Forensic Toxicology THE FOLLOWING ARTICLE APPEARED IN THE APRIL 1998 ISSUE THE POISON SLEUTHS DEATH BY IODINE -Dr. Anil Aggrawal "Good morning doctor. Oh, my God, what are you doing today? You have the dead body of an old man. He has some brownish-yellow stains too around his mouth. What happened to him? Please tell me." "Good morning Tarun. The name of this 57 year old man is Ramlal. He was living alone in this house. He had no children, and his wife expired some time back. From all the accounts of neighbors, it appears he was having some depression. There were other reasons for depression too. He was a gambler and had taken a lot of money as loan from his friends. Some of them were pressing him to return his amount, and some were even threatening him with dire consequences, if he did not return the amount soon. The main among these was a person known as Mahto. He was seen entering Ramlal's house yesterday evening. Nobody knows what happened after that. Today morning when the maid came to Ramlal's house and knocked at his door, nobody opened the door. She got suspicious and called the neighbors. The neighbors broke the door open and found Ramlal dead." "Oh, I see. So definitely Mahto must have killed Ramlal." "Don't jump to conclusions Tarun. How do you know he didn't die a natural death?" "Well.....I thought that was the most natural conclusion to make. But come to think of it, Ramlal could well have died a natural death too." "But surely he didn't die a natural death. The reason is that a bottle was found in the room containing some dark liquid. The bottle was marked "poison" and it was half empty. As you can see Ramlal's face, the angles of his mouth are stained. It does appear he had taken this liquid." "Oh, yes, now I see. The area around his mouth is stained brownish yellow. So do you think Mahto gave him this poison?" "Well, this is what police is thinking. They have come to a startling conclusion. According to them, Mahto went to Ramlal's house to ask for money, but when Ramlal couldn't give him the money, Mahto wanted to get even with him, and gave him this poison. They have called Mahto, but he is denying this allegation completely. He says, that he did go to Ramlal's house and demanded his money, but when Ramlal expressed his inability to pay up, he left after giving him another warning." "It is quite possible that the police would torture Mahto to arrive at the truth." "Well, the possibility can not be ruled out. But I have examined Ramlal's dead body, and it appears to me Mahto is indeed innocent." "Oh, my God. How can you say about Mahto's innocence by just looking at Ramlal's dead body?" "Tarun. I have examined the contents of the empty bottle. It containes a strong tincture of iodine. It is the medicine which one applies to abrasions and wounds. It is used as an antiseptic. Iodine has a strong odor and a very bad taste. This poison can not be given to anyone as a poison...." "Do you think Ramlal never ingested the contents of the bottle, and died by some other means?" "No, Tarun, Ramlal did ingest the contents of the bottle. In fact, I have found signs on his dead body, which point to death by iodine. Not only this I have recovered some iodine from his stomach too. But the iodine was not given to him with homicidal intention. He ingested it himself with suicidal intentions. He probably did it so, because he was very depressed. He was not able to pay up his debts. Yesterday night Mahto visited him and demanded his money again. It dawned upon Ramlal, that he would not be able to stall his creditors for long, so after Mahto left, he consumed iodine to kill himself." "So iodine is such a strong poison, that it can kill? Well, can you tell me a little bit about iodine, so that I understand better how you detected iodine in his body?" "Tarun, Iodine was discovered by the French Chemist Bernard Courtois (1777-1838) in 1811. It might interest you to know that he was not interested in discovering a new element at all. He was actually in the buisiness of manufacturing potassium nitrate which was needed for making gunpowder. He used to get potassium nitrate from potassium carbonate (potash), which in turn he got from seaweed. As one of the steps to get the potassium carbonate, he had to heat the seaweed in acid. One day in 1811, he added too much acid and, on heating, obtained a beautiful violet vapor. On condensing the vapor, he produced dark lustrous crystals. This was in fact iodine. Courtois had in fact unwittingly discovered a new element! The element was given its name 3 years later by Sir Humphry Davy from the Greek iodes (like the violet). The name clearly refers to its unique color. It was originally prepared from the ashes of kelp and other seaweeds, just as Courtois had done. However at the present time, the major sources of iodine are natural and oil field brines, from which they are separated by a special process known as ion exchange chromatography. Kelps are very rich in iodine. I may tell you that although iodine in large amounts is poisonous to our body, it does need iodine in very small quantities. It is needed by the thyroid gland to make the hormone thyroxine. If someone's diet is deficient in iodine, his thyroid gland may enlarge. This disease is known as goitre. Kelps are so rich in iodine, that people who consume kelps don't suffer from goitre at all." "Oh, I see. How much iodine is required by our body daily?" "Tarun, the daily requirement of iodine is about 150 micrograms/day in adults, of which the thyroid gland takes up about 70 micrograms. Rest of the iodine is used for some other essential purposes. Some commercial preparations containing iodine are povidone-iodine and tincture of iodine. These are basically used as antiseptics and disinfectants. Ramlal probably kept the tincture of iodine in his general medical chest, as most of us do. Povidone-iodine is primarily used