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Palomares and the H-bombs

Dear Reader,

Now some doomsayers may have tried to tell you that once radioactivity appears in soil that you should give up all hope, also on the otherhand some false prophets of insincere reassurance will just tell you to stop worrying and that “everything will be OK”. My advice is not to trust either of these two false friends.

The story of the air crash which involved four H-bombs has popped up again, the BBC report that the local people in Spain are fifty years after the air crash unhappy about what has been done.

The BBC report suggests that the local farmers have a problem getting a good price for their produce at market. I would like to point something out.

The plutonium in the H-bombs would have been in the form of the metal, during the accident this would have been burnt into plutonium dioxide. Now the thing to note about plutonium dioxide is that it is very hard to dissolve in acid, also it is not mobile in soil. Any plutonium which was in a water soluble form is likely to have bonded to the soil minerals thus making it impossible for plants to absorb it via their roots.

M.I. Sheppard and D.H. Thibault, Health Physics, 1990, 59, 471 to 482 gives the binding constants for most metals to the four common soil types. It lists for plutonium the following Kd values.

Sand, 150 L/kg

Loam, 1200 L/kg

Clay, 5100 L/kg

Organic, 1900 L/kg

This means in a bucket containing a mixture of clay type soil and water that the plutonium content of the soil (Bq per kilo) will be 5100 times higher than the plutonium content of the water (Bq per litre).

Hence when 1000 Bq of plutonium is added to a litre of water mixed with a kilo of clay type soil, then the soil will absorb 999.8 Bq of plutonium while 0.2 Bq of plutonium will stay in the water. This calculation is for a static batchwise experiment but it will help experts in the field make predictions about the mobility of plutonium solutions in soil.

Another good bit of news is the fact any plutonium dioxide in the dust will not be well absorbed if it is swallowed (dust on the surface of the food), so orally the plutonium dioxide is not a great threat to life and limb. If you were to swallow a well sintered particle of plutonium dioxide it will pass unchanged through your digestive system.

However plutonium dioxide in the lungs is very dangerous to a persons health, I think that a key thing to do in Spain is to keep the plutonium in the most contaminated soils from entering the air as a dust. I think that the ban on building, farming or walking in the contaminated area is a good idea. But I think that it might be a good idea to pour concrete or asphalt onto the worst hot spots to try to fix the soil to keep it from becoming mobile again.

One of the problems with plutonium is that the colloidal particles of clay can make the plutonium mobile, while the plutonium does not move freely through the soil in aqueous solution the colloidal particles can move through the cracks in the soil. Thus sealing the soil would help to stop the plutonium from reaching the surface again in the form of dust.

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Testilying and the environmental movement

Dear Reader,

Twenty years ago or so the late Dennis Evans told me a story about some cops who thought that they would tell a “white lie” to protect society (I have no idea where this vile story occurred or if Dennis had made it up or not). What happened was these boys in blue raided a drug dealer’s hotel room. They find some packets of cocaine. Then to make sure that the man went away for longer they plant some extra packets of cocaine. I imagine that they wanted to make sure that the judge sent the vile coke dealer away for decades rather than just sending him to HMP holidaycamp for a few years.

The core thesis of the prosecution was that the man was a cocaine dealer who was mixing cocaine with sugar to turn a larger profit and that all the packets had come from a common source. The fact that different packets had different sugar levels made it look like the dealer was mixing purer cocaine with sugar to make a less pure grade.

The police’s expert issued a report on on cocaine content of each packet where he/she lumped all the adulterants together. It is a common habit for people in the illegal drug trade to mix illegal drugs with other materials to increase their profit. So it should not be a total shock for the police to have observed some evidence of such behaviour.

Dennis was contracted as an expert witness for the defence, he retested the cocaine and made a point of measuring the different sugars (glucose, fructose, sucrose etc) in the cocaine batches. He found a purer packet which the police claimed was the parent of the less pure cocaine contained a sugar which did not appear in the less pure packets.

