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A breakthrough in the odor retention technology

The research made in 2005 at the Oak Ridge Shark Lab by Eric Straud, a chemist, and Samuel Grabber, a shark expert of the University of Miami, again confirmed that the odor of cupric acetate repels sharks and is highly efficient.

International and Russian scientists needed more than 5 years of thorough work and a lot of tests to determine the efficient mixture based on cupric acetate and sulphate, which would resist impact of sea water and retain its odor.

Grogol Aroma today is the most efficient individual shark protective means based on cupric acetate, cupric sulphate (blue stone) and is capable of retaining its effect for up to 15 minutes in sea water environment. The surprising extension effect has been achieved by using acrylate copolymer - a substance, which creates a film on skin allowing for the active agent to remain on the skin for a longer time in water environment. This component is used in sunsreening cosmetics to make UV filters remain on the skin during bathing. Cetearyl izononoat, ceteareth-12, cetearyl alcohol, glyceryl stearate, glycerin, cetyl palmitate, ceteareth-20 all together compose a complex emulsifier, or being more accurate, the "Evimul CM" self-emulsifying system. It was introduced in the agent in order to make skin absorb the mixture better. And the sodium salt of ethylendiaminetetraacetic acid (EDTA Na) is the complexing agent, which stabilizes copper.

The Grogol LLC Company is the only owner of the Grogol Aroma trade mark and possesses a patent for use of the components, which allow to stabilize and extend the effect of cupric acetate and sulphate application due to chemical reactions of the components.

PATENTED FORMULA

The patented Grogol Aroma invention is related to satisfaction of human vital needs, namely to protective compounds, particularly to the means that directly impacts skin to protect it from exposure, and is to be applied before swimming in sea and ocean basins.

The objective of the invention is the development of a repellent that would protect people and retain and extend the effect of active agents when swimming in seawater.

This assigned task is met through the inclusion of active agents in the individual shark repellent, such as cupric sulphate and cupric acetate, film-forming material, complex emulsifier, stabilizer, and water.

Besides, the individual means can contain acrylate copolymer as the film-forming agent; and the following components as the complex emulsifier: cetearyl izononoat, ceteareth-12, cetearyl alcohol, glyceryl stearate, glycerin, cetyl palmitate, ceteareth-20; methylisothiazolinone and sodium salt of methylparaben as the preservative; triethanolamine as the pH regulating agent; sodium salt of diaminetetraacetic acid as the complexing agent; propylene glycol as the moisturizing agent; with the following compositional structure, wt.%:

  • cupric sulphate Ц 0.5 Ц 1.0
  • cupric acetate Ц 0.3 Ц 0.6
  • propylene glycol Ц 1 Ц 3
  • methylisothiazolinone Ц 0.1 Ц 0.2
  • triethanolamine Ц 0.07 Ц 0.08
  • sodium salt of methylparaben Ц 0.03 Ц 0.05
  • sodium salt of diaminetetraacetic acid Ц 0.05 Ц 0.1
  • complex emulsifier Ц 2.5 Ц 3.5
  • crylate copolymer Ц 1 - 3
  • and the rest is water.

For comfortable use, the individual means is made in the form of a liquid that is to be sprayed onto a human body.This invention is accompanied with a detailed description and examples of its forms and use.To prepare the individual shark repellent means, one must add the complexing agent, the preservatives, the active components of cupric sulphate and cupric acetate to the prescribed quantity of water. Then, the moisturizer, the film-forming material, and the complex emulsifier are to be added in a sequence.

Dispersion is achieved by mixing the components until the required emulsion concentration is reached.

The offered individual means is designed to repel sea predatory fishes - sharks - and to prevent them from attacking humans. Due to acrylate copolymer, cupric acetate, and cupric sulphate (blue stone), it is capable of retaining its effect for up to 15 minutes in seawater. Besides, it has the attributes of a resistant and highly dispersed emulsion, which can be easily applied and remains on human skin for a long time.This individual means is highly absorbed by skin and causes no allergy.  The offered invention is available under the patented Grogol Aroma trademark.

 

History of using cupric acetate and sulphate

In March 1942, Doctor Henry Field who had just returned from a PR mission and Doctor Harod J. Coolidge started discussing the psychological factor of working with the military men on the shark topic. Doctor Field got interested in this topic after he had had a chance to see with his own eyes the activity of sharks during his flight over the Caribbean Sea and hear the pilots expressing anxiety about the sharks. Doctor Field and Doctor Coolidge prepared a joined memorandum to President Roosevelt on the possibility of developing a shark deterring factor.