as a vaginal disinfectant. Tincture of iodine is usually applied on cuts and abrasions, to prevent them from getting infected. Tincture of iodine consists of 2% iodine, 2.4% sodium iodide, 47% ethyl alcohol and rest is water. Then there is the strong iodine tincture, which was found in Ramlal's house. It consists of 7% iodine, 5% potassium iodide, 83% ethyl alcohol, and water. It might interest you to know that the word tincture comes from the Latin tinctura (dyeing), which in turn comes from tingere (to dye). This Latin word also gives us the common English word tint. It is interesting that the word tincture is applied only to alcoholic solutions. Medicine and dyeing may appear to have no connection at all, but in fact there is an interesting link. In pharmacy alcoholic solutions are commonly called tinctures because many dyes will dissolve in alcohol but not in water. Tincture of iodine is reddish brown in color. In addition to tincture iodine, another preparation, Lugol's iodine is also available which consists of 5% iodine and 10% potassium iodide and the rest is water." "Oh, the information is interesting indeed. Can you tell me what symptoms does one experience if he is given iodine?" "I would like to tell you, it is not easy for someone to give iodine to others for homicidal purposes, because it has a characteristic color, odor and taste. Iodine vapors too have a characteristic odor and taste and are intensely irritating to the eyes, mucous membranes, and skin. In several countries, such as the US, the maximum allowable concentration is 0.1 ppm (1 mg/m3). Ppm, as you know stands for Parts Per Million. Even at this concentration, i.e. 0.1 ppm, some people may experience eye irritation. Higher concentrations may lead to excessive tearing, tightness in the chest, sore throat, headaches, irritation of the respiratory tract, and water-logging in the lungs, similar to that seen with chlorine gas exposure. Iodine is a powerful irritant and vesicant, which means it can cause skin eruptions. Symptoms may occur through inhalation, skin or eye contact, or ingestion. Iodine vapor may cause brown staining of the cornea. A 7% solution of iodine, which as you know now is the strong iodine tincture, is corrosive to the eye and the skin. Owing to its strong oxidizing action, iodine acts as an acid corrosive, precipitating cell proteins. Symptoms of iodine ingestion include unpleasant metallic taste, brownish-colored vomit, diarrhea, weak pulse, and retention of urine. There may be corrosion of skin and and mucus membrane with brownish yellow stains. Finally there may be delirium, stupor, and collapse. Changes in the body involve staining of the walls of food pipe and of stomach walls and rapid development of pneumonia-like symptoms." "Doctor, how much iodine is sufficient to kill a person?" "Tarun, about 3-4 g of elemental iodine or 30-250 mL of strong ticture can kill a person. Death usually occurs in the first 48 hours. However death can occur as early as about ½ hour after ingestion to as late as 52 days." "Oh, I see. Well, in the current case how can you prove to the court that Ramlal did die of iodine poisoning?" "As I told you, I found Iodine in his stomach. Iodine can be detected in stomach by some deceptively simple tests. If the stomach contents contains iodine, it may be made to sublime, by taking the stomach contents in a beaker and warming it gently. The purplish iodine vapours may be made to condense on a watch glass placed on the top of the beaker. Another test involves adding 1 ml of starch solution to 10 ml of stomach contents. A blue-black colour will develop immediately due to the formation of starch iodide. If death has occurred after 2-3 hours, some iodine may have reached urine too. To detect iodine in the urine, we add 5 ml of chloroform and a few drops of nitric acid to 10 ml of urine and allow to stand for 3 minutes. A pinkish violet chloroform layer forms, which confirms the presence of iodine in the urine. I have done all these three tests on Ramlal's body and have found iodine in stomach contents as well as in the urine." "You said you found some signs on Ramlal's body also which pointed towards iodine poisoning. What are those signs?" "Tarun, the main sign is the brownish or yellowish stains of skin, which you can see on Ramlal's body. Furthermore all internal organs such as liver and spleen are found engorged with blood. Sometimes there is a characteristic odor too from the body, but this is very rarely perceptible. Now since we have proved that this is a case of death due to iodine, we can easily prove that Mahto couldn't have given this solution to Ramlal. Come, let us tell the police about it, so they can release Mahto." "Oh, how very clever of you doctor. This was a most interesting discussion. It is doubtful if Mahto could have been proved innocent without your excellent detective work. Tell me what are you going to tell me the next time?" "Tarun, next time, I would tell you about a very interesting poison- Barium "