Armed with this information the defence was able to prove that the story that the police were telling was false. They showed that someone (the police) had planted at least one packet in the room. They then suggested to the jury that all the cocaine had been planted in the room. The man then was acquitted on all charges and walked away from the court, I imagine without a stain on his vile character.

While some people might think “I have nothing to do with drugs” and “I am not a policeman” so this story has nothing to do with me. I would say that these people are being very foolish, this is a cautionary tale about telling a “white lie” to get the job done. This is an example of testilying and the vile perils it brings.

It is better to tell the truth about something even if you think by exaggerating that you will be more likely to get the outcome that you want.

Before we go any further I would like to make something clear to those of you who are not regulars here on my blog, I have to agree with the greens, antinuclear lobby or whatever you want to call them or be called yourself (if you are a member of the antinuclear lobby) that the Chernobyl and Fukushima events are horrible. These are events which need to be avoided where possible, and if total avoidance is not possible then these types of events need to be mitigated to eliminate the threat to the general public.

My (or your) revulsion at serious nuclear accidents is not however a license to exaggerate or attempt to use these events to score cheap political points. Frankly those who use these events for selfish ends disgust me just as much as the 19th century mill owners who thought it was quite reasonable to force young children to work in dangerous factories, clean chimneys or go down the coal mine.

My loathing of serious nuclear accidents is one of the reasons why I devote time and energy doing research on trying to prevent a nuclear accident causing harm to the general public. In order to protect ourselves against reactor accidents we need to understand them, part of the quest to understand them involves a quest for truth and an insight. During this quest I am doing my best to share whatever grains of truth I uncover with others, and also to point out silly ideas when I find them. One of the things which irks me is when people exaggerate the consequences of an event, the fact that an event is horrible is not a license to lie. To me the exaggeration of the event is as wrong as a person falsely claiming that it is less bad than it really is.

It has been claimed that the cesium from the Chernobyl accident causes heart disease in adults and children, the core of the idea is that cesium goes into the heart and that the radioactive cesium then damages the heart. Next the person falls down dead from heart disease or at least becomes in invalid.

We need to ask ourselves if the radioactive cesium is able to damage the heart, some time ago (2008) a Yann Gueguen et. al. published a paper (Cardiovascular Toxicology, 2008, 8(1), 33-40) in which they exposed rats to cesium in their drinking water. The amount of cesium was 150 Bq per day for three months. Now the rats weighed 560 grams, which means that they were drinking 267.85 Bq per kilo. Now if we scale this up to a 75 kilo man then he would have drinking 20 kBq per day. As each year has 365.25 days then this 75 kilo ratman will be drinking 7.338 MBq of cesium each year.

We are making the assumption that the cesium behaviour in rats and humans is the same and that the same dose / activity coefficient should be used for both species.

Based on my ALI as a classified radiation worker which is 1.5 MBq of cesium-137 (oral), the rat man will be drinking 4.9 times the ALI which is based on a 20 mSv dose. So the 75 kilo ratman will get a 97.84 mSv dose from the cesium. So this amount of cesium is a very large amount of cesium.

I hold the view that if a member of the general public is getting a 98 mSv dose from an nuclear accident which happened decades ago that something is deeply wrong. This is a dose which is far in excess of what I am allowed to be exposed to at work. So while this study might be an interesting one it is set at a level of cesium which I think is too high.

I suspect that some differences between rats and humans exist, I have checked and the biological half life of cesium in rats is shorter (11 days) than it is in humans (B. Le Gall et. al., Biochimie, 2006, 88(11), 1837-1841). So rats are able to get rid of cesium from their bodies faster than humans can. The estimates for the biological half life of cesium in humans range from about 1 month to 4 months. If we take the UN’s estimate that biological half life to be 100 days then we can compare rats and humans.

