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Facebook and young earth

Dear Reader,

I have little urge or time for the social media site known as facebook, but occasionally I will visit it. I was reminded that I had posted years ago on this blog about the “young earth” theroys and radioactive decay. Now for your information the “young earth” hypothesis is that the conventional wisdom that the earth is many millions of years old is wrong and that the earth is much younger.

One site which is putting forwards the “young earth” theroy can be seen here, this site appears to be written by someone who holds a religous faith who also holds the view that the age of the earth is an important issue. They are expressing a creationist view that they hold. They have a series of principles which they call “the principles of scientific creationism“. I am not going to reproduce them in full but here is a sample of them. I have included their their views in italics with my comments in plain text.

  • The physical universe of space, time, matter, and energy has not always existed, but was supernaturally created by a transcendent personal Creator who alone has existed from eternity.

This is something which science can not address, the question of did the universe start as a result of a big bang (or some other process) which was set in motion by God is not something which science is able to address and typically science is not attempting to prove the existence (or absence / nonexistence) of God.

  • The phenomenon of biological life did not develop by natural processes from inanimate systems but was specially and supernaturally created by the Creator.

The problem with the bible is that it gives no details about the manner in which God created the living things on this earth. Even if we assume that God did create the sea, fishes, trees, animals and humans the bible in Genesis 1 does not give any indication of how this was done by God. The hypothesis that a all powerful and all knowing God created a universe and then set in motion a series of events which God knew would result in the first humans evolving from something like plants which live in ponds is not in my view incompatibly with either the bible or Darwin’s work.

  • Each of the major kinds of plants and animals was created functionally complete from the beginning and did not evolve from some other kind of organism. Changes in basic kinds since their first creation are limited to “horizontal” changes (variations) within the kinds, or “downward” changes (e.g., harmful mutations, extinctions).

As I said already the bible (at least in Genesis 1) does not comment on mechanism by which the different creatures and plants were created.

  • The first human beings did not evolve from an animal ancestry, but were specially created in fully human form from the start. Furthermore, the “spiritual” nature of man (self-image, moral consciousness, abstract reasoning, language, will, religious nature, etc.) is itself a supernaturally created entity distinct from mere biological life.

As I said already the bible (at least in Genesis 1) does not comment on mechanism by which the different creatures and plants were created. While it might not be a pleasant prospect that humans evolved from monkeys or some other animals. I can not see a reason why the fact that I have much of my DNA in common with monkeys, cats and dogs makes me any less a man.

I will concentrate on a question which I know something about, this is the question of can we trust radioactive decay clocks to allow us to date objects such as rocks. In this page one of the young earth people (Brian Thomas) points out that the decay rate of Si-32 and Rn-222 have been shown to not be constant. I want to look at the evidence, one paper which they cited was “Possible effect of solar tides on radon signals” by G. Steinitz, O. Piatibratova and P. Kotlarsky, Journal of Environmental Radioactivity, 2011, 102, 749-765. In this paper the authors claim that they see evidence of a change in the rate of the radioactive decay rate of radon. Now if we assume that they are right it is important to note that another later paper suggests that with Cs-137 it is impossible to see any change of the rate of decay (half life) as a function of time while for Ba-133 it is possible to see a change in the rate.

Now an important difference between Ba-133 and Cs-137 is that barium-133 decays by electron capture to Cs-133 while Cs-137 decays by electron emission (beta minus) to form Ba-137. The later paper (“Concerning the time dependence of the decay rate of 137Cs“, J.H. Jenkins, E. Fischbach, D. Javorsek II, R.H. Lee and P.A. Sturrock, Applied Radiation and Isotopes, 2013, 74, 50-55) quite wisely comments that the claimed effect can not be observed for all radionuclides. To me this later paper about Ba-133 and Cs-137 does make a major hole in Brian’s argument. He was claiming that radioactive decay rates in general are not fixed, in the paper by Jenkins et. al. evidence is shown and an argument is made that an effect can be seen with some radioisotopes (radionuclides) but not with all of them.

I hope to get back to this issue soon with something more on it.

Sound mind and sober habit ?

Dear Reader,

It has come to my attention that in the USA a man started shooting at people in the baggage reclaim area of an airport. What he did was to transport a gun by checking it in as hold luggage, he then reclaimed it. Went off to the toilet (bathroom in US english) and loaded it before embarking on his murderous rampage.

You will be interested to know that the law enforcement authorities in the USA have arrested this man, he is alive and apparently unharmed. Now this event raised some deeply disturbing issues.

According to the Daily Mail and adn the man who is suspected of having done it had some mental health problems and also had been charged with “fourth-degree assault and damage of property in January 2016, stemming from a domestic violence incident.” While the Guardian did not report that he had been in trouble for domestic violence.

As a person who was for some time a named person on a Swedish explosives license (for scientific work on fireworks) I have a view of the matter which might be slightly different to that of the general public. If a person is to be issued in the UK with either a firearms or explosives license then they must show both a genuine need to have the license and that they are a fit to hold the license for the objects or materials listed in the license.

When I went through the application process I am sure that the official at MSB applied a similar two part assessment of me and the project. The official wanted to know why I wanted the license to do the work (this relates to need) and also about me and the facility where the work was to be done (fitness). At one point I asked if I needed to prove I was (in UK terminology) a person of “sound mind and sober habit“, I was told that “it was not needed”. I suspect that MSB would have looked at me without me doing anything to make the judgement regarding the “sound mind and sober habit” question.

I think that the event at the airport is a reminder that the US should set up a licensing system, right now I think that they should concentrate on the “fitness” issue rather than the “need” issue. I know that many people in the US do not like the idea of the state knowing about their guns, I think that I have thought of a way of dealing with that problem.

I reason that if a valid gun license is needed to transport a gun by air, use a public (or private commerical) shooting range or a series of other acts then a person could apply for a license to allow themselves to do these things. If on the otherhand they do not want to transport it by courier or air or pay for access to a range then they might not have to be required to take out a license. My reasoning is that if they want to keep their gun on their own land and use it there then it might be reasonable to exempt them from the license requirement. Now lets look at some of the things which have been reported.

