated - many great - scientists and engineers who worked on behalf of nuclear energy have failed, so has renewable energy failed, and so, as the data above shows, it is failing, and so the laws of physics require that it will fail.

I did what I could in my thousands of posts here and elsewhere, sometimes at the cost of being shut up, as was the case some years ago when I was banned at Daily Kos by the scientifically illiterate journalists who run the place, for um, telling the truth:

The great climate scientist Jim Hansen has published in the primary scientific literature a paper with something called scientific references, data that shows that nuclear energy 1.8 million lives. (Environ. Sci. Technol., 2013, 47 (9), pp 4889–4895) Hansen shows that were it not for fear and ignorance, nuclear energy might save 10 million lives more, with just a minor tech.

It follows that anti-nukes are not merely enemies of the people, they are murderers, pure and simple, murderers whose weapons are fear and ignorance.

Have a nice of evening.

Comment in: GETTING TO ZERO: Is renewable energy economically viable?

20,000 posts is a milestone, not an accomplishment. I noted in an earlier post here that we will never see a value at Mauna Loa under 400 ppm in our lifetimes, if ever.

Paper in Nature Climate Change: We will never again see monthly readings less than 400 ppm...in our lifetimes.

The author of the paper cited therein, wrote the following about the 400 ppm figure:

...A point of interest is the passing of 400 ppm in the Mauna Loa record. Although there is nothing physically significant about this concentration, it has recently become an iconic milestone in popular discourse regarding the ongoing rise in atmospheric CO2 (for example, ref. 15). In the last two years, CO2 has fluctuated around 400 ppm through the annual cycle, which has amplitude of approximately 6–7 ppm at Mauna Loa. 2014 was the first year that monthly CO2 concentrations rose above 400 ppm, and in 2015 the annual mean concentration has passed 400 ppm for the first time, but the monthly mean concentration fell back below 400 ppm for three months at the end of the boreal summer, reaching a monthly mean of 397.50 ppm in September. Adding the recent mean growth rate of 2.1 ppm yr−1 to this value would suggest a 2016 September concentration of 399.60 ppm. However, on the basis of the observed and forecast Niño 3.4 SSTs as of November 2015, we predict a Mauna Loa CO2 concentration in September 2016 of 401.48 ± 0.53 ppm (Fig. 3)...

...In the longer term, a reduction in CO2 concentration would require substantial and sustained cuts in anthropogenic emissions to near zero. Even the lowest emissions/concentrations scenario assessed in the IPCC Fifth Assessment Report projects CO2 concentrations to remain above 400 ppm until 2150. This scenario, RCP2.621, is considered amongst the lowest credible emissions scenario, and relies on assumed development of 'negative emissions' methods whose potential is considered limited22. Indeed some argue that RCP2.6 is now beyond reach without radical changes in global society23. Hence our forecast supports the suggestion24 that the Mauna Loa record will never again show CO2 concentrations below the symbolic 400 ppm within our lifetimes.

El Niño and a record CO2 rise (Richard A. Betts, Chris D. Jones, Jeff R. Knight, Ralph F. Keeling & John J. Kennedy, Nature Climate Change 6, 806–810 (2016))

If you're young, I'm deeply ashamed of what my generation has done for yours, but as old man in the waning years of life, looking back, let me say that the wasted time is the time you will regret when you run out of it.

May we chat again, but if not, as Spike Lee put it, "Do the Right Thing."

Enjoy the remainder of the weekend.

Eleven of the 37 weeks of 2016 have shown CO2 increases higher than 4.00 ppm...

...over the same week of 2015 at the Mauna Loa observatory.

Up-to-date weekly average CO2 at Mauna Loa (Accessed September 18, 2016)

The reading for the week ending September 11, 2016 of 401.33 ppm is 4.03 ppm higher than the reading in the same week last year.

Before 2016, there were only 8 such readings in the entire history of the observatory's record of 2020 such readings going back to 1975.

They were the weeks ending September 6, 1998 (4.67 ppm), February 3, 2013 (4.54 ppm), September 27,1998 (4.49) ppm, April 18, 2010 (4.38 ppm), August 16, 2010 (4.17 ppm), May 6, 2012 and April 13, 2014, both at 4.01 ppm.