I have done some calculations for rats and humans and based on the difference in the biological half life I think that cesium should be 9.1 times less toxic to a rat than it is to a human. So we should revise down out doses for the “rat man”. If we take this correction factor then the rat man used in this experiment if it had been a human would have had a 10.78 mSv dose (0.8 MBq intake)

Now I think a key part of the reasoning behind “chernobyl heart” is the idea that the cesium goes into the heart, I was looking in the literature at animal studies where the experimental animals were fed cesium-137. I found a second paper (Jean-Marc Bertho et. al., Radiation and Environmental Biophysics, 2010, 49(2), 239-248) where mice were contaminated with cesium-137 (20 kBq per litre) in their drinking water.

This paper stated that human exposure to cesium-137 in contaminated areas is in the range 20 to 2100 Bq per day, which works out as giving a worst case amount of 767 kBq per year. While I think that this amount of cesium is a large amount in the general public’s diet it is well below my ALI (Annual Limit of Intake) and far below the level which I worked out by scaling the rat up to the 75 kilo “rat man”.

The mice were feed the cesium in their diet from the age of four weeks onwards, I looked at the intake of the these mice and the females drank 465 Bq per week and the males drank 507 Bq per week. As the female mice (at 20 weeks) had a weight mass of 23 grams and the male mice had a weight mass of 30 grams we can make a first guess of what human level of exposure we are considering.

The 75 kilo “mouseman” would be getting 1.27 MBq per week while a 65 kilo “mousewoman” would be getting 1.31 MBq of cesium per week. This will work out as 66 MBq per year for the mouseman and 68 MBq per year for the mousewoman. This is a lot of radioactivity.

We are assuming here that the biological half life of cesium in mice is the same as it is in humans and that all other cesium biochemistry and biophysics is the same in both species. Again if we work out the biological half life of cesium in mice it works out being shorter than it is in humans. Using the data from J.M. Llobet et. al., Journal of Environmental Contamination and Toxicology, 1998,61, 289-296 it appears that the biological half life in mice is about 7 days. Thus based on the different biological half-lives the cesium will be 14 times less harmful to mice than men.

So micemen will now be getting an intake of 4.7 MBq per year. This is still a lot of cesium-137 to get in your diet.

Now back to the paper of Bertho, the important thing in this paper is that no clear signs of damage to the mice were seen. Also if you read the paper the radioactive cesium content of the heart (in Bq per gram) is less than the kidneys and the normal muscles of the mice. This paper makes me think that we need to take great care when we consider the possible link between chernboyl cesium and heart disease. This is because the cesium does not seem to be localizing inside the heart in the same way as iodine localizes inside the thyroid.

The next thing to be careful of is the fact that cesium-137 (together with its daughter barium-137m) emits three different forms of radiation. The average beta decay energy of cesium-137 is 188 keV, this is quite a low average beta energy when compared with yttrium-90 (933 keV) and phosphorus-32 (695 keV) but it is about the same as Sr-90 (196 keV). But it is a bit higher than carbon-14 (49 keV). So we can safely assume that some of the beta energy of the cesium which is in the heart will be deposited in the heart.

But 662 keV of the decay energy of the cesium will be in the form of gamma rays, even if the cesium is in the heart then much of this energy will escape from the heart. On average 363 keV of energy will fly away in the form of neutrinos. These are particles which are unlikely to interact with a slab of lead as think as the earth. So I think we are safe to assume that only part of the decay energy of the cesium which is in the heart will be delivered to the heart tissue.

Also bear in mind that the beta and gamma radiation are both low LET (Linear Energy Transfer) radiations. This means that ionization tracks formed by these radiations are long and diffuse, as a result these radiations are less able to damage living tissues. The issue of self repair needs to be considered, the background of radioactivity in a normal human body together with cosmic rays causes all tissue to be subject to ionizing events. The damage from most of these are repaired by the cells.

I think it would be a good idea if those who are making statements supporting the idea that cesium-137 causes cardiac damage to people should address the issues of how much cesium is in the heart and how much of the radioactive decay energy of the cesium is delivered to the heart.