SCIENCE IN CRIME DETECTION-14 CONTUSIONS - THE VITAL EVIDENCE A remarkable case came to me in the summer of 1992. Bali Ram, a nine‑year‑old stepchild of Hari Ram and Bhairon Devi had fallen down the stairs and had fallen down the stairs and had died. Actually, when he fell down the stairs, there was a big hue and cry in the neighborhood. Some neighbors came to the spot immediately and brought the child to LNJP casualty. The child was declared dead on arrival and sent to me for post mortem examination. A few facts about the family may be said her, before we go on further. HariRam had lost his first wife Kasturi about 5 years back. She had died of tuberculosis. Bali Ram was Kasturi's son. After Kasturi's death, Hari Ram became a recluse for almost two years, but gradually the shock of his wife's death faded and Hari Ram married for the second time. From the beginning, it was apparent that Bhairon Devi, the new bride hated Bali Ram intensely. In the beginning, she would merely ignore him but gradually she started handing him more severe punishment. She would often beat him and deny him food. I got this history from the neighbor. The moment I got this history, I became very cautious and decided to look for clues that might give me the correct story. The boy had died from head injury which he had sustained during the fall from stairs. There were several fractures on his skull, and the brain inside showed blood clots. This was ample proof that he had indeed fallen down the stairs. However, the clues that could give me some 'behind‑the scene' story still eluded me. Finally I turned over the body and looked for injuries more closely. There were several contusions on the back. these are also known as bruises. In common parlance, in Hindi, we know these as " Neel ". These are commonly caused by blunt force application. I had looked at these contusions before starting the post‑mortem, but at that time I thought that they were produced by fall from stairs. Contusions can indeed be produced by a fall from the stairs. However, when I looked at them closely, I found them to have some pattern. These contusions are known as patterned contusions and are quite helpful in the forensic work. They tell us the shape of the object which was used to hit the deceased. If the hitting object was a lathi or an iron rod, the contusions would be linear in shape. If a hockey stick was used to beat the deceased, the contusions would take the shape of hockey stick and so on. Look at the figure A and you would realize that the contusions indeed have a pattern. I tried to decipher what the object could be, but the exact object eluded me. Then suddenly, like a flash of lightning, the object came to my mind. It had to be a coat‑hanger. The contusions looked exactly like that. I told this fact to the police officer Tejpal. I thought that Bali Ram was first mercilessly beaten by Bhairon Devi and then pushed down from the stairs. If this point of view could be proved, it would change the whole scenario from an accident to murder! The case was beginning to take a serious turn. Bhairon Devi was summoned by Tejpal, the investigating officer, and questioned. She reaffirmed that Bali Ram had indeed fallen down the stairs and she hadn't beaten him. She asserted that she loved Bali Ram like her own child. How ever her neighbors refused to confirm her assertion that she loved Bali Ram like her own child. They asserted that she often beat Bali Ram. Finally Tejpal decided to search her house. The specific thing he was looking for, was the hanger with which Baliram was supposed to have been beaten. Finally he indeed found the hanger and brought it to me. When I matched the shape of the hanger with that of the contusions, the shapes corresponded completely. (See figure B). This testified that the boy was indeed beaten. This evidence broke Bhairon Devi and she confessed the whole crime. She was duly prosecuted by the court on my evidence and sentenced to life imprisonment. This case amply illustrates, how a seemingly trivial clue can turn a case entirely.

Forensic Toxicology THE FOLLOWING ARTICLE APPEARED IN THE SEPTEMBER 1999 ISSUE THE POISON SLEUTHS DEATH BY YELLOW KANER -Dr. Anil Aggrawal "Good morning doctor. Oh, my God, what are you doing today? You have the dead body of a very young girl today. What happened to her? Please tell me.” “Good morning Tarun. The name of this six year old girl is Radha. Her father is a Secretary to the Government of India, and fairly well-to-do person. He had only one child. Yesterday she was playing along with her friends under a tree in a park near her house. The time was around 4 pm. There were about 5-6 other boys and girls with her. They were apparently fine when they were playing. Suddenly Radha started vomiting. She had diarrhoea too. She was rushed to the hospital, where the doctors thought she was having gastro-enteritis, and she was being treated along those lines. The doctors also noted some additional symptoms. I have talked to the doctors who treated her. And they say that they noted clamminess of skin, coldness in extremities, dilation of pupils, sunken eyes and delirium. The pulse was slow and feeble in the beginning, but later it became fast and irregular. After a few hours she had convulsions, then paralysis, and finally death. She died at about 8 am in the morning today." "Oh, that is most terrible doctor? Why do you think she died? Did she die of any natural disease? Or did she die of infections such as gastro-enteritis?" "Tarun, it doesn't look like natural death to me. The symptoms are pointing towards a poison which affected her heart. So probably we are talking about some heart poison here. I have gone to the place where she was playing, and I was surprised to see that there were lot of Yellow Kaner plants in the garden where she was playing. These plants are known to botanists as Cerbera thevetia or Thevetia peruviana. In normal everyday parlance, they are known as Pila kaner or be-still tree. I am inclined to believe that either she took the seeds of that plant by mistake, or somebody gave it to her on purpose.” “That’s most preposterous. I have seen Kaner plants growing along the roads, but I never believed it was such a dangerous poison” “Oh, sure they are poisonous. The yellow oleander or be-still tree is a native of tropical America and is now widely cultivated as an ornamental shrub in tropical and subtropical regions of the world, including India. It is a small shrub with milky sap. Leaves are evergreen, alternate, ribbon like, about 6 inches long, 3/16 to 3/8 inch wide, dark and glossy above and pale beneath. Flowers are more or less fragrant, funnel form, yellow or peach-colored, rarely white, 2 to 3 inches long and to 2 inches wide, the five lobes