If a man has been acting strangely and had claimed to the FBI that he has been subject to mind control, then surely it would be reasonable to ask the question of “if he of sound mind ?“. One of the symptoms of schizophrenia is delusions, now the vast majority of people with schizophrenia are quite harmless. They tend to be more of a threat to themselves than others as a result of the way they behave. But it would be prudent for society to prevent a person who is delusional from having access to a firearm until they have obtained medical clearance to show that they are not a danger to themselves or others.

A man who has been charged with a violent crime such as domestic abuse clearly needs to be checked regarding the “sober habit” part of the question. While my biggest concern about a person who has a record of domestic abuse is that they might use a firearm or explosives to attack their partner or ex-partner. I would say in general that a domestic abuser is not a person who I would regard as being of “sound mind and sober habit“.

It is clear to me that regardless of how the NRA and the gun lobby feel about it that the US needs some form of licensing to own, keep or possess guns. Maybe this event would have been prevented if the airline had been required to see that the man held license(s) which would have permitted him to have the gun both in the place where he checked in the gun and where he was flying to.

I hold a view that it is reasonable for a person who has been charged with or arrested for some crimes to have any firearms which they own / possess taken off them by the police. However with many things abuses of the law must be prevented. I hold the view that for a law to be obeyed, some degree of respect for the law must exist. By abusing a law this law (and laws in general) will no longer be respected.

One safeguard I see is that if guns (or any other legally held article) is taken away by the police then it should remain the property (in law) of the person it was taken from. If either the police / public prosecutor drop the matter or a court orders the matter closed (in favor of the person) then the police should have to take responsibility for the prompt return of the property in the same state as it was when they took it away.

For example if the police seize a car from an innocent man then they should return the car as soon as the legal basis which they might have had at first no longer exists. I also hold the view that the keeper of the car should be paid the hire cost or a replacement car to compensate him / her for the loss of the use of the car. Also rather than being able to charge a storage fee for the car the police should have to provide the person with a partial refund for any road tax or insurance which had been purchased on the car. Also if the car is damaged, rusts or otherwise degrades while the police have it then they should have to take responsibility for getting the car repaired.

Also if the police were to take a so called dangerous dog from a person and the dog has been ordered to be returned to the person then the police should while they have the dog be required to look after the dog’s welfare (provide it with walks, feed it, keep it clean etc) while they have the dog. They should also be required to return the dog. If it is a dog which must be muzzled in public then to return the dog without a muzzle or reasonable warning to the owner in a public place then the owner should not be regarded as being guilty of having an unmuzzeled dog in a public place. Instead it would be reasonable to regard the police as being responsible for this crime.

It would be reasonable for me to hold the view that bashing holes in other people’s houses with rocks is a crime (vandalism). To set in motion an event which causes unlawful damage to the property of another person where you do not come into contact with the other person’s property, such as rolling stones down the hill towards the otherperson’s house should still be regarded as vandalism. In the same way if you perform an action which causes an act which is normally regarded as unlawful to be performed by another person against their will then you should face the penalty for the crime rather than the person compelled by your actions.

An interesting problem exists when the police lose, dispose of or damage an item which is not commercially available. For example if they seize artwork (how about Vincent VanGogh’s Sunflowers) from a person wrongly (but while they have the sincere belief that they are acting lawfully) and then rip the painting while transporting it, then this would be a difficult thing to replace or compensate a person for. I think we would need a whole room of law Profs to work out the right answer.

Another problem is that some items might be legal to own / possess but only if they were transferred to a person before a particular date. For this I have a simple solution, if the US police for example were to confiscate wrongly a M16 or antique Thompson sub-machine gun which was legally held by a person and then dispose of it wrongly. Then I reason the best way for the law to deal with the problem is for the goverment to transfer an identical item to the person and then that item is treated in law as if it was the original one. Thus the goverment would have to transfer a restricted item to a person to reverse an involuntary and wrongful transfer of a restricted item from the person to the state. The alternative is for the state to have to pay far in excess of the resale value of the item to the owner.

I suspect that the gun issue in the US is not going to be an easy matter to fix, but something needs to be done to iron out the problems.

Reckless use of pesticides

Dear Reader,

It has come to my attention that a person in the USA caused the deaths of four members of his family when he attempted to use a restricted pesticide to kill bugs at his home in Texas. What this man did was to use a product which is not intended to be sold to or used by the general public. In the UK the use of this chemical is strongly limited to professional users who have to undergo special training before they use it.

It was aluminium phosphide, this is one of the more dangerous pesticides which is in current use. It is a solid which on contact with water (or acids) will generate phosphine gas. The take home message is if you face a pest control job which you can not solve using over the counter products sold to the general public then unless you have the special training (and equipment) required to use a professional use only product then leave work with such a product to a professional (and I hope competent) pest control worker.

You might wounder what aluminium phosphide is, it is AlP, it is a solid with the same crystal strucutre as zinc sulfide (zincblende). Here the aluminium and phosphrous atoms have tetrahedral coordination environments. This is a compound with a cubic cell (a = 5.451 Å). The fractional coordinates of the atoms are

Al 0, 0, 0

Al ½ ½ 0

Al ½ 0 ½

Al 0 ½ ½

P ¼ ¼ ¼

P ¾ ¾ ¼

P ¼ ¾ ¾

P ¾ ¼ ¾

We can make a xyz file for a single unit cell.

18
XYZ file : Unit cell AlP
Al 0 0 0
Al 5,451 0 0
Al 0 5,451 0
Al 5,451 5,451 0
Al 0 0 5,451
Al 5,451 0 5,451
Al 0 5,451 5,451
Al 5,451 5,451 5,451
Al 2,7255 2,7255 0
Al 2,7255 2,7255 5,451
Al 2,7255 0 2,7255
Al 2,7255 5,451 2,7255
Al 0 2,7255 2,7255
Al 5,451 2,7255 2,7255
P 1,36275 1,36275 1,36275
P 4,08825 4,08825 1,36275
P 1,36275 4,08825 4,08825
P 4,08825 1,36275 4,08825

Here are three views of the unit cell for you to look at

alpview1

alpview2

alpview3

It should be clear that the empirical formula of the compound is AlP. We have eight aluminiums at the corners of the cell, each is shared equally between eight cells, we also have six aluminiums on the faces. Each of these six aluminiums is shared between two cells. This gives us a total of four aluminiums.