Also they should consider the natural radioactivity (carbon-14 and potassium-40) which is in a normal clean and uncontaminated human body.

Well that is all for now, I will return with more of my thoughts later.

The big earthquake one year on

Dear Reader,

We are coming up to the first anniversary of the Fukushima accident which was provoked by a big earthquake. Now as ever it is important to avoid going to one extreme or another. When we get sick a spoon full of medicine might make us feel better but that fact is not a license to drink the whole bottle in one go !

While I am very strongly in favour of improving safety standards in the nuclear industry and I am sure that some important lessons can be learnt from the Fukushima event, but we should not close down the whole nuclear industry just because of this accident. I always do point out that the burning of coal does release a vast amount of radioactivity into the air.

The majority of radioisotopes from nuclear power plants are short lived beta emitters which tend to go away quickly, the radioactivity in coal tends to be long lived alpha activity. As the alpha emitters tend to be so much more toxic and as they are long lived this is a nasty menace which people tend to forget about. So do not allow anyone to talk you into switching to coal as a way to close down scary looking nuclear plants.

Now on the subject of radioactivity, it is important to bear in mind that wind farms need neodymium for the magnets. The extraction of this metal often requires it to be extracted from monazite which is a radioactive mineral. So before anyone trys to sell you the idea of clean green wind power as an alternative to nuclear power then ask where the neodymium for the magnets comes from. The great problem with “greenness” is that you need to look at the whole life cycle of the object or the system, you also need to look at where the materials required for a device come from as well as what waste the device forms and how you are going to dispose of the device when it is no longer wanted.

I worry that unless the right degree of care is taken with the ore processing that the extraction of the neodymium will create large amounts of radioactive waste which might not be managed in a safe, environmentally sound or reasonable way.

But lets think for a moment about the radioactivity from the Fukushima accident, in common with chernobyl after the short lived iodines the most important radioisotope is Cs-137. This is a medium to long lived isotope which contributes to much of the dose which members of the public will get in the medium and long term after the accident. I saw a paper in the literature by J. Jandl, J. Novosad, J. Francová and H. Procházka, Veterniarni Medicina (Praha), 1989, 34(8), 485 to 490 which is on the subject of cesium removal from deer meat. What these Czech workers did was to pickle meat, by ion exchange the cesium came out of the meat and was lost into the pickling liquid. As only the meat and not the pickling liquid is consumed by humans this offers a method for the decontamination of meat.

The same idea has been written about by some Germans (R. Wahl and E. Kallee) in Nature, 1986, 323, 208. These workers reported that after five days 95 % of the cesium had been lost from the meat. They also reported that the meat tasted very good. So based on this work I would like to suggest that we should consider treating some foods after gathering them to lower their radioactivity content and thus make them fit for human consumption.

Molecular boxes

OK a bit more about prussian blue and what are known as coordination polymers. The idea of a coordination polymer is that it is a repeating network where bridging ligands link each metal centre to the next, thus making a polymer.

To understand them we need to build up to it, it is not a good idea to try to run before you walk. Lets start with a metal complex which has lone pairs poking out into space ready to bind to something else. Err Oh Err how about [CpFe(PR3)(CN)2]this is a 18 VE complex. For those of you who do not know what the 18 VE rule is then I suggest that you read Tony Hill‘s book which will explain the 18 VE rule. A copy of organotransition metal chemistry by Anthony Hill can be obtained from the RSC.

Here is a picture of the anion, you can see it has the two nitrile groups which each have a lone pair on the nitrogen atom.

The cyclopentadienyl iron triphenylphosphine dicyanide anion

Now here is a complex where the Cu(PCy3) group is used, this group is a weak lewis acid so it has the ability to bind to lewis bases such as the lone pairs of the cyanide groups of the iron fragment.

You can now see the square-ish arrangement of two copper atoms (green) and two irons (yellow), what you are looking at may be a bit of an “atomic fog” but do not worry yourselves too much.