spirally twisted and not spreading. Fruit is somewhat diamond-shaped -distinctly so in cross section. It is about one and half inches wide and 5/8 inch thick. It turns from green to yellow; then the thin layer of flesh becomes completely dehydrated, the skin becomes black and wrinkled and disintegrates, exposing the bony, light brown, attractive stone, which contains two to four flat gray seeds. The sap of the plant may cause skin inflammation in sensitive individuals. Chewing the bark or seed kernel causes a slight numbing sensation and a feeling of heat in the mouth, and purging. Ingestion of a toxic dose causes burning in the mouth, tingling of the tongue, dryness of the throat, headache, vomiting, purging, excitement followed by drowsiness.” “Sounds like a very dangerous plant to me. Are all parts of the plant poisonous? Also please tell me, which poisons are found in this plant?” “Except for the thin layer of flesh covering the stone, all parts of the plant are poisonous, especially the seeds, which contain 3.6 to 4 per cent of the cardiac glycoside thevetin. This toxin is one eighth as potent as ouabain and very similar to digitalis in activity, about which we have talked last time. Also present are thevetoxin (C30H46O10), similar to but less toxic than thevetin; neriifolin (C33H61O30) more potent than thevetin in action on cat heart; peruvoside (C30H44010); and also ruvoside (C30H46010). There has also been reported a bitter principle that acts on the central nervous system and produces tetanoid convulsions.” “Doctor, how much portion of the plant can cause death in a human being?” “Nothing is positively known about the fatal dose in human beings, although experiments have been done on animals. Fifteen to twenty grams of dry leaves are fatal to the horse; lesser amounts are fatal to cattle. Since such fatal experiments can not be conducted on human beings, our knowledge of the fatal dose of Cerbera thevetia depends upon actual cases of death which have occurred following its ingestion. A single seed has caused death in a child; 8 to 10 seeds in an adult. About 5-10 leaves of the plant are also said to be fatal. The root is very poisonous.” “Oh, I see.” “Tarun, this plant is a very popular ornamental in warm regions of both hemispheres, especially in dry coastal areas because of its resistance to drought and salinity and because it is not eaten by goats and cattle. It is often planted in numbers as a hedge. Grazing animals instinctively avoid this plant, and that is why this is a very popular plant as a hedge in India. Besides India, it is also found in other parts of the world. It is occasionally seen in the southern half of Florida and California, is very common in the West Indies, Latin America, Africa, and the Orient. In the Hawaiian Islands it has been declining in popularity with the realization that it is the most frequent local cause of human poisoning. The fruit flesh is eagerly consumed by chickens and is casually eaten by humans in Ghana and Queensland. The handsome stones, after polishing, are worn as pendants, tied together as rattles, or strung with other seeds in necklaces. Many myths and legends are associated with this plant. In the West Indies, the stone is carried in the pocket in the belief that it will ward off hemorrhoids. In East Africa, it is put in the hand of an infant at birth as a good luck token. Quantities of the seeds have been exported from Hawaii to the mainland of the United States for extraction of thevetin as a substitute for digitalis, but 40 per cent of the patients receiving this drug have suffered gastrointestinal disturbances. Indian scientists believe the more recently discovered peruvoside holds greater promise in cardiac therapy. In Africa, the seed kernels are occasionally chewed to cause purging. In the Philippines, half of one leaf is given as an emetic and purgative. The sap and bark have been utilized in small amounts to treat malarial fever as well as to induce vomiting and purging, but overdoses have caused paralysis and death. The sap has been applied to sores and ulcers, also to tooth cavities and decayed teeth to relieve toothache. It is said to cause the teeth to disintegrate. In Brazil, the seed is taken as an abortifacient. In Indonesia, immigrants from India have been seen to dry and smoke the leaves. The toxicity of the plant has been generally known since the sixteenth century. Its Sanskrit name "Ashwamarak" is translated as "horse killer. Early European explorers in tropical America reported that the Indians used the seed for homicidal purposes. In India, the seeds are commonly employed for suicide and homicide, and in Bombay they are used for killing cattle. They have poisoned pigs in Queensland.” “Looks like a very interesting plant to me. Have there been cases of poisoning with this plant before?” “Several cases of Yellow Kaner poisoning have been recorded in India. In 1900, a woman in India took two seeds in a suicide attempt. The following day, she experienced vomiting, purging, pain in the throat, headache, and fainting spells alternating with drowsiness. Her pupils were normal; heart action was weak and pulse slow. She recovered after three days of treatment. In November 1962, a four-year-old boy in Poona, India, swallowed a seed at 6 P.M., vomited 15 to 20 times, was hospitalized, was found very restless, with sunken eyes but normal pupils, dry tongue, and cold extremities. An electrocardiogram showed severe abnormalities. The following morning diarrhea occurred; on the second day the pulse became irregular, and it remained so for 36 hours. Treatment was continued for eight days; then the child was discharged with normal pulse and heart action. Some interesting cases have come from Queensland, Australia. In one case, a 3-year-old girl played "tea parties" under a yellow oleander tree in her backyard. She later developed persistent