We have four phosphorus atoms (in a fetching orange) which are totally inside the unit cell. Thus we have a 1:1 ratio of aluminium to phosphorus atoms.

 

Gamma spectroscopy under different conditions

Dear Reader,

While working on the project for SSM I had to make some measurements by means of gamma spectroscopy using a high purity germanium detector, note that it is not a high purity geranium detector. Being a main group chemist I do occasionally allow myself a joke. One such joke among main group chemists regards the fact that germanium sounds a little like a flowering plant which is popular in the UK.

What happens in a high purity germanium detector is that gamma photons enter a crystal of germanium which has a high voltage (2 to 3 kV) applied to it. When the photon deposits energy in the crystal this produces charge carriers (free electrons and holes). As a result of the event charge flows through the crystal, the electronics measures the amount of charge, and from that it is possible to work out the amount of energy which was deposited in the crystal during the event.

This sounds all very simple and easy but in real life it is not easy, for example some energy can enter the crystal in the form of the photon and some of this energy can then escape from the crystal as a result of Compton scattering or pair production.

Also the photons from the radioactive decay event must be able to enter the detector, also they have a finite probability of being able to interact with the crystal. The issue of penetration and overpenetration add a new layer of complexity, it causes the sensitivity of the detector to change greatly as a function of the energy of the photons.

Also the radioactivity can generate secondary radiations, for example beta particles which strike high Z (atomic number) materials can generate characteristic X-rays and braking radiation (Bremsstrahlung). During my efforts to make some measurements I created what I think is a good set of spectra which show off some of these effects.

My first problem was that I wanted to verify that I had iodine-131, I choose to put some methyl iodide which contained a lot of radioactivity into the detector. I knew that putting the vial into the detector would overload the detector, so I used a trick to cut down the gamma flux. I put the sample inside a lead pot. Or lead pig, this greatly reduces the photon flux near the vial. I knew that the activity calibration already made for that detector with a different geometry would not work, but all I wanted to do was to verify the identity of the radionuclide.

In some ways I got a better answer than the one which I would have had if I had used an unsheilded vial with less activity in it, I was more able to observe the higher energy gamma photons from the radionuclide. This was because the lower energy photons from the radioactivity were strongly attenuated by the lead pot.Here are the gamma spectra for iodine-131 recorded under different conditions.

Firstly here is the gamma spectrum for the radioactive iodine in a LSC vial.

i131lsclinear

i131lsclog

I have shown both a view of the graph with a log and a linear scale on the y axis. Now here are the graphs for the radioactive iodine inside a lead pot.

i131piglinear

i131piglog

What you should be able to see is that the high energy end of the spectrum is now more important, the moderate energy gamma line for I-131 at about 300 keV is much weaker, as a result the higher energy gamma lines are now more important in the spectrum.

It is also interesting that when we look at the low energy end of the spectrum that the lead pot changes things greatly.

i131lowenergy

What we have here are some x-ray peaks and a low energy gamma line. It is important to understand that the beta decay of the iodine forms a xenon atom in an excited state. The capture of an electron by the xenon atom can result in the generation of photons. In this case it is k line photons. The radioactive iodine also emits gamma rays with about 80 keV energy. Please keep in mind that the energy calibration of the spectrometer is a bit off, it tends to over report the energy of the events.

The lead pot was responsible for the generation of some lead K x-rays. What I suspect happened was that the gamma rays from the radioactive iodine with 300 or more keV interacted with the pot and generated plenty of fast moving electrons. This would have been by both the photoelectron and the Compton effects. Those electrons which were generated close to the surface of the lead pot were able to excite lead atoms, these lead atoms then emitted x-rays, here you can see the K alpha and K beta lead x-ray photons. The lead pot was able to screen out the 80 keV photons from the radioactive iodine so the X-ray generation must have occurred on or near the outer surface of the lead pot. One interesting experiment would be to put a pure high energy beta emitter such as strontium-90 inside a range of lead pots and then count these with the HPGe gamma spectrometer.

If I was to have covered the outside of the lead pot with a layer of copper then these lead x-rays would have been attenuated. One option for getting the best shielding out of a lead (or DU) object is to cover the object with copper, then aluminium and then finally plastic. The idea is that the secondary radiations from the lead (fast electrons and X-rays) will be captured in the copper. The copper being a lighter element is less able to generate x-rays from the electrons and it will also offer some attenuation of the lead x-rays. The lower energy x-rays generated in the copper will then be attenuated by the aluminium. Finally the very low energy x-rays generated in the aluminium will be captured in the plastic.

It is interesting that the lead shielding for the gamma spectrometers are lined with copper sheet to try to reduce the formation of secondary radiations by the action of cosmic rays (and other background radiation) and the radiation from the sample in the spectrometer on the lead shielding. It is also interesting to note that photographic film is more sensitive to high energy gamma rays if it is placed in contact with a thin lead sheet.

During the Fukushima event some people claimed that workers at the site were issued with lead sheets to make their dosimeters less sensitive, under some conditions by wrapping a dosimeter in lead sheet it would be possible to make it over report a dose of gamma rays. A lot will depend on the energy of the gamma rays, while a thin lead sheet will make a dosimeter under-report things like x-rays from a dental radiography set (70 kV tube) it will make the dosimeter over report the dose from a high energy gamma emitter such as cobalt-60. The old fashioned film badges which we used to use back in 2000 for gamma dose measurement of people had a series of metal filters designed to allow the badge to make better measurements of gamma photons with different energies.

Note that before you put anything into a gamma spectrometer it is important to wrap it in a plastic bag. If you have ever been a responsible dog owner you will know how to pick up dog poo (or other objects) using a plastic bag in such a way that you never touch the dirty side of the plastic bag. Put your hand into the bag, pick up the object and then turn the bag inside out and tie it shut. I did this with the lead pot containing the radioactive iodine and then just to be sure I bagged it a second time. I reason that no harm can come from using a second bag, and just in case something went wrong during the first bagging the second bag added while the singly bagged object was on a clean bench would reduce the potential for the transfer of radioactive contamination yet further.