The diiron dicopper square complex

As I feel kind here is a picture of the inner core of the complex, I have removed the carbon groups attached to the phosphorus atoms.

Copper iron square complex without some of the groups to give you a better look

Now if we use three cyanides to link a metal to three other metals we can make a cube, well it is a bit of a distorted cube. I am sure that the more able minded persons reading this can understand how this is step towards a infinite solid with lots of cubes in it. Here is a picture of it. Before you ask the cage is anionic, and the atom at the centre of the cage is a potassium. This complex was published by T.B.Rauchfuss in the Journal of the American Chemical Society, 2007, 129, 1931.

The cube of eight cobalt atoms bridged by 12 cyanide ligands

The cube is capped with cyclopentadienyl and tetramethylcyclobutadiene ligands. For those of you who can not see through the atomic soup (or atomic fog) here is the cube without the capping ligands.

The cobalt cage without the capping groups

* If as a university teacher you do not get on with Tony Hill’s book then you can always replace this with another book.

Prussain blue

Dear Reader,

I have explained how cyanide can bind to metals such as iron to form complexes, these complexes have lone pairs poking out which can bind to other metals. Here is a picture of a unit cell of prussian blue.

A unit cell of a cesium nickel iron cyanide

The carbons are black, the nitrogens are blue, the irons are purple, the nickels are gold coloured and the green atoms are the cesium.

More about Prussian Blue

Dear Reader,

I would like to enlighten you further about this wonder solid, in the last post I explained what cyanide is and how it has the right orbitals for bonding to metals. I have shown you the orbitals on cyanide and how I will show you how they bind to metals to do things.

Firstly one of the sp orbitals (green) on the cyanide forms a sigma bond to the metal.

Sigma bond formation between the cyanide and the metal

The next picture has the red and blue orbitals on the cyanide and the metal which interact to form the pi bond between the metal and the cyanide. This is at the same time as the sigma bond forms, in this way while electron density is transferred onto the metal from the cyanide through the sigma bond the cyanide removes electron density from the metal into the antibonding pi orbital. This is why cyanide is known as a pi-acid ligand, it also makes the ligand field of the cyanide very strong.

The green sp orbital is left behind and it pokes out into space to allow the bridges to be formed to the next metal.

The p orbitals in red and blue which form the pi bond between cyanide and the metal and the sp orbital (green) which forms the lone pair which allows bridges to be formed to the next metal

More about prussian blue

Dear Reader,

Now some of my readers have become interested in Prussian blue, this is the miracle drug which removes cesium from human bodies. I was recently reading the work of Peter W. Stephens et. al., Inorganic Chemistry, 2010, 49, pages 1524 to 1534. His paper is about the crystal structures and magnetic properties of mixed oxidation state manganese versions of Prussian blue. This has allowed us to use X-ray technology to look inside a prussian blue crystal.

Here is a chance to look at the potassium version of the prussian blue, it is clear that the potassium atoms are in channels which run through the solid.

K2Mn{Mn(CN)6}

The way in which the prussian blue works is to allow out the potassium, the cesium ions then diffuse in to take the place of the potassium ions. When the potassium ions are replaced in this solid with cesium the larger cesium ions cause the solid to change slightly. Here is a picture of the cesium solid.

Cs2Mn{Mn(CN)6}

I checked the literature and other prussian blue like model compounds have similar structures, one early report was made by R. Rigamonti, Gazzetta Chimica Italiana, 1938, 68, 803-809. Where this italian reported a potassium salt of Co[Fe(CN)6]. I think that due to the ligand field energy effects this was a simple cubic solid which looked just like the cesium one which I showed above.

Now I am going to tell you the story about how I found out about Prussian blue, years ago in 1999 I went on an adventure to eastern europe. I joined Josef Novosad’s research group for a while. While I worked with Josef on phosphorus chemistry (we both share an affinity for this element), between making some interesting compounds which may have improved our understanding of dithioimidodiphosphinates and enjoying the delights of Brno (it is a very wonderful place) we did talk about chemistry.