vomiting, sweating and bradycardia. Cardiac arrest occurred during her transfer to hospital and she could not be resuscitated. Another young girl was "dared" by her brother to eat the fruit of the yellow oleander. She did, and later developed severe vomiting and a variety of cardiac arrhythmias which persisted for three days before she recovered. In southwest Africa, two European children were poisoned by eating the seeds, and one died in six hours. In Southern Rhodesia, a death occurred two hours after ingestion of one seed." "Looks like this plant has really caused deaths! In this case doctor, how are you going to prove to the court of law that this child died of Cerbera thevetia poisoning?" "Tarun, I have examined her stomach, and have found remains of some leaves which look very much like Cerbera thevetia leaves. This is a very strong indication that she was given the leaves of Yellow Oleander to eat. I did not stop at that. I examined the extracts of her heart muscle and it demonstrated the presence of poisons found in Thevetia leaves or fruit. This is ample proof for any court of law to assume that Radha died of Yellow oleander poisoning. Actually when I saw Kaner plants growing in the garden nearby, I got suspicious. I thought that there might be some foul play involved in this. I found out that the father of this girl, one Mr. Sharma, had sacked one of his juniors Katkar about a year before, and since then Katkar held a grudge against Mr. Sharma. I may tell you that Katkar was a fairly intelligent man, and in his college, he had studied botany and chemistry with keen interest. Apparently he was aware of the poisonous nature of the Cerbera thevetia plant. He wanted to get even with Mr. Sharma very keenly. He had observed that there were Cerbera thevetia plants in the nearby garden, and that Mr. Sharma's only child Radha used to play there. On that fateful day, he came to the child and somehow coaxed her to chew those leaves. I really don't know what he told to the child, but her friends who were playing at a short distance away are saying that they did see Katkar talking to Radha, and Radha subsequently chewing the leaves of Kaner plant. You might think that it is very silly for a child to listen to such strangers, but you must keep in mind that a six year child does not have much judgement of her own. She apparently chewed some leaves on Katkar's insistence and that was the cause of her death. Come, let us tell the police to catch Katkar, because it is he who is responsible for her death. "That was very clever of you doctor. Without your clever deduction everybody would have thought Radha died of some mysterious natural disease. This was a most interesting discussion doctor. Tell me what are you going to tell me the next time?" "Tarun, next time, I would tell you about a very interesting poison. You would normally think it to be a vitamin, essential for growth, but it is a very dangerous poison too. I will talk about Vitamin A next time."

Forensic Toxicology THE FOLLOWING ARTICLE APPEARED IN THE FEBRUARY 1999 ISSUE THE POISON SLEUTHS DEATH BY POTASSIUM PERMANGANATE -Dr. Anil Aggrawal "Good morning doctor. Oh, my God, what are you doing today? You have the dead body of a middle aged man today. The corner of his lips seem to be stained with some dark black substance. What has happened to him? Please tell me." "Good morning Tarun. The name of this middle aged man is Sagar, and he is about 45 years old. He died in the hospital today morning. Yesterday night, he was having his dinner when suddenly he developed a burning pain in his abdomen. He had nausea and vomiting too, and the vomited material contained some brown material. He complained of intense thirst too. Because of this, the was brought by some of his neighbors to the hospital. But while the doctors were still investigating, he died today morning. Now since the doctors had not arrived at any diagnosis, the police has handed over his body to me. They want me to tell them, how Sagar has actually died." "So what are you going to do now?" "I have taken a detailed history from the police. The police tells me that Sagar was a builder, and he was running a very successful business. He however had business rivalry with a person called Nath. Apparently his business endeavors had caused great losses to Nath. Nath however kept visiting him often and posed as if he was his friend. Deep in his heart however, he wanted to get rid of him. Yesterday Nath visited him in his house for the New Year celebrations and gave him a bottle of red wine too for celebrations. Sagar was a sucker for red wine, so immediately after Nath left, he started consuming the red wine. However I am told that before Nath left, Sagar treated him to some very nice champagne from his own stock. But after Nath left, Sagar opened the wine bottle and emptied it in no time. After that he started having his dinner, but soon he started having all those symptoms." "Oh, I see. Looks like there was something in the red wine, which caused these symptoms. Is it?" "Probably you are correct Tarun. I became suspicious when I saw these dark stains on Sagar's face. You also noticed these stains, didn't you? Furthermore, the inside of his mouth and foodpipe were also stained. From these and certain other post-mortem findings which I am going to tell you later, I could zero down only on one poison....." "What is that poison doctor? Please tell me." "Tarun, it is a very rare poison. You probably never even imagined it is a poison. It is potassium permanganate or KMnO4." "Really? Yes, I never believed Potassium permanganate could be a poison too. In fact as far as I know, it is used to treat certain poisonings." "You are right Tarun. In certain poisonings, such as poisoning by Opium, potassium permanganate solution indeed is recommended. Doctors actually wash the stomach with this solution, because potassium