My second problem was that I wanted to get a quench curve for liquid scintillation counting with large chemical amounts of methyl iodide present, any of my readers who are organic chemists will know how methyl iodide is a toxic and very volatile liquid which is difficult to pipette out. While my one of favorite pipettes (200 microlitre) is unable to measure out 20 or 50 microlitre volumes of methyl iodide a 10 microlitre pipette can dispense 5 microlitres it as the diameter of the tip is much smaller. But for 10, 20 and 50 microlitres I used a gas tight syringe designed for gas chromatography work.

Rather than trusting my pipetteing with this volatile liquid, I choose to use the gamma spectrometer to check my volumes. By making a measurement of the number of counts per second I was able to make an independent measurement of the radioactivity in the LSC vials. I will save the results of this for another day.

Homopathic medicine

Dear Reader,

Some years ago I read an article about a woman who choose to use homopathic medicine instead of “normal medicine” to treat her breast cancer. Sadly she died a horrible death, I think it was worse care than that given to Adolf Hilter’s mother (Klara). Klara also died of breast cancer, but she had a conventional doctor (Eduard Bloch) who did his best to treat her cancer and ease her symptoms. While sadly her cancer was too advanced when she contacted her doctor, she did have surgical treatment which could have saved her (if she had been treated at a more early stage). Sadly she had a secondary tumor which then killed her.

The thing which shocks me is that a pair of doctors about 100 years ago did a better job for Mrs Hilter than the alternative healers did for the woman in that sorry tale.

One of the drugs used to treat Klara was iodoform, this is triiodomethane. If a person was to just trust the wikipedia entry on Klara Hilter then it is not clear what the intent of the doctor was when he used this compound on Klara. However one science blog explains how iodoform has been used in medicine for wound dressings. Unfortunately for both Klara Hilter and the modern woman whose breast cancer was mismanaged the tumor grew so large that it broke the skin.

I have to say that I would expect less from Eduard Bloch and his coworkers about 100 years ago than I would of a modern doctor, imagine.

No decent X-ray equipment

No Ir-192 for brachytherapy

No Co-60 or Cs-137 for decent teletherapy sets

No modern drugs

So I would say that Mrs Hilter’s doctor was doing a much better job for Klara than the modern homopathic doctors. I hold the view that homopathic doctors are not real doctors, homopathic medicine is something which claims a mechanism which is not supported by science. It is interesting that young Adolf was very pleased with the efforts of his mother’s doctor, it has been reported that he had a great liking for Eduard Bloch even while Hilter knew that Eduard was jewish. Sadly the fact that a Jewish doctor had tended his mother in her final illness did not make the older Hitler understand that the antijewish policies of the nazi state were deeply wrong. It is important to understand that Hitler and the nazi state did not just harm jews, they hated (and harmed) gipsys (roma), slavs, homosexuals, freemasons, Jehovah’s witnesses and a range of other people who did not see the world the world the same way as themselves. Sadly I am unable to understand the reasons why Adolf Hitler did the things he did, as the choices made in this vile man’s mind can not be explained with chemistry we will not discuss them in my blog. Now back to chemistry.

Iodoform is a simple molecule which has been used for dressing wounds, one of the concerns with a case like Klara’s one of the concerns was infection. Now you might wounder what iodoform is, it is a simple molecule with the formula CHIwhich has C3 symmetry. The molecule is tetrahedral in shape, if it is turned on the same axis as the CH bond then it can be turned three times by 120 degrees to get something with exactly the same atomic coordinates.

F.Bertolotti, N.Curetti, P.Benna and G.Gervasio recently reported the solid state structure of iodoform in J. Mol. Strucutrue, 2013, 1041, page 106. they were not the first people to do strucutral crystallography on iodoform. The first report was in the 1950s by T.L.Khotsyanova, A.I.Kitaigorodskij and Yu.T.Struchkov, Zh.Fiz.Khim.(Russ.)(Russ.J.Phys.Chem) , 1953, 27, 647. I have looked and the two groups got very similar results.

The unit cell dimensions for the original determination were

a = 6.830, b = 8.830 and c = 7.530 Å

alpha = 90, beta = 90 and gamma = 120 degrees

The more modern determination has the following cell dimensions

a = 6.555, b = 6.555 and c = 6.985 Å

alpha = 90, beta = 90 and gamma = 120 degrees

This makes the cell very much noncubic, one side has a different length and also one of the angles is clearly not 90 degrees. This makes it a hexagonal cell, the space group is P63. Here is one view of a unit cell.

iodoformcell

Iodoform cell showing the two molecules in the cell.

iodoformcell2

Second view of the cell showing clearly that it is a hexagonal cell

If we look at the bond angles in the iodoform molecule angle I1 C I1b is 114.85 degrees, the angle I1a C I1b is 114.85 and the last angle I1a C I1 is 114.85 degrees. This means that the molecule is distorted away from a perfect tetrahedron by repulsion between the large iodine atoms. The H C I angle is 103.35 degrees. Here is a ball and stick view of a single iodoform molecule from the side.

sideviewballandstickiodoform

Side view of iodoform, ball and stick view

Here is the view from the same angle now using a spcae filling model

sideviewspacefillingiodoform

Side view using space filling model

Now if we take a view from the top along the axis of the CH bond we should be able to see that the molecule has a C3 axis.

topviewspacefillingiodoform

Lastly the C-H distance in iodoform is 1.136 Å while the C-I distance is 2.118 Å. Iodoform is not normally made by the reaction of methane, methyl iodide or methylene diiodide (diiodomethane) with iodine. Instead it is normally made by the reaction of a methyl ketone such as acetone with iodine under alkaline conditions. We might be able to go through the mechanism of this reaction another day.

For those of you might want some light relief about homopathic medicine, I suggest that you look at this film. Which is a black comedy about how homopathic doctors would treat a car crash victim. It is even better than seeing internet Hilter getting mad about the parody films.

Trinitite II

Dear Reader,

I have reexamined the gamma spectrum from the trinitite, and I have some news for my loyal readers. What I did was to look at someone else’s gamma spectrum of trinitite and then try to match peaks.

Here is the spectrum

trinitite9

Gamma spectrum of trinitite

What we can now see are two peaks (51.7 and 129.3 keV) which are due to the gamma emissions from plutonium-239. Also we can see a set of three lines due to uranium L lines X-rays.