There are now 18 such readings, including one over 5.00 ppm, 5.04 ppm to be exact, on July 31 of this year. There was one other reading, 4.78 ppm, June 6, 2016 that exceeded all previous readings ever recorded.

Readings in the 20th century of this type averaged 1.54 ppm. In the 21st century, that same average is 2.09 ppm. For 2016 it is 3.52 ppm.

Since the destruction of the nuclear reactors, and thousands of buildings, at Fukushima, after which Japan shut it's nuclear reactors to see if they were "safe" and replaced them with power generated by burning dangerous fossil fuels using plants that kill people 100% of the time they operate, and not just after huge tsunamis, the average for these figures is 2.37 ppm.

In the last ten years, the world has squandered, other people use the word "invested", approximately two trillion dollars on so called "renewable energy" mostly on wind and solar infrastructure that will all be landfill within the next 30 years.

It didn't work; it isn't working; and it won't work.

If any of this troubles you; don't worry, be happy.

The City of Los Angeles has announced that it will be 100% powered by so called "renewable energy" "by 2030."

We can add this to the tens of thousands of announced programs and forecasts of "renewable energy by such and such a date" going back over half a century, beginning with Amory Lovins 1976 announcement that the United States would be producing 16 quads of solar energy "by 2000" (the entire planet as of 2016 doesn't produce 2 such quads), and extending right up to the present day.

Most such announcements choose a "by such and such a date" time point that will take place after the soothsayer offering it will be dead, but no matter.

All such predictions have been delusional. All are cases of people lying to themselves, something we are all happy to do, since it places the onus of action on our children and grandchildren to do what we have not done, and in fact, can't do, since so called "renewable energy" is, 1) not renewable, and 2) not sustainable, and 3) not realistic.

The world was previously powered by so called "renewable energy" up until the early 19th century, when so called "renewable energy" was abandoned because the bulk of the world's population, even more so than today, lived short, miserable lives of dire poverty.

But again, don't worry. Be happy.

It's the thought that counts, not results.

Have a wonderful week.

Paper in Nature Climate Change: We will never again see monthly readings less than 400 ppm...

...in our lifetimes. As anyone familiar with my record here will know, I have been reporting on the disastrous climate events that have been taking place in 2016 where the carbon dioxide concentrations have been climbing at a record pace.

My last entry on this topic was here: July 31, 2016: Mauna Loa carbon dioxide levels 5.04 ppm higher than one year ago.

For the first time in recorded history, the weekly year to year comparisons at the Mauna Loa carbon dioxide observatory have exceeded a 5.00 ppm increase over levels a year ago.

On July 31, 2016, the concentration of carbon dioxide at Mauna Loa was 403.47 ppm; one year ago it was 398.43 ppm.

Mauna Loa Weekly Trends, accessed Aug 7, 2016

During summers in the Northern Hemisphere, carbon dioxide levels fall slightly from the peaks usually observed in April or May; the minimums usually occur in September. The 2016 max, observed during the week ending on April 10, 2016 was 408.31 ppm.

All of humanity's efforts to address climate change have failed. This includes all the, rhetoric, charts and graphs about the "triumph" of so called "renewable energy" on which we bet, foolishly as it turns out, our planet's atmosphere.

Some folks in the primary scientific literature have commented on it as well.

The paper attached comes from the journal Nature Climate Change:

El Niño and a record CO2 rise (Richard A. Betts,
Chris D. Jones, Jeff R. Knight, Ralph F. Keeling & John J. Kennedy , Nature Climate Change 6, 806–810 (2016))

Some excerpts:

The introduction:

The long-term rise in atmospheric CO2 concentration, approximately 2.1 ppm yr−1 over the past decade, is caused by anthropogenic emissions arising from fossil fuel burning, deforestation and cement production1, 2. The annual growth rate, however, varies considerably as a result of climate variability affecting the relative strength of land and ocean carbon sources and sinks. The annual growth rate measured at Mauna Loa, Hawaii3, 4 is correlated with the El Niño–Southern Oscillation (ENSO), with more rapid growth associated with El Niño events5, 6, 7, 8, 9 through drying of tropical land regions and forest fires. To test the predictive value of this relationship, we present a forecast, made in October 2015, of the CO2 concentrations throughout 2016 based on the relationship, and verify against observations available so far. We predict the monthly mean CO2 concentration at Mauna Loa to remain above 400 ppm even in its annual minimum in September, which would not have been expected without the 2015–2016 El Niño...