permanganate oxidizes the opium. Similarly in many other poisonings, doctors wash the stomach with potassium permanganate solution. But unfortunately permanganate acts as a poison too. In fact about 10-20 g of potassium permanganate is enough to kill a person." "Is it? Oh, I think, we are on the trail of yet another interesting poison. Doctor please tell me more about Potassium permanganate (KMnO₄)?" "Tarun, potassium permanganate is a common substance, and it may be acquired without restriction by members of the public. Yet poisoning by it is uncommon and although in the case of Sagar we are probably facing a death due to this substance, in fact fatal poisoning by KMnO4 is rare. This must not cause its danger to be overlooked or underrated. Children in particular must be protected against the ingestion of colored crystals which may be eaten in mistake for sweets. In fact, I am personally aware of a child aged about 22 months who died after eating some permanganate crystals which his father used for gardening. Tablets of KMnO4 are still on sale in the USA and as Condy's tablets in Australia. In India too, this substance is not difficult to acquire. You may be surprised to know that KMnO4 has been used for illegal abortions." "Really? How??" "Potassium permanganate is an irritant substance. It irritates the uterus too, and may cause it to expel its contents. This has made the use of KMnO4 very popular in illegal abortions. Some women simply ingest it, while some make its solution and introduce it in their uterus through the vaginal route. Some women simply introduce crystals of KMnO4 in their vagina in order to procure abortion. The insertion of tablets of potassium permanganate into the vagina to procure abortion first came to notice in Spain and Italy during the 1930s. The practice spread to the USA in about 1936. This practice was noticed in England during World War II. It was thought that this 'new way to miscarry' was introduced to England by American servicemen, and indeed the tablets of KMnO4 were being hawked outside the local antenatal clinic of several doctors! You may be surprised to know that the mothers of newly married brides often regarded a box of these tablets as an appropriate gift to their daughters on the eve of their wedding!" "Oh, that is indeed most interesting. Probably it was because proper methods for abortion had not been developed by then?" "No, proper methods for abortions were there, but unfortunately abortion was not legal in most countries at that time. For instance in India, abortion became legal only as late as 1971. Before this time, if any married or unmarried woman became pregnant, the only way for her to have an abortion was to resort to such dangerous "household" methods. Although abortion has become legal in most countries, yet this practice has not yet have been abandoned in most of the countries. The reason is that most unmarried girls - for fear of society's censure - still don't want to disclose they have fallen pregnant. They prefer to do it themselves by these dangerous methods. They learn of these methods from their friends, acquire KMnO4 from somewhere and then try it out on their own. This has caused several deaths too. Douching with potassium permanganate is also very common..." "What is douching doctor?" "Women make a solution of KMnO4 and then with the help of an appropriate instrument, push this solution into their uterus. The douching may be done with intent to procure an abortion or only for hygienic reasons as KMnO4 is supposed to be an antiseptic. If however, the solution is too concentrated, it can have dangerous and probably fatal consequences." "Oh, I see. Has it been used for some other illegal activities too?" "Yes, potassium permanganate has been used to produce fictitious injuries. A trick is often employed by soldiers to simulate the lesions of tertiary syphilis by applying a tablet of permanganate to the skin for 10 to 20 minutes..." "Doctor what is tertiary syphilis? And what do you mean by lesions?" "Tarun, syphilis is a venereal disease which spreads by sexual contact. It affects the victim in several stages. Tertiary syphilis is the last stage of this disease, which commences several years after the sexual contact with an affected partner. By lesions, I simply mean the various abnormal and harmful changes which occur because of disease. A peculiar lesion in tertiary syphilis is a perforating ulcer of the feet. Such a lesion can be produced by applying potassium permanganate on the feet for several minutes..." "But why would a person want to produce such a lesion?" "Many persons want to simulate disease in order to get medical leaves. This trend is very common in the Army, where getting leaves is very difficult. Such people who pose that they are ill, yet are not, are called malingerers. A case of a soldier has been described who swallowed a solution of permanganate to simulate 'coffee ground' vomit. Such kind of vomit is usually seen in gastric ulcers. So probably this soldier wanted leave on this ground." "Oh, that is most interesting. Has it been used for other illegal activities too?" "Well, not for illegal activities, but certainly for some dangerous activities. For instance potassium permanganate solution was used at one time, notably during and after World War I, as an irrigant of the urethra and bladder in the treatment of gonorrhoea. The reasoning behind it was the same - it acts as an antiseptic." "Doctor, you told earlier that KMnO₄ is used for stomach wash in certain poisonings. Does it not kill the patient then?" "Tarun, when KMnO₄ is used for stomach wash, it is used in a solution of the strength 1:5000. It acts as an irritant in higher concentrations - about 1:1000. I may tell you that from the color of the KMnO4 solution, a rough idea can be made about the concentration. When the solution has a faint pink colour, the