We might ask why are we seeing uranium x-rays coming from a sample which contains so little uranium. One explanation which I think is very reasonable is that the alpha decay of the plutonium-239 forms uranium-235 which is formed in an electronically excited state. The uranium-235 then undergoes a rearrangement of the electrons to form the X-rays. This has been observed by others during XRF studies on plutonium metal.

This is further evidence that the sample contains the radionuclides which should be expected from the trinitiy test. So now I have managed to prove that the sample contains plutonium.

As the sample also contains americium-241 I think it would be reasonable to next make an attempt to find the lines for neptunium X-rays. These could be a further sign that the sample contains americium. I can not think of any other alpha emitters which will be present in large / moderate or even less than tiny amounts in the trinitite.

I will have to think further about the sample.

Toxic lubes ?

Dear Reader,

As I suspect that most of my readers will understand how and when they have sex and with who is a very personal matter. Now it has come to my attention that Gwyneth Paltrow has been condemning the use of “lube” as her naturopathic doctor told her that “lube” is dangerous. Now I would like for the record to point out that I do not work for the “Drug Industry” and have no other vested interest in the “Drug Industry“. Nor do I work in the “lube industry” or get any money from them.

Maggie Ney her doctor had condemned “lubes” such as KY gel because they contain parabens, she claimed that

Parabens have actually been found inside breast tumor cells. And while we cannot conclude that parabens cause breast cancer, we can certainly argue that our bodies do not efficiently metabolize and eliminate it from our bodies. So when the FDA (which does not even regulate what goes into our lubricants) claims that the amounts of parabens are too low to pose a toxic effect in the body, they may be correct if we’re talking about a single exposure. The problems is, parabens are in our moisturizers, makeup, shaving creams, and facial cleansers. With multiple, daily use of these products, parabens and other chemicals are accumulating in our bodies, being passed onto our children, and playing a significant role in the health of our reproductive system.

Lets consider the ideas in this paragraph, we will start with the orange text. Now if I was to take a cancer cell regardless if it was lung, skin, liver or breast it would contain water. Maggie claims parabens have been found in breast cancer cells and then suggests that these substances could be responsible for the cancer. This might be an attempt to confuse the reader.

To my mind with the general public, they are almost always going to misunderstand the letter of the text as meaning “parabens can cause cancer”. I would say that a responsible doctor or medical scientist should take care to avoid leading the reader down a wrong path.

The great problem with cancer is that it originates in a single cell, this mutant cell keeps on dividing so it will be impossible to find this cell in a person who has clinical symptoms of cancer. So the substances in the cell at the moment it is removed from a person as part of a sample of a tumor will not be the substances present in the cell when it turned into a cancer cell. Also she has failed to show that the parabens were responsible for the cancer. Her link between the presence of parabens in cancer cells and the suggestion that they were part of the carcinogenic (cancer forming) process is on the same level as a person claiming that the water in cancer cells was responsible for the origin of the cancer.

One of the problems with the paper in 2004 in which P.D. Darbre, A. Aljarrah, W.R. Miller, N.G. Coldham, M.J. Sauer and G.S. Pope reported the concentrations of paraben esters in breast cancer tumors (Journal of Applied Toxicology, 2004, 24(1), 5-13) was that they failed to give any data for normal healthy breast tissue. This was pointed out by the editors of the journal. So already the significance of the finding of parabens in breast cancer samples has been called into doubt. This weakness in the paper which is a key part of Maggie’s argument is something which we should also consider when deciding what sort of under arm sprays to use or lubes to smear on our bodies.

For those of you who want to see what methyl paraben looks like then here is a diagram of the molecule.

Methyl paraben, methyl 4-hydroxybenzoate

Methyl paraben, methyl 4-hydroxybenzoate

Those of you who want to see the shape of the molecule through the miracle of x-ray crystallography should consult D. Vujovic and L.R. Nassimbeni, Cryst.Growth Des. , 2006, 6, 1595.

Next my English grammar expert points out that the use of the “and” I highlighted in red, is an example of rather bad written english. But we will not be making this post an english language lesson.

Next we look at the statement in blue, now this is an example of poor writing. Firstly the text is too informal and poorly defined. The text So when the FDA (which does not even regulate what goes into our lubricants) can be understood in several different ways.

Firstly I was to make a “lube” and market it only in Sweden then the FDA would not regulate it at all, so it would be correct for me to write “The FDA does not regulate my lube”. Equally if someone was to buy a lube which was made and marketed in Denmark and use it on holiday in France then they could quite correctly write “The FDA does not regulate my lube”. Instead of a single person writing (or talking) we were to have a group of people expressing an opinion then they could write (or say) under those conditions

“The FDA does not regulate our lube”

An alternative and meaning which could be understood from the text is the claim that the “FDA does not regulate what substances are used in lube”. I think that as a “doctor” that Maggie should be very careful with the way in which she writes and speaks. She should aim to avoid speaking in an ambigous manner, I would advise her for many reasons to make sure she writes clearly. But then when I looked at the FDA web site and made a search there for “sexual lubricant” then I found this group of documents bundled together into a single pdf. This is one of many such collections of documents, I do not want to endorse any particular brand and this is given as an example of some letters which have gone between companies which wish to market lube and the FDA.

After reading the documents in the pdf I have given a link to, I came to the conclusion that the FDA does regulate the marketing of “lube”. Part of this regulatory process includes a consideration of what is added to the lube. Keep in mind that multiple licenses are required for a drug to be brought to the market and sold or issued to people.

Consider for a moment as an example an asthma inhaler, now I am sure that some of my readers will be aware that cold air, infections, exposure to allergens, running, chopping wood, vigorous dancing or even sex can trigger breathing trouble in people who have asthma.

The drug must be shown to be safe and effective before a license is issued for the drug to be allowed as a treatment for a condition. For example salbutamol has been shown to be a safe and effective drug.

The drug must be made by a company which has a series of licenses (GMP etc etc) to be able to make pharma grade batches of the chemical which is intended to be used as the drug. The drug has to be made under special clean conditions, rather than being made under “normal” conditions.

The device which delivers the drug to the person taking it needs to have a license before it can be put on the market. Questions such as how well does it manage to deliver the same dose each time to the user need to be considered. Also how much of the drug is delivered to the lungs and how much is lost in the mouth could be an important issue with an asthma inhaler.