The relationship between 1998 and 2016:

Historically there have been markedly large annual CO2 growth rates in El Niño years (Fig. 1), probably due to warming and drying of tropical land areas resulting in reduced carbon uptake by vegetation growth, increased carbon release by fire and drought-induced tree mortality. In 1997, dry conditions in Indonesia and Malaysia allowed human-ignited fires to escape control and ignite carbon-rich peatlands, which continued to burn for some months. An estimated 0.81 to 2.57 GtC were emitted to the atmosphere as a result11, equivalent to 13–40% of global annual mean carbon emissions from fossil fuels at that time and hence a substantial contribution to the anomalously large CO2 growth rate that year12. During La Niña events, when the equatorial Pacific is colder than average, the annual CO2 growth rate is slower.

The recent El Niño, now in its declining phase, was comparable with the 1997–1998 event in some respects. Although maximum SSTs were cooler in the eastern tropical Pacific, the Niño 3.4 index was 2.6 ± 0.30 °C over November 2015 to January 2016 (larger than November 1997 to January 1998) and most tropical land regions were again anomalously dry. Once again, drought conditions allowed human-caused fires in Indonesia to burn large areas. Estimates for 2015 suggest that the total greenhouse gas emissions from these fires is equivalent to 0.4 GtC, with large uncertainty — less than those in 1997 13, but still larger than for non-El Niño years.

Some comment on the "meaning" of 400 ppm:
...A point of interest is the passing of 400 ppm in the Mauna Loa record. Although there is nothing physically significant about this concentration, it has recently become an iconic milestone in popular discourse regarding the ongoing rise in atmospheric CO2 (for example, ref. 15). In the last two years, CO2 has fluctuated around 400 ppm through the annual cycle, which has amplitude of approximately 6–7 ppm at Mauna Loa. 2014 was the first year that monthly CO2 concentrations rose above 400 ppm, and in 2015 the annual mean concentration has passed 400 ppm for the first time, but the monthly mean concentration fell back below 400 ppm for three months at the end of the boreal summer, reaching a monthly mean of 397.50 ppm in September. Adding the recent mean growth rate of 2.1 ppm yr−1 to this value would suggest a 2016 September concentration of 399.60 ppm. However, on the basis of the observed and forecast Niño 3.4 SSTs as of November 2015, we predict a Mauna Loa CO2 concentration in September 2016 of 401.48 ± 0.53 ppm (Fig. 3)...

And now the depressing part, wherein the bold is mine.

With the growth rate expected to reduce again after the El Niño, could the annual minimum CO2 concentration fall back below 400 ppm again next year or further in the future? This is exceptionally unlikely. In the instrumental record that covers the last half-century, annual growth rate has always been positive as a result of ongoing anthropogenic emissions, and the amplitude of the seasonal cycle has not varied substantially. Both the annual mean and September minimum CO2 concentrations have therefore increased year on year. This was the case even in years with large La Niña events or major volcanic eruptions that temporarily caused cooling and greater net uptake of CO2 by the biosphere, resulting in smaller, but still positive growth (Fig. 1a). For example, in the large La Niña in 1999–2000, the growth rate remained above 1ppm yr−1. Unless a very large volcanic eruption injects substantial quantities of aerosol into the stratosphere, we would expect concentrations continue to rise further above 400 ppm in the next few years.

In the longer term, a reduction in CO2 concentration would require substantial and sustained cuts in anthropogenic emissions to near zero. Even the lowest emissions/concentrations scenario assessed in the IPCC Fifth Assessment Report projects CO2 concentrations to remain above 400 ppm until 2150. This scenario, RCP2.621, is considered amongst the lowest credible emissions scenario, and relies on assumed development of 'negative emissions' methods whose potential is considered limited22. Indeed some argue that RCP2.6 is now beyond reach without radical changes in global society23. Hence our forecast supports the suggestion24 that the Mauna Loa record will never again show CO2 concentrations below the symbolic 400 ppm within our lifetimes.

If any of this bothers you, don't worry, be happy.

Those assholes at Greenpeace are continuously and constantly predicting that sometime after they and everyone else who had to sit through their tiresome repetitive and illiterate bullshit will be dead, the world will be a 100% renewable nirvana. The fact that they have been predicting this endlessly and continuously and that things are getting much, much, much worse, and not better, has no meaning.