One of the things which Josef told me about was what he did in his youth, he told me that he was given a job by the communists working on uranium in farmyard animals at a research centre close to Brno. But after the Chernobyl accident he was moved onto cesium in farmyard animals. What used to happen at Josef’s research site was that an animal would be given a dose of 1 MBq of Cs-137, then using additives to the animal’s feed the workers would then try to remove the cesium from the animal.

Before anyone gets worried about the effect of the cesium on the farmyard animal lets do an estimate of the dose which the animal gets. If we assume that the animal is identical to a typical human in size and that it is identical to a human then we can use the data for humans. Using the radiation protection advice from a US university we can get a thing called an ALI for oral exposure to Cs-137. The ALI is the Annual Limit of Intake which for Cs-137 in the US is 100 microcuries. As 1 Ci = 37 GBq this works out as a dose of 3.7 MBq to the animal being the limit. The US limit is worked out based on a 5 rem dose to the body. So the animal will get 1.35 rem. Now some of you might be getting a bit confused with the different radiation units. Here is a look up sheet

100 rem = 1 Sv

100 rad = 1 Gy

1 Curie = 37 GBq = 37000 MBq = 37000000 KBq = 37000000000 Bq

1 milli Curie = 37 MBq

1 microcuries = 37 kBq

So our “animal” will have got a 13.51 mSv dose, this dose is far too small to cause “radiation sickness”. If we repeat the calculation using the ALI value used in Sweden (based on a 20 mSv dose) which is 1.5 MBq then our animal gets a dose of 13.33 mSv. This is not a dose which will make the animals die of radiation sickness and if we use the accepted dose to chance of cancer conversion factor of 5 % for a 1 Sv dose then if we assume that the LNT model is right then if the animal was a human then it would have a 1 in 1500 chance of getting cancer as a result of the cesium intake. As most farmyard animals weigh more than a human the real dose to the animal would be likely to be lower.

To put it in perspective if I got a dose of 13.3 mSv at work then I know that my radiation protection officer would be very very concerned about me but I would not have gone over the yearly limit for a classified radiation worker, but if I got that dose in one month in Sweden then it would trigger an investigation into me. Such a dose is in the range where the national radiation protection authority would want to know what I was doing and how I got the dose. However if a member of the public got that dose at work then I imagine that the national radiation protection would be hopping mad to say the least ! The occupational dose for a non radiation worker is only 1 mSv per year, as a non-radaition worker is unlikely to be wearing a film or TLD badge then it might take quite a lot of extra work to work out the dose compared with the effort needed to estimate a dose for a dosemeter wearing radiation worker.

But lets get back to the prussian blue.

Josef told me that he tried almost every transition metal, I think that he did not try using nickel as nickel is toxic. He then used the batches of the “prussian blues” to try to clean the animals up. What Josef found was that no two batches of prussian blue which he made worked quite the same way in the experiments. So my advice to anyone planning on making prussian blue for medical use in Japan is that the production of the medical grade solid is not a simple matter, I have to confess that I do not know how to reliably make medical grade prussian blue.

If you want to read about Josef’s cesium work then see  H. Prochazka, J. Jandl, J. Novosad, O. Neruda, J. Hejzlar and S. Spelda, Veterinarni Medicina, 1991, 36, 341 to 348. The paper is entitled “Affection of Radiocesium Retention in Miniature Pigs”

The abstract of this paper comments that stable cesium (1 mg per kilo of body weight) is not effective as a means of removing cesium from pigs. Josef and J. Jandl published another paper in which they used a modified zeolite to treat sheep which were contaminated with cesium. This paper can be found at “In-Vivo Reduction of Radiocesium by Modified Clinoptilolite in Sheep”, Veterinarni Medicina, 1995, 40, pages 237-241.

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