I see the same thing with the marketing of a “lube”, the substances in it must be ones which are regarded as “safe” in their intended use. Also the product must be able to deliver the substance in a safe way, issues such as microbiology need to be considered.

Next we will look at her statement in green, this is on the subject of how long these will stay in our bodies. I have already sent an email to Maggie Ney via the comments form on the website of her medical practice regarding the biological half lifes of the parabens. So far she has failed to reply. It so happens that two papers have been published in which the safety case for human exposure to two paraben esters have been reviewed. For methyl paraben, M.G. Soni, S.L. Taylor, N.A. Greenberg and G.A. Burdock wrote a paper entitled “Evaluation of the health aspects of methyl paraben: a review of the published literature”, (Food and Chemical Toxicology, 2002, 40(issue 10), pages 1335-1373) was the review on the substance. The abstract of the review contained the important phrase methyl paraben “is hydrolyzed to p-hydroxybenzoic acid, conjugated, and the conjugates are rapidly excreted in the urine. There is no evidence of accumulation.”

For those of you who might wounder what a paraben is, then it is an ester of 4-hydroxybenzoic acid. This is a carboxylic acid which is found in a range of fruits as a natural product. For example it was detected in coconuts by G. Dey, A. Sachan, S. Ghosh and A. Mitra, Industrial Crops and Products, 2003, 18(2),  pages 171-176. While in currants this carboxylic acid was found by K. Maatta, A. Kamal-Eldin and R. Torronen, Antioxidants & Redox Signaling, 2001, 3(6), 981-993. It gets even better, methyl paraben has been isolated from countless plants, reports of its isolation as a natural product go back into the 1960s.

While for propyl paraben the same authors reported very similar results in their survey of the literature in Food and Chemical Toxicology, 2001, 39(issue 6), pages 513-532.

I hold the view that if Maggie wants to continue to make these claims about parabens she should provide some evidence to show how M.G. Soni et. al. are wrong, her personal view that parabens are harmful is far less important than a pair of reviews which each cite over 100 papers. We should be striving towards evidence based medicine, here I see a conflict between Maggie and her claims (not supported with evidence) and the scientific literature.

Maggie also makes the interesting comment that anything which is safe to eat is generally safe to smear on one’s body before sex. Now lets explore this, now before some of you might think that this is going to be an exercise in school boy smut should understand that they will be disappointed if they expect Dr Foreman to be writing about something obscene.

We will start off with sugar containing products, now I know that many of us like sugar. It contributes to the taste of many nice and yummy products. It is found in fruit, sweets and many other products. I know that the food industry is accused of over using it, but when used in moderation it makes things taste very nice.

The problem I see is that sugar in the wrong place can result in mayhem, I would be interested to know if Maggie has considered the problem of Candida type yeasts. If one was to use some sugar rich substance as a lube, I see a danger that it might disturb the microbiology of the private parts. This could result in some rather unpleasant effects.

I also considered the possibility that Candida can feed on starch, I checked the academic literature and quickly I found an example of a form of Candida which can feed on starch. It so happens that the Candida tropicalis BPU1 isolated from goats can feed on potato, tapioca, or jack seed starch to form polyhydroxybutyrate (PHB). If you want to read the paper then see P. Priji, S. Sajith, S. Sreedevi, K.N. Unni, S. Kumar and S. Benjamin, Starch-Starke, 2016, 68(1-2), 57-66.

I looked in the literature for papers about starch and the yeast (Candida albicans) which is the form of candida common in humans, I found one by K. Bramono, R. Tsuboi and H. Ogawa (Mycoses, 1995, 38(9-10), 349-353) in which the authors reported that this yeast did not form alpha-amylase but it did form alpha-glucosidase. This is an enzyme which is able to break down starch into glucose. Also the yeast was able to grow on maltose which is a disaccharide. This suggests to me that it is possible that starch containing foods could cause something to happen, the final comment I will make on this organism is that by treatment with UV light and ethidium bromide it was possible to form a version of this yeast which was very good at converting starch into alcohol (ethanol). This was reported by A. Aruna, M. Nagavalli, V. Girijashankar, S.P.D. Ponamgi, V. Swathisree and L.V. Rao, Lettters in Applied Microbiology, 2015, 60(3), 229-236. While I hope it is unlikely that this mutant yeast would ever be able to escape from the lab or industry and establish itself in humans it does suggest that the parent version of the yeast can feed on starch.

In case you want to find out what ethidium bromide is then here is a picture of it, it is a nasty mutagenic dye used in DNA research.

Ethidium bromide

Ethidium bromide

I note that the KY liquid and the jelly both contain hydroxyethyl cellulose, in general cellulose is much harder to digest than a starch. This alone will make the KY gel much less likely to act as a food for the yeasts and bacteria. There are some organisms which have the enzymes needed to digest cellulose but many lifeforms are unable to do this. The paper by A. Martinez-Richa (Polymer, 1998, 39(14), 3115-3119) indicates that as the hydroxy groups in cellulose are replaced with 2-hydroxyethyl groups the rate of digestion by cytolase decreases. A series of products are sold under the names of cytolases, these are enzymes for the digestion of things like celluloses.

Now I can not claim to be an expert on the biology of Candida but this paper does raise a great concern. I think any of my readers who are concerned about starch based products being used for sexual purposes might be well advised to ask either a gynecologist or a microbiologist about this issue.

KY jelly as that sold in the UK contains some glycerol (propane-1,2,3-triol, Glycerin) which can be used by many microbes as a source of food but with the preservatives present in the gel I suspect that it will not be much of a problem. Glycerol can be used as a food by some bacteria, for example see A. Murarka, Y. Dharmadi, S.S. Yazdani and R. Gonzalez, Appl Environ Microbiol., 2008, 74(4), 1124–1135 explains how E. Coli can be used to convert glycerol into some industrial chemicals. It can also be used by some yeasts as a source of energy, but I suspect that the preservatives in the gel will stop this glycerol causing any problems.

Glycerol

Glycerol

The KY liquid also contains sorbitol and propylene glycol, these are polyalcohols which are non toxic. The sorbitol is a sugar which is slightly different to glucose, it provides less energy per gram and I suspect that it is a poorer fuel for bacteria / yeast than glucose would be. As it will only be present in a small amount I suspect that a small amount of this sugar will be less likely to cause some microbiological mayhem than a strong sugar solution such as honey.