As you may know, Greenpeace is not an organization where people do science, science being a practice in which results trump theory. You can't get into Greenpeace if you're aware of the contents of an engineering or biology or chemistry or physics or math book - but if you join Greenpeace you sure can talk, and talk, and talk - especially on subjects you know nothing about - even as the rest of us, and all future generations choke, and choke, and choke and choke.

So called "renewable energy" didn't work; it isn't working; and it won't work, but it's not results, but the thought that counts.

Have a lovely weekend.

Fun with Chemistry: Recovering the rare element gallium from dead solar cells.

Last night I was reading several papers in the literature concerned with what the badly screwed future generations might do with all the solar cells we've been manufacturing in recent years, despite the fact that they have failed to do a damned thing to address the accelerating rate of climate change.

The solar industry is tiny and clearly useless despite soaking up trillions of dollars, and there are many rote assumptions that claim they are "green" (as in environmentally benign) and "sustainable" (they can be used indefinitely).

As is the case with many rote assumptions, they are wrong.

The paper to which I will refer here is this one: Separating and Recycling Plastic, Glass, and Gallium from Waste Solar Cell Modules by Nitrogen Pyrolysis and Vacuum Decomposition (Lingen Zhang and Zhenming Xu, Environ. Sci. Technol., 2016, 50 (17), pp 9242–9250)

Some text from the paper:

The first solar cell was invented at Bell Laboratories in 1954. After the energy crisis of the 1970s, the products of solar cells started to be used in civilian fields. Converting the energy of sunlight into an easily usable form is one of the most attractive solutions to the shortage of fossil energy.(1) Photovoltaic energy has been known as the cleanest energy in the 21st century. With the rapidly expanding of photovoltaic market, the output of solar cells is growing by about 28.14% a year in China.(2) The solar cells have been widely used in transportation, communications, space, and other fields. Crystalline silicon has become an important and dominant semiconductor material in most of solar cells.(3) Apart from Si wafer-based module, gallium arsenide (GaAs) which is a compound semiconductor has been used for decades to make ultrahigh-efficiency solar cells because of its advantages, including their high photoelectric conversion efficiency and excellent antiradiation performance.(4, 5)...

...Gallium, as an important strategic resource, has been categorized as one of 14 mineral resources by the European Commission in extreme shortage.(11) The world reserve of gallium has been estimated to be 18 000 tones, which is merely one tenth of gold.(12) In nature, gallium has no ores of its own at all; rather it occurs in trace and minor amounts in various associated minerals types, such as bauxite, zinc, tin, and tungsten ores.(13, 14) Hence, it has led to strong interest for recovery of gallium from wastes. At present, various researches have been developed to recycle gallium. Technologies include acid leaching,(15) organic solvent,(16, 17) chemical precipitation, electrochemistry,(18, 19) and supercritical extraction(20) etc. I.M. Ahmed(21) proposed extracting method by Cyanex 923 (a mixture of four trialkylphosphine oxides) and Cyanex 925 (bis(2,4,4-trimethylpentyl) octylphosphine oxide) in kerosene from hydrochloric acid medium to recycle Ga(III). Although these studies have focused on recycling gallium resource, environmental improvement are still challenging due to limitations on using large volume of acid/alkali/organic reagent with high concentration.

The bold is mine. That bolded remark doesn't sound all that "renewable" to me.

The authors propose nitrogen pyrolysis and vacuum decomposition which is (they say) cleaner. Here's some of their investigation of the "clean" process.

The effect of temperature on the organic conversion rate was investigated in the range from 573 to 1073 K at 0.5 L/min N2 flow rate lasting 30 min. It could be seen from Figure 6(a) that the organic conversion rate was low when temperature was 573 and 623 K, which was 19.61% and 36.02%, respectively. But when temperature reached 673 K, the organic conversion rate sharply increased and exceeded 98%. With the temperature over 773 K, the organic conversion rate reached approximately 100%. It indicated that the pyrolysis temperature of plastic components was 773 K. We analyzed the organic components of oil products from 773 to 1073 K. The results were summarized graphically in Figure 7(a). We found that the organic components of oil and gas products had obvious changes with the increasing of temperature. When the temperature reached 773 K, alkanes and olefins were main organic components in the oil products. But, some naphthenes, acetophenone, and methyl naphthalene, etc. began to be detected in pyrolysis oil products with the temperature rising to 873 K. When the temperature arrived 973 and 1073 K, anthracene, phenanthrene, and homologues of benzene were main components of pyrolysis oil products. For pyrolysis gas products from panel materials (as shown in Figure 7(b)), benzene rapidly increased with increasing of temperature. But, components of gas products were not change. Therefore, the temperature of pyrolysis should be controlled under the condition of 773 K.