concentration is about one part per million. When the concentration rises to 1 part in 76,000 (65 mg/4.5 l) the fluid becomes purple. Because of its color, the solution has been used for staining also. Those who use the chemical as a stain for flooring and woodwork, working with a concentrated solution, must exercise care. Deep staining of the skin of the hands is immediate and prolonged contact can cause damage to the skin. There was a time when permanganate was used to dye white hair a chestnut brown." "Oh really?" "Yes, and I can tell you certain other interesting facts about permanganates too. Permanganates are normally stable in crystalline form but zinc permanganate can become explosive. In fact, storing it in tightly stoppered bottles can be highly dangerous. When handling these containers one should exercise utmost caution." "Doctor, do you think Nath mixed Potassium permanganate in something which he gave to Sagar?" "Yeah, looks like. Remember he gave a bottle of Red wine which Sagar immediately consumed after he left. Potassium permanganate can be easily dissolved in red wine because the colors of both are similar. Moreover the taste of red wine would mask the taste to potassium permanganate. Furthermore, Nath ensured that Sagar was not completely in his senses by having some drinks with him in his house. He knew that after he left his house Sagar would consume the red wine, and he would get severely poisoned." "Doctor, has Potassium permanganate been used for homicide often?" "Not really. It has more often been used for suicidal purposes, but accidental poisoning also occurs, notably in children under the age of four years, who usually mistake the red colored crystals for sweets. Adults, however, have taken the poison by mistake. A solution of permanganate may easily be mistaken for wine. And as I already told you, in the past it occasionally caused poisoning when taken orally as an abortifacient." "What is an abortifacient doctor?" "Tarun, abortifacient is a drug which causes abortion. Another popular - although wrong - belief is that it is a remedy for amenorrhoea. Amenorrhoea means absence of menstruation. Normally a girl should start menstruation at about the age of 13 years, but if the menstrual cycle does not start, the condition is known as amenorrhoea. Ideally when faced with such a symptom, a woman should contact a doctor, but many women prefer to treat themselves by folk remedies, and potassium permanganate is one of the folk remedies for amenorrhoea. Pills containing 65-130 mg of potassium permanganate, taken shortly before the expected period are supposed to cure the condition." "Doctor, what symptoms does the person get when he ingests potassium permanganate?" "Tarun, the symptoms are exactly as seen in Sagar's case. Staining of the tissues is very obvious. Some patients may have brown stains on the face, in linear form running down from an angle of the mouth on to the chin as you have seen in Sagar's case. The eyes and face may be stained if crystals fall on to the face. It is more usual to find discoloration of the interior of the mouth. If seen soon after poisoning the colour is purple-brown, but within minutes this changes to brown or dark brown and, later, following the formation of manganese dioxide, it may be coal black. A slight metallic lustre may also be apparent. I have seen Sagar's food pipe and it is coal black from the inside. This is a very clear indication that he had ingested potassium permanganate. I may tell you that potassium hydroxide is a product of the action of permanganate on the tissues, so corrosion of the foodpipe and stomach may be present. It is however superficial. The lips, gums, teeth, tongue, tonsils, pharynx, and the upper end of the larynx are all likely to be discoloured, inflamed and superficially corroded. This is especially severe at points where any crystals may lodge inside the mouth or throat. Occasionally, crystals may be seen on the lips, inside the cheeks or at the back of the throat and in the piriform fossae, especially when unusually deep." "What are the piriform fossae doctor?" "Tarun, the word piriform comes from the Latin pirum which means a pear. These are deep pear shaped pockets on either side of the pharynx. They are present at just the point where the pharynx ends and oesophagus starts. These pockets are at the sides. In fact any swallowed object - like pins for instance - is likely to get entangled in these pockets. If crystals of KMnO4 get lodged in piriform fossae, they can corrode these areas. Burning pain from the mouth to the pit of the stomach occurs soon after the ingestion of permanganate. Nausea and vomiting are not long delayed and the latter may become intractable. The vomit contains purple-brown or brown material which may be mistaken for altered blood from a bleeding peptic ulcer, i.e. 'coffee ground' vomit. Fluid loss by vomiting may cause intense thirst. A number of the patients experience difficulty in speaking or swallowing; this may persist for several days. About half of the patients complain of epigastric pain and tenderness. This may be accompanied and exaggerated by distension of the abdomen. The stools are black due to manganous sulphide. Potassium permanganate can come in contact with the air passages and when it does that, it provokes severe swelling of the air passages. Irritation of the trachea and bronchi leads to difficulty in respiration, and a persistent, spasmodic cough. Any sputum produced may contain dark flecks. A lethal dose, e.g. about 20g, usually kills in from 20 to 90 hours. When potassium permanganate is introduced into the uterus death may occur in only 12 hours." "Doctor, I have known enough about potassium permanganate to interact intelligently with you. Now tell me how you are going to convince the court positively that Nath killed him by giving KMnO4 in red wine?" "Tarun, I have got