Further, there were long discussions between military commanders, which resulted in the decision that the development and implementation of a shark repelling technology would be very useful for the moral state of the survived people and would decrease their anxiety. In June 1942, the Bureau of Aeronautics issued a directive initiating the development of research, which would discover shark deterring factors. In July of the same year, the Bureau of Aeronautics communicated the Committee of Scientific Research, Development and Exploration of the Seas of the Committee of Medical Research for preliminary testing. Having received reports on shark attacks on the shipwrecked, the Vessel Committee expressed intention to develop a device, which would be suitable for use by all the naval forces helping them to repel sharks. And in April 1943, the Vessel Committee launched a project, within which the Naval Research Laboratory (NRL) started research on the solution of this task jointly with the Committee of Scientific Research, Development and Exploration of the Seas.

First research woks

The testing started in June 1942 in Woods Hole of the Institution of Oceanography, Massachusetts. Alive sea dogs were taken from the docks of the Institute and put to laboratory reservoirs. From July till September, several series of controlled experiments were carried out using 150 different repellents, including poisonous fishes, ink, poisonous gases, sharp unpleasant odors, and other chemicals. Groups of 3 to 5 sea dogs were watched individually during these tests. Each group had a record card, in which scientists made notes. They recorded the reaction of sharks to bait processed with certain repellent and not processed one. Each test lasted 1 to 2 hours on the average.

The results received in the tests were not satisfactory enough. Various irritant agents and such a repellent as sharp unpleasant odor did not give any effect. Ink clouds only worsened the sharks' vision but not repelled them. As for poisoned meat, it was found out that sharks ate it just like the nonpoisonous one. Of course, they died later on, but poison did not suit as a repellent for protecting people. Only 3 of 150 various repellents gave some certain effect: toxilic acid, cupric acetate, and decaying shark meat. Because of such discouraging results, this project was neglected for some time.

Discovering cupric acetate as a shark repelling material!

The chief researcher and a professional shark catcher Stewart Springer proposed the idea of using decaying shark meat based on his fisherman's experience. Fishermen found out that areas, in which there was decaying shark meat, were free of alive sharks. Researchers of Woods Hole concentrated their efforts on studying the decaying of shark meat as the last resort. During laboratory tests it was discovered that this process resulted in releasing a chemical agent - cupric acetate - which releases acetic acid when dissolved in water. Thus, it was determined that cupric acetate is the very shark repellent. As bluestone and acetic acid turned out to be the most efficient sharks repellents, it was decided to join together ions of copper and ions of acetate. This was a breakthrough, which resulted in deriving cupric acetate as the most efficient shark protective means. First tests of this agent in laboratory reservoirs were promising, so field tests were scheduled.

Field tests

First field tests were carried out in the Gulf of Guayaquil near Ecuador between December 6, 1942 and February 10, 1943 by the Committee of Scientific Research, Development and Exploration of the Seas (CSRDES). During the research, four chemical agents were evaluated: toxilic acid, cupric acetate and extract of decaying shark meat. The test series were carried out in three directions at different depths under consolidated control; shark attacks were recorded in each line during the day. Report No. 5 dated February 28, 1943, which was provided to CSRDES, specifically stated that tests with cupric acetate as a shark repellent had 100% success. Because of the success of cupric acetate, other repellents were considered to have failed tests. Further research was concentrated on the repelling properties of cupric acetate.

Additional research was carried out by the Naval Research Laboratory in cooperation with CSRDES in the Gulf of Mexico near Florida coast between May 1943 and January 1944. During these tests, cupric acetate was approbated at various depths and in various conditions. The tests included various fishers' technologies, baits, and even garbage to handle the behavior of sharks. To simulate the situation, survival vests with the "chemical pie" attached to them were placed between the surface and 12-feet depth. A great variety of sharks, which were noticed during the experiment, showed different results. If the concentration of cupric acetate in the "pie" was low, sharks showed 80% of their activity, and whenever the concentration of cupric acetate was higher, their activity went down to 50%.