Um...benzene. I'm sure they'll be absolutely safe, since all recycling facilities for electronic waste are absolutely safe.

The arsenic is recovered as diatomic arsenic gas which distills away.

The process is in no way quantitative.

he effect of temperature on the recovery efficiency of gallium was investigated in the range from 973 to 1273 K, maintaining system pressure of 1 Pa and reaction time of 40 min. As shown in Figure 9(a), the recovery efficiency of gallium increased sharply with an increase of temperature from 973 to 1023 K. The recovery efficiency reached 60.9% when the temperature was 1023 K, and then its rise began to slow. The recovery efficiency of gallium increased to 76.4% with the temperatures reached 1273 K. Figure 9(b) showed the theoretical and experimental evaporation rate of Ga particles. In theory, the evaporation rate of gallium should be increased with the increase of temperature, according to Langmuir-Knudsen eq (eq 3). However, the evaporation rate has not changed in our experiment. The experimental evaporation rate of Ga presented nearly linear relationship with temperature, which was range from 5.64 × 10–5 to 2.12 × 10–4. Its explanation may be that on the one hand, first, the decomposition reaction of GaAs is happened, which needed a high temperature and then metallic gallium can volatilize.

Well, whatever gallium and arsenic remains, we can always take it to a "green landfill."

It's amazing how much handwaving and how many ill thought out beliefs, dogmatic beliefs, get attached to the solar industry, since for many decades it was all theory and no practice.

The practice is quite different. Trillion dollar quantities of resources have been thrown at this industry in the last ten years, with the result that the annual increases in the dangerous fossil fuel waste carbon dioxide is the highest ever observed.

It is expected that in about twenty years, about two million tons of used and dysfunctional solar cells will need disposal on this planet. cf (Sustainable System for Raw-Metal Recovery from Crystalline Silicon Solar Panels: From Noble-Metal Extraction to Lead Removal (Byungjo Jung†, Jongsung Park‡, Donghwan Seo†, and Nochang Park*, ACS Sustainable Chem. Eng., 2016, 4 (8), pp 4079–4083)

Enjoy the coming weekend.


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Can Bisphenol A Be Replaced By a Derivative of Vanilla?

Recently I remarked in this space that one possible route, maybe the only route, to fixing carbon dioxide from the air - something that will prove necessary for future generations since our generation did nothing whatsoever to address climate change - will involve making products from biomass that effective sequester carbon.

The difficulty of taking a lab route for usefully fixing CO2 to an industrial level.

In recent years there have been many discussions of this approach in the scientific literature, and I came across an interesting paper that puts a fun - and interesting - spin on the topic.

The paper is here: Synthesis and Characterization of Bio-based Epoxy Resins Derived from Vanillyl Alcohol (Joseph F. Stanzione III, ACS Sustainable Chem. Eng., 2016, 4 (8), pp 4328–4339)

Many people are aware that there is growing concern that many plastics, in particular polycarbonates, are co-polymerized with bis-phenol A, which can leach out of the plastics and is a known endocrine disrupting chemical owing to some structural features making it similar to some steroidal compounds in the estrogenic pathway. Polycarbonate plastics are the tough, hard plastics commonly used for water storage bottles, baby bottles, etc.

An excerpt from the text of the paper is here:

Thermosetting polymers, such as epoxy, vinyl ester (VE), and unsaturated polyester (UPE) resins, have found utility in a wide range of industrial and commercial applications including adhesives, coatings, and composites.(1, 2) Epoxy resins dominate the thermosetting polymers market making up roughly 70% of all thermosetting polymers,(3) due to their outstanding thermomechanical properties comprising high glass transition temperatures (Tg’s) and high glassy moduli (E′’s) at 25 °C as well as good chemical resistance, when polymerized with an appropriate curing agent.(1, 2, 4) Unfortunately, the majority of commercial thermosetting polymers currently being produced are synthesized from nonrenewable, petrol-based chemicals. Since the inception of the first commercial diglycidyl ethers in the 1940s, the epoxy resin industry has been dominated by the petrochemical-based diglycidyl ether of bisphenol A (DGEBA).(1, 2, 5) This bisphenol A (BPA)-based epoxy resin is found in over 90% of thermosetting epoxy resins worldwide, in a market with a global production currently exceeding 2 million tons per year.(3)