D-Sorbitol (also known as D-Glucitol)

D-Sorbitol (also known as D-Glucitol)

The propylene glycol is a non toxic replacement for ethylene glycol which is used in both food and antifreezes. The reason it is far less toxic than ethylene glycol is that it can not be converted into oxalic acid or some other toxic C2 compound such as glycolaldehyde and glycolate (glycolic acid).

Propylene glycol

Propylene glycol

Likewise some gels such as KY jelly contain some gluconolactone which is a sugar, I do not know how much is present in the gel but due to the fact that the gel contains some antibacterials I suspect that this small trace of sugar will not pose a problem. This additive may be present to squester any unwanted trace metals which appear in the gel, this substance can chelate to a metal ion using the hydroxyl group which is alpha to the carboxylic acid which exists when it is in the open chain form. The addition of this to the product will be likely to increase the shelf life of it.

I have looked and the open chain version of this lactone has been converted into crystaline solids which have been investigated with X-ray crystallography, T. Lis, Acta Crystallogr.,Sect.B:Struct.Crystallogr.Cryst.Chem., 1979, 35, 1699 reports a polymeric manganese compound. Here two carboxylic acid groups (COOH) have lost a proton, these forms a negatively charged species which binds to the manganese cation (positive ion). At the same time an alcohol on the next carbon to the carboxylic acid binds to the manganese, two waters are attached to the manganese atom and to complete the metal complex an alcohol from the acid binds to the metal. I was going to draw a picture of it and then I saw the hydrogen bonding network, as I can not do justice to it I will not try to draw it.

The complex of this acid with a tris-(2-aminoethyl) amine complex of cobalt is more manageable, this is a simple complex which was documented by M.Pfister, S.Illi and P.Klufers, Z.Naturforsch.,B:Chem.Sci. , 2013, 68, 739 which explains clearly how I imagine that this molecule can bind to a metal. One of the advantages of binding to a metal is that it can make the metal less available for bacteria and other microbes to use. One of the ways in which a human body suppresses the growth of “germs” is by keeping its iron locked up in chemical forms which the germs can not access.

The KY jelly contains some chlorhexidine, this is an antibacterial agent which is used in mouth washes and many other antibacterial products. One interesting thing about chlorhexidine is that it can not be used at the same time as normal soap or an anionic detergent. This is due to the fact that the anionic detergents inactivate the chlorhexidine becuase the chlorhexidine is a cationic surfactant. The best detergents to use with chlorhexidine are neutral ones such as block copolymers of ethylene oxide and propylene oxide.

The gel also contains some sodium hydroxide, this might sound horrible but a small amount of sodium hydroxide when added to starch has an interesting effect. It causes the starch to swell up. This is because starch is a mild acid, starch is slightly more acidic than water so a slurry of starch will react with sodium hydroxide to form the sodium salt of the starch. I suspect that with the vast number of hydroxy groups present in hydroxyethyl cellulose that it can also bind to sodium ions in a similar way to corn starch.

So far I think that KY gel or another similar product designed and marketed by a mainstream drug company is going to provide you with a safe experience. Sadly no pharma company can offer a warranty that your sexual relationships will go perfectly and that you will live happily ever after with your partner. Well if only they could offer you such a deal !

I would also like to point something else out, those of my readers who are easily horrified should stop reading this post now ! Trust me this one is nasty with a capital N ! So not read the text in yellow if you are squeamish.

Many years ago as a PhD student I read of a nasty product tampering case in the USA. A man held an extreme belief that people who use contraception are going to bun in hell, regardless of how outlandish and offensive we might find this belief we can not criminalize a person’s belief or their thoughts. However acting on these beliefs or thoughts can be criminal. What this man did was to get a job in a condom factory, he decided to give the users of condoms an early taste of hell by smuggling an extra hot chili sauce into the factory which he later applied to the condoms while they are being packed.

He was convicted of a crime, and I think he was lucky to get away with probation. My father holds the view that this person should have got jail time as it was a hate crime. His reasoning is that a hate crime should earn the criminal a more lengthy stay inside. I have to agree with him on that. My legal adviser comments that a hate crime is a crime against society as a whole and not just the person or company which is being attacked.

Those of you of a sensitive nature can start reading again, this horrible story clearly shows that Maggie’s claim “When it comes to lube, if it is safe to eat, it is generally safe to apply” is clearly wrong. I think that the word “generally” is a funny word, it can have two meanings. It can either mean that the majority of things in a class are safe or it can mean all things in the class have the same characteristics, one can say that a chemical reaction is so general such that all substances of a given class will do reaction X. For example all secondary alcohols can react with chromium(VI) oxidants to form ketones. To my mind the use of “generally safe to apply is bad scientific writing as it can be understood in two very different ways. A good scientist or even a reasonable one will attempt to write and communicate in such a way that it is impossible to misunderstand the message.

While I might have picked an extreme example in the form of the capsaicins and the related compounds in chilli peppers, other foods contain substances which when taken in a particular way can cause injury. For example I know the inhalation of cinnamon powder his harmful (look up the cinnamon challenge and please for goodness sake do not try it).

I hold the view that many food substances might be safe to swallow in moderate amounts but when applied to the wrong part of the body the results can be rather disagreeable. Another example would be the fumes from onions and horseradish, while eating an onion or putting horseradish sauce on your beef might be OK. Exposing your eyes to the fumes from either is rather disagreeable.

It was interesting that Maggie Ney suggests oils as a alternative to these lubes made by the big companies, I have to question how good an idea this is. One sorry tale I know about is that relates to cosmetic breast implants. Now years ago as we all know silicone was marketed for breast implants. What happened was that a series of high profile court cases occurred when women claimed that their silicone implants harmed their health. Now I do not want to take sides over this matter. As a result of the court cases the world’s leading producer of silicone withdrew from the medical / cosmetic market so a search started anew for a new material for filling breast implants. One of the materials which was used was soy oil. Now we might think that something which is a food substance would be harmless for use in an implant and for smearing on our bodies. But there is a nasty sting in the tail in this case.

