"Amitraz is a dimer (two identical molecules linked together) which easily
degrades."

Actually Amitraz is a compound that if viewed perpendicular to the long direction has a mirror image plane of symmetry that is perpendicular to the axis of the long direction.  This plane passes thru the central atom in the  molecule.  This is important as the mirror plane says the molecule can not be optically active and thus can not have other optical isomers.  In optically active molecules the biological activity can vary in type and intensity greatly from one isomer to another.  There is a well known case where one isomer is a valuable medicine and the other causes massive birth defects for instance.  It also says the molecule is not a dimer as you can not split the center atom in half.

Randy is correct that the paper I quoted just showed that amitraz degradation in both honey and wax was very rapid.  To be concerned about the biological effects of the amitraz degradation products is perfectly valid and would have been a required part of the registration package.  So, to assume something is being hidden is not really a valid assumption.  Those initial hydrolysis products may well be harmless.  I will go over what I could find in the following paragraphs.

The metabolic degradation pathways of amitraz and its hydrolysis products have been well studied in plants, animals and insects.  Most of the degradation ends up oxidizing the methyl group on the 4 position of the benzene ring to what amounts to a benzoic acid derivative.  That is what I would expect knowing chemistry and a tiny bit of biochem.  Such compounds are generally well excreted in urine and feces and I find citations that show radio tracer experiments showed this is a major pathway for getting rid of these compounds according to the following publication.

http://www.inchem.org/documents/jmpr/jmpmono/v098pr02.htm 

But a fairly quick search did not turn up any papers that detail the toxicity of  the individual metabolites or hydrolysis products.  As these molecules have been known a long time and are products of a pesticide the toxicity had to be studied as part of the registration package.  But such data is often never published in a public source.  They do not look to me like the kinds of molecules that would be suspected to be problems in low exposures so perhaps no one in academia looked at them or if they did the results were of no significance from a human risk standpoint and thus not publishable.

The whole central part of the amitraz molecule is required for it to bind to the receptors that cause it to be toxic to mites.  Hydrolysis destroys this central part thus the hydrolysis products are not going to be biologically active in the same way the parent molecule is active.  None the less, I will give my usual warning.  All chemicals are toxic if the dose is high enough.  I am sure this is true of the amitraz hydrolysis products also.

It is not a word game when it is said that amitraz degrades rapidly in honey and wax.  That is a well proven fact.  When chemicals degrade there are always other chemicals produced.  The atoms are never destroyed except in nuclear power plants or atom bombs.  Even in those cases while atoms are destroyed new atoms are formed.  From  a pesticide registration standpoint what the regulatory agencies must be told is what the degradation products are and how much of each is formed.  For each of those degradation products the registrant must supply toxicity data that shows that no harm will be done to the consumer, the applicator or the environment due to those degradation products.  It is accepted that water and carbon dioxide and a variety of naturally occurring molecules such as formates or acetates will do no harm when they are the degradation products.  For anything that is suspect you are going to have to do feeding studies on the degradation products and show that in the amounts that a consumer, an applicator or the amount that would get into the environment would do no harm.  Generally this means you need to learn what the metabolites of the initial degradation products are and also study those second step degradation products.  Or even third or fourth or fifth step degradation products.  You need to go far enough to account for all the radio label that is fed and determine how it is either incorporated into the animals normal metabolism or excreted.

So, the safety largely boils down to do I trust the registration agencies to do their jobs?  There are two kinds of employees in federal agencies like the EPA.  You have career scientists and lawyers who actually do the work and are long term.  All of those employees that I have known were tough as nails and smart as hell.  You did not BS them or they handed you your head on a platter.  Then you have the political appointees at the top who are by and large meaningless space fillers over the long term.  Short term they do lots of damage and cause lots of confusion.  Over the long term the former are the ones who wield the real power as eventually they are the ones that actually make decisions.  It just takes a lot of patience to work in government.  If I had ever had one of those jobs I likely would be in jail for killing someone at the top for doing something incredibly stupid.  I have a great deal of faith in the career employees and none at all in the political appointees regardless of who appoints them.  Very few of the political appointees have much training or back ground that qualifies them for their job.  There are notable exceptions.

Randy states he uses large volumes of formic acid and implies he has experienced no significant safety issues. I have run chemical reactions that used a pound of sodium cyanide.  I have run chemical reactions where I used a pound of lithium aluminum hydride.  That is enough LAH to blow a concrete block lab wall to bits.  I sat on top of a thousand gallon reactor controlling the feed rate of one ingredient while that reactor was making its virgin run making several hundred gallons of perchloric acid.  The space shuttle solid booster rockets used ammonium perchlorate as an oxider.  I was in Las Vegas when they had an ammonium perchlorate explosion in Henderson which was 15 miles away.  I felt the shake.  I understood what precautions I needed to take and had the proper back ground of training to do those operations safely.  All of them could easy kill an operator without adequate training.  We do not let untrained people drive rail road trains or fly jet airplanes.  Yet, we allow bee keepers to use formic acid who have no clue what safety precautions they should have at hand.  I agree that Formic Pro is a big safety improvement over MAQS.  With MAQS you often have liquid in the bottom of the container and that liquid is a splash hazard.  In addition to a bucket of water containing some sodium bicarb I would suggest anyone using MAQS should have within reach at all times a gallon bottle of plain water they can pour into their eye in case of a splash.  If it is going to take you ten minutes to get to a water faucet to wash your eye out you might as well keep working.  In ten minutes the damage is likely irreversible and you are in the market for a cornea transplant.  Any of the formic acid products is more dangerous by a big margin than breathing some oxalic acid fog from a sublimer in my opinion.  All the oxalic will do is make you cough really hard and in a few minutes you are ok.  Another significant danger is blowing the top off one of the fast sublimers like the ProVap and getting a face full.  Now you are talking thermal burns and I do not care how fast you hit it with water the damage is done before you do have time to do anything.  It is also very easy to avoid the problem.  Simply never get your face in line with the lid on top of the sublimer.  Perfectly safe as long as you know how to handle the apparatus, but very dangerous if not trained.  I worry a lot about untrained people and chemical handling.  Without training how do you have any idea what you should worry about?  People on here worry about amitraz and what it might do to them because it is synthetic and do not worry about formic acid or oxalic acid because they are natural.  How many of you know that formic acid and oxalic acid are made commercially in high pressure chemical reactors involving nasty and poisonous starting materials.  I do not know of a good book on how to safely handle chemicals.  The problem is what you need to know first some chemistry so you have some idea of what the risks are and what questions to ask.  Then you need to know what to search for on the internet.  A great starting point is a Material Safety Data Sheet.  But the cautions on an MSDS assume you already know a lot about safe handling.  Do you know how to take off gloves without exposing your self to what is on the outside of the gloves?  If not gloves are not of much use.  For toxicity stuff do you look for acute tox data, chronic tox data or allowable daily intake data?  Which you look up depends on the question you are asking.

The Beirut ammonium nitrate explosion last week is a good example.  If you learned any chemistry at all you should have learned about the Texas City ammonium nitrate explosion and should have known that ware house was a bomb waiting to go off. Yet that warehouse was allowed to store that stack of explosive for years.  Is there no one in that country that learned any chemistry?  Or is it a case of politicians  are too busy doing important stuff like stealing and lying to waste time listening?  I have long marveled that the world does as well as it does when such things that are fully predictable and well understood happen.

Dick

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