DGEBA is a product of two main reactants, BPA and epichlorohydrin, with epichlorohydrin, historically synthesized via a multistep pathway starting with propylene.(1, 2, 6, 7) There is currently no renewable source for BPA; however, Dow Glycerin to Epichlorohydrin (GTE) Technologies and Solvay Epicerol have recently reported processes for the synthesis of epichlorohydrin from bio-based glycerol, a byproduct of biodiesel production.(8, 9) BPA (4,4′-isopropylidenediphenol) is typically synthesized via an acid catalyzed electrophilic aromatic condensation of phenol and acetone with a stoichiometric ratio of 2:1, yet the process uses large excesses of phenol to reduce the formation of higher molecular weight oligomers.(10, 11) BPA is used as the base molecule in thermosetting epoxy resins, as the bisphenolic structure provides molecular rigidity to the polymer network; thus, promoting their outstanding thermomechanical properties.(11) However, the use of BPA in epoxy resins has received a great deal of scrutiny and debate, while concerns of human exposure to BPA, a known human endocrine disruptor, via leaching from resins and food and beverage can coatings are driving the search for a suitable alternative that is both renewable and nontoxic.(3, 12)

The Dow process for producing epichlorohydrin from glycerol, a generally worthless side product of the production of biodiesel and soap, is described here:

Glycerin as a Renewable Feedstock for Epichlorohydrin Production. The GTE Process (Briggs et al Clean 2008, 36 (8), 657 – 661)

The idea is to take a "generally worthless" product and make it worth something. Polymers derived from glycerol are fixed carbon that is removed from the atmosphere.

Now for the fun part, the chemical whose flavor I love, vanillin, actually the alcohol made by reducing vanillin.

The authors write:

In the present work, we report the electrophilic aromatic condensation of vanillyl alcohol (1) with guaiacol (2) to produce bisguaiacol (BG) isomers (3). The reaction is given in Scheme 2, in which the major structural bisguaiacol isomer formed was determined to be para–para. The synthesis of bisguaiacol avoids the use of carcinogenic and highly volatile molecules like formaldehyde and acetone as the hydromethyl group present on vanillyl alcohol already provides the necessary handle and reactivity for facile and desired phenolic coupling and methylene bridge formation.

To produce a bio-based epoxy, BG (3) was then reacted with epichlorohydrin (4) to produce a diglycidyl ether of bisguaiacol (DGEBG; 5) as shown in Scheme 3. To study the influence of the methoxy moiety attached to the aromatic ring on cured polymer properties, diglycidyl ether of vanillyl alcohol (DGEVA) and diglycidyl ether of gastrodigenin (DGEGD) were also synthesized in the same manner as DGEBG (Figure 1). Furthermore, as DGEVA and DGEGD can be considered useful bio-based epoxies, diglycidyl ether of hydroquinone (DGEHQ; Figure 1) was also synthesized in order to study the influence of the methylene spacer between the aromatic ring and the glycidyl ether. The epoxy resins were cured, either by themselves or with a commercial BPA-based epoxy resin, with stoichiometric equivalents of Amicure PACM (4,4′-methylenebiscyclohexanamine; Figure 1). The thermomechanical properties of the cured polymers were tested via dynamic mechanical analysis (DMA) to determine if these resins are suitable alternatives to current commercially available petroleum-based resins.

For those who are interested in organic chemistry, here is scheme 2:

Here is scheme 3, regrettably not high quality as a graphic, but if you know some organic chemistry, you can fill in the blanks:

Recall that the authors are proposing to use epichlorohydrin derived from glycerol, so the molecules in scheme 3 are entirely derived from biomass.

Vanillin is of course available from vanilla beans, but it is mostly available on an industrial scale from the hydrolysis or thermolysis of lignin, the structural component of wood and straw that is not cellulose. (Many similar compounds are also obtained from the digestion of lignin, many of which will prove to have other uses.)