The subject has been reviewed by S. Monstrey, A. Christophe, J. Delanghe, S. De Vriese, M. Hamdi, K. Van Landuyt, and P. Blondeel, Plastic and Reconstructive Surgery, 2004, page 847. Here it is explained that the super refined soy oil used in the implants tends to react with oxygen to form new products including some which are carcinogenic. The idea of substances such as malondialdehyde sodium (3-hydroxy-2-propenal) forming inside my body is not a welcome or comforting idea. This compound is a dielectrophile which could crosslink biomolecules in a similar way to glyoxal. The malondialdehyde would be formed by the oxidation of the linoleic acid groups which are present in the soy oil. Other horrible oxidation products could form in the oil, I would like to know if Maggie knows about the problem of the instability of biodiesel, when compared with traditional road diesel fuel (DERV) made from petroleum the FAME biodiesel is more unstable. I have seen some papers in which oxidation processes which involve the carbon double bonds (unsaturation) are involved in some oxidation processes which are not possible in mixtures of alkanes or most alkyl aromatics (normal diesel fuel). I will assume that no one is going to try to create a diesel fuel which contains large amounts of cumene (isopropyl benzene) or similar compounds. Cumene is a rare example of a alkylarene which is very able to react with the oxygen of the air.

FAME biodiesel is a refined plant oil which has been converted into methyl esters. I would like to know how Maggie and the people who might follow her plan to keep the oils fresh without using things like BHT as a stabilizer. I know that many oils contain tocopherols but the more the oil is refined then the lower the greater the chance that these will be removed by the refining process. I would like to know if the natural tocopherol content of the oil will be sufficient to keep it from forming nasty chemicals by going rancid during storage. Again this is an example of how a food substance is not universally safe for humans.

Now while I have concentrated on American products, I would like to consider for a moment some Swedish products. Now some of my readers might misunderstand the Swedes and their attitude to sex, rather than either being rather repressed or sex mad what the Swedes are is “open” about sex. This does not mean that they do it in the open or public places, what this means is that they are willing to talk more openly about it than the British.

In Sweden there is an organisation named RFSU (Swedish Association for Sexuality Education) sell condoms, pregnancy tests and other sex related items. Now while some of their products are things which I would rather not discuss here they do sell lube. It is interesting that the Swedish version of the RFSU site has a link to the RFSU shop which is absent from the English version, I will have to tell RFSU about this. RFSU market a range of lubes, some of which are aqueous based products while they also market a silicone based lube. They also market a product which is both water and silicone based. I suspect that the product based on both silicone and water will be an emulsion. An emulsion is a combination of two liquids which are not miscible. I will not discuss the silicone based products any further in this post. We will save those for another day.

It is interesting that RFSU market some products which are free of parabens, for a list of what the Kick range contain see here. I considered the question of how does a paraben free product stay stable and I noticed that the aqueous product contains the following substances.

Aqua, Propylene Glycol, Glycerin, Hydroxyethylcellulose, Phenoxyethanol, Lactic Acid, Sodium Saccharin, Benzoic Acid, Sodium Hydroxide, Dehydroacetic Acid

This list might look long and scary, but lets go through it step by step.

Aqua is water, unless you are nervous of “dihydrogen monoxide” then I would not worry about this substance. We have already discussed propylene glycol and glyerin, they are similar to each other in their purpose and relatively harmless.

The hydroxyethyl cellulose is a version of cellulose which we have already considered. The phenoxyethanol is an interesting one. It is an antibacterial, while it is not paraben it is still a preservative.

phoch2ch2oh

Phenoxyethanol

The lactic acid and sodium hydroxide are likely to be there to control the pH. I know that in a normal woman that lactic acid is found in the vagina so the use of lactic acid plus some sodium hydroxide to set the pH of the product seems to be a very reasonable choice by the designers of the Swedish product.

lactic-acid

Lactic acid (2-hydroxypropanoic acid)

The sodium saccharin appears to be an odd choice of chemical, it is a sweetening agent used commonly in foods. But a quick search of the literature does reveal that it is able to inhibit bacteria. So it may be present to prevent microbes from spoiling the product. I also notice that benzoic acid is present, this is a substance which prevents the growth of yeasts, again a substance intended to make the product be more stable.

The last substance is dehydroacetic acid which has some antibacterial properties, it has been reported that Collie as a young man made some interesting discoveries about this substance. He found that it could be converted into orcinol. Sadly I know very little else about this substance other than the fact that it is a cyclic compound which is a masked polycarbonyl. The interesting thing is that both the Cambridge database and Wikipedia both have data which suggets that dehydroacetic acid is C8H8Owhile a book (Chemistry of Plant Natural Products: Stereochemistry, Conformation by Sunil Kumar Talapatra and Bani Talapatra) suggets that it is a slightly smaller molecule.

dehydroacetic-acid

Dehydroacetic acid and the ring opening reaction with water

But when we think about this moelcule it is clear that on heating under acidic conditions that it will lose carbon dioxide (decarboxylate) to form a triketone with the formula C7H8O3 which then undergoes an aldol reaction with itself followed by some minor reactions to form the orcinol. The triketone can form a cyclic compound with a formula of C7H8O2 which the book labeled as dehydroacetic acid.

The aldol reaction will form 3,5-dihydroxy-5-methylcyclohex-2-en-1-one which can dehydrate and then undergo a keto-enol tautomerism to become aromatic and thus form orcinol. Here is part of the reaction in the following figure.

steps towards orcinol.png

Formation of 3,5-dihydroxy-5-methylcyclohex-2-en-1-one from dehydroacetic acid.

What will happen next is that the dehydration and the keto-enol tautomerism will form the diphenol (orcinol).

orcinol-formation

Final stages of the formation of orcinol

While the formation of orcinol from dehydracetic acid is interesting, it is a bit of a diversion. I would like to point out that I know too little about dehydroacetic acid to be able to make a judgement as to how much is good or bad to put in a product. However looking at the Swedish product it does appear to be a product where none of the ingredients are screaming danger to me.

Lastly I would like to point out that soy oil will degrade condoms and also stain the sheets / clothing more than a water / hydroxyethyl cellulose based lube.

So far I am not convinced that “lube” is dangerous, unless you smear it on the vines which Tarzan swings from tree to tree with. I have taken the time to contact Maggie to see if she wishes to reply to some of the comments raised in this blog. But so far she has not chosen to comment.

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