Cupric acetate is a colorless substance, therefore, in order to see the dispersion of the agent, they added for the first time a colorant as an experiment during tests in June 1943 near the Florida coast. Supported by the results of research near the Mississippi shore in August 1943, the dark colorant proved to increase the efficiency of the repellent through affecting visual sensing channel of sharks. Dark colorant could be used as a cover-up, allowing some time for escaping (just like squids and octopuses do). Another important factor related to psychological aspect was that the user could see the chemical weapon in action. The Naval Research Laboratory applied for help to chemists who were developing water dissoluble colorants that would be compatible with cupric acetate. After a series of experiments, the dark colorant of nigrosine type was introduced. When dissolved in water, this colorant made water black or dark blue. In the NRL report dated February 25, 1944 and called "First Partial Report on the Use of Chemical Materials as Shark Repellents", the nigrosine colorant was highlighted as an efficient visual stimulus conducive to repelling sharks.

NRL researchers came to the conclusion that in order to achieve the maximum effect it was necessary to produce a mixture of cupric acetate and the colorant. The properties of both materials if joined into one substance could affect several organs of sense at a time, which would certainly improve the efficiency of the repellent. The final mixture consisted of 80% of nigrosine colorant and 20% of cupric acetate. Two series of three tests were scheduled for May 27 and July 3, 1944 in Mayport near the Florida coast. Experimental individual packs were produced for these tests, which consisted of a "chemical pie" in a waterproof container. These tests finally confirmed that this mixture was efficient as a shark repellent.

On July 15, 1944, the Vessel Committee issued preliminary certificate R51S48 (INT) for the "Shark Chaser" (a survival vest with repellent). The individual pack in the vest was filled with 5.5 ounces of the "chemical pie" with the repellent. The "pie" was packed into a cotton bag secured with a vinyl copolymer cover with textile coating. This dimensions of the device were 8 љ x 4 љ x Њ inches, a cotton band for fastening to inflatable survival vests and a lace with a pin for fastening to vests, which had silk cotton inside, were attached to it. The device functioned the same way as a painting marker. There was a snap on button on the outer side of the envelope containing the repellent. The "chemical pie" at this time had the following ingredients: 76% of colorant, 19% of cupric acetate, and 5% of dissoluble adhesive wax.

The official certification and standardization of Shark Chaser took place on October 1, 1945. Before this date, the device had been considered experimental. In the USA, civil vests with the repellent differed from the military ones with their single-time use and absence of a cotton band.

Release

On September 23, 1944, NRL issued the final report on the usage of chemical materials as shark repellents. Based on the report, the USA became the first country to have bought shark repellents in large quantities. The USA acquired 85,000 pieces of the product under a purchase contract.

In June 1944, the Bureau of Aeronautics purchased 2,500 packs for field testing. Those experimental packs were the same as those used in research works carried out in May and June, they did not have safety pins and the "chemical pie" was placed into a paper bag secured with a waterproof envelope marked "Life Jacket Shark Chaser". In January 1945, the USAF Provisional Wing initiated the purchase of 160,000 vests with Shark Chaser.

Researchers who had participated in the Shark Chaser development project understood that it was impossible to develop a 100% efficient repellent based on the knowledge they had. Therefore, the 67% efficiency of the received material was acknowledged satisfactory. The main attention in surviving when facing a shark was paid to the mental approach and morale, and the agent based on cupric acetate served as a significant bonus for the human in this fight. Finally, the results of the tests carried out in laboratory and field conditions were contradictory to some extent. Further research and corrections of the device depended on its real application on the battleground.

After the war, the design of Shark Chaser was changed. The cotton bands were replaced with nylon ones, yellow initially, and red later on. The shark repellent continued being used by the US military forces even in the eighties.

Some reports of survivors and other documentary publications of those times contain mentions of using chlorous capsules or pills in naval aviation as shark repellents. These documents come from 1942-1944 and they are not just occasional isolated mentions. Therefore this information must be taken into account. However, the research works carried out at Woods Hole of the University of Oceanography proved the inefficiency of chlor as a shark repellent. Besides, it is not clear how and where the idea to use chlor as protection against sharks appeared, and it is needless to say that there are no documents that officially recommended to use this chemical agent.

According to the information contained in the documents, the mentions of using chlor pills were received from battlegrounds. So we only guess how the idea to use chlor pills appeared. Probably, the marine folklore conduced that, or maybe the military men thought like this: chlor is an efficient irritant for a human, so why not trying it to sharks? It is not improbable that it was used just for encouragement (the simple knowing of having at least some weapon against this dangerous predator could improve the chances of survival).

However, the efficiency of the agent based on cupric acetate has shown a real repelling effect to sharks, and this has been repeatedly documented, unlike the story of chlor pills.

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