The authors report that the resulting polymers have excellent properties, comparable to the properties of the petroleum based thermosetting polymers.

There's a long way between bench top chemistry and commercial applications, but, nonetheless, it's interesting I think.

I wonder if the leachates will taste good. I personally love the vanilla flavor; can't get enough of it. I'm a vanilla kind of guy.

Have a nice evening.

A Brief Note of Warning on Fatalities Associated With the Storage of Wood Stove Pellets.

This one came as a surprise to me, but I stumbled across it while going through the scientific literature this afternoon. Apparently in recent years there have been nine fatalities associated with the storage of wood pellets for wood pellet stoves.

Influence of Oxygen Availability on off-Gassing Rates of Emissions from Stored Wood Pellets (Irene Sedlmayer et al, Energy Fuels, 2016, 30 (2), pp 1006–1012)

From the text:

In times of increasing energy demand, concerns about climate change, and decrease of fossil resources, the attractiveness of alternative fuels such as wood is growing. Wood pellets are high in energy density, easy to handle, and homogeneous in quality.(1) Thus, they are most competitive with fossil fuels for heating purposes among wooden fuel types. Accordingly, the worldwide pellet market has been growing. In 2008 the worldwide pellet consumption was about 10,000,000 tons increasing to 13,500,000 tons in 2010.(2) A statistical report by the European Pellets Council published in 2014 reports the worlds wood pellets production reached 24,500,000 tons in 2013.(3) According to the same report, about 2/3 of the global pellet consumption is attributed to heating. So far, Europe remains the largest pellet consumer market responsible for around 80% of the world’s wood pellet consumption. Estimates of the European Pellet Council further indicate that at least 55% of the European pellet consumption is utilized on the residential heating sector, <50 kW.(3)

Wood pellets are known to emit various gaseous emissions during production, transportation, and storage.(4-9) Nine fatal accidents occurred since 2002 during storage or transportation of mostly big bulks of wood pellets but also in small scale stores.(10) Subsequent investigation indicated increased concentrations of CO, CO2, VOC, CH4,(4, 5, 11, 12) and H2(13) and simultaneous depletion of O2(14, 15) in pellet stores leading to a toxic breathing atmosphere. According to Svedberg et al.(12) O2 declined to levels from 16.9 to 0.8% in closed storages like ocean vessels. However, the concentration of oxygen in ventilated pellet storages strongly depends on the efficiency of ventilation. It can be assumed that in an appropriately ventilated pellet storage room, the oxygen concentration is approximately equal to the oxygen concentration of ambient air.

Reference 10 is here: Lethal Carbon Monoxide Poisoning in Woo dPellet Storerooms—Two Cases and a Review of the Literature (Saskia Gauthier et al, Ann. Occup. Hyg., Vol. 56, No. 7, pp. 755–763, 567755–763 (2012)).

A description of the fatal accidents are found in table 2 of the text. Of the nine deaths, only one was associated with storage in a private home.

My recommendation is that if you're using wood pellet stoves one should store them in a well ventilated space such as a shed or garage that is aerated. They should probably be cycled with the oldest being burned first. A carbon monoxide detector in the area or storage is advisable, particularly if the storage place is confined. It might be wise to store them in a sealed container.

I'm not sure why this is not a problem with the storage of wood for fireplaces. Probably it is related to surface area, since the wood pellets I've seen are small, um, well, pellets.

I have wood burning fireplace in my home with a circulating air fan to heat my home. In recent years I've been less and less inspired to use it - even though I use downed wood from trees on my property that would otherwise rot releasing carbon dioxide - since I am aware that about half of the seven million air pollution deaths that take place each year are from the combustion of biomass, particularly indoors. My home is regrettably heated by dangerous natural gas which is less of an air pollution source than wood, at least in a purely chemotoxic sense, but noxious all the same in a climate sense. About 50% of the electricity supplies in my state is for the time being supplied by nuclear energy, so when possible I do use electric space heaters.

(I'm not sure we're going to have all that many winters in New Jersey in the future, since we bet the planetary atmosphere on so called "renewable energy" with the result that the rate of climate change driving carbon dioxide releases is rising, not falling. So called "renewable energy" didn't work, isn't working and won't work.)

But in any case, if you have a wood pellet stove, be safe.

Enjoy the rest of your Sunday afternoon.
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