the wine bottle seized, and I have analyzed its washings. It has shown traces of KMnO4. How could KMnO4 come in a wine bottle? Obviously someone had put it there. And who else except the one who gave the bottle to him, and that too his business rival. Moreover I have found all the changes in Sagar's body, which are found in deaths due to KMnO4. As I told you, the changes produced by potassium permanganate are essentially those produced by an irritant and mildly caustic poison, but distinguished by brown-black staining of the tissues. I have found the staining of tissues in Sagar's case all over - over his face, inside his mouth, foodpipe and stomach. All these organs show congestion too, which is seen in ingestion of irritant poisons like KMnO4. I have also analyzed the contents of his stomach and I have found KMnO4 there as well. This is enough evidence to nail Nath. Come, let us tell the police to arrest Nath at once. He should not escape the legal net." "Very clever doctor. This was a most interesting discussion doctor. Without your masterly deduction, Nath could never have been caught. People might have thought, it was an accidental or perhaps a natural death. Tell me what are you going to tell me the next time?" "Tarun, next time, I would tell you about death by diesel fumes." "

SCIENCE IN CRIME DETECTION-31 CE

Forensic Toxicology THE FOLLOWING ARTICLE APPEARED IN THE MAY 1999 ISSUE THE POISON SLEUTHS DEATH BY AFLATOXINS -Dr. Anil Aggrawal "Good morning doctor. Oh, my God, what are you doing today? You have the dead body of a young man today. What has happened to him? Please tell me." "Good morning Tarun. The name of this young man is Suman Dubey. He is 25 years old and unmarried. He died this morning in his rented house. He was living alone in this house. He was basically a farmer, but had recently shifted from his village to live in a suburb of Delhi. He was doing some odd jobs for carrying out his livelihood. But he was also getting assistance from his family in his village. I mean, he used to get most of his food supplies from his village." "That's alright doctor. But how exactly did he die?" "Tarun, I am coming to that. For quite some time he was complaining of some vague symptoms. For instance, he was having pain in the abdomen and loss of appetite. He also noted some loss in weight, and a vague swelling of the abdomen. Since he was from a rural background, he did not believe in modern medicine. He was a staunch believer in traditional medicine only. He kept on ignoring his symptoms for quite some time. Last week he visited his village, where he consulted a local doctor. The doctor, after examination told him, that he was getting slow poisoning from some source. He believed that some of his foe was administering poison to him." "Oh, really? And who was he?" "We don't know yet. But the moment Dubey was told about it, he believed it. In fact, he told his family that his milkman wanted to poison him, and was probably poisoning him by giving him a daily supply of poisoned milk. He was daily taking one liter of milk from a milkman called Ramnath." "But why would Ramnath want to kill him?" "That is exactly the question, Dubey's parents asked him. We know this, because we have now interrogated Dubey's parents. Suman Dubey was unmarried as I have already told you. One day, Ramnath came to Dubey's house to deliver the milk along with his young and nubile sister Sita. Immediately Dubey fell in love with her. Once or twice, when she came alone to deliver the milk to Dubey, he even made attempts to make passes at her. Sita immediately complained about this matter to her brother, who came to his house to resolve the matter. There was a big fight between the two. The whole neighborhood knew about it. After this Ramnath stopped delivering milk to Dubey. This was quite expected. But then quite unexpectedly Ramnath again started delivering milk to Dubey. Dubey was initially quite surprised, but he agreed because in this way, at least he could be in touch with Sita." "Oh, I see" "But when the village doctor told Dubey that someone was trying to poison him, he immediately realized why Ramnath had started delivering the milk to him again. Probably Ramnath wanted to get even with him by killing him. He thought that the best way would be to kill Dubey was by giving him small quantities of poison through the daily supply of milk. So he resumed the milk supply to him." "Oh, it indeed appears to me that Ramnath killed him through slow poisoning. Is slow poisoning possible doctor?" "Oh yes. Arsenic is notorious for this. One could give this poison in very small amounts over a long period of time, and the victim would die of slow poisoning. There are several other poisons which could be used for slow poisoning. Dubey's parents have lodged a strong complaint against Ramnath, and the police has apprehended him. He however is asserting that he is innocent and that the police should release him immediately." "What is your opinion in this case doctor?" "Tarun, I am a scientist, and I believe in hard facts. I have done an autopsy on this man, and have come forward with some amazing findings..." "Like what?" "The thing that caught my attention immediately was that his liver was enlarged. I took some liver cells from there and looked them under the microscope. I was surprised to find that Suman Dubey was suffering from a form of liver cancer, known as hepatoma. This finding set me thinking and I did certain other tests. I measured his blood glucose, and I found that it was much less than what it should have been. In technical terms, he was suffering from hypoglycemia, which in plain and simple words means "low sugar in the blood". I also found a chemical known as alpha fetoprotein in his plasma..." "Doctor, these symptoms don't appear like that of a poison to me. It rather appears to me that he died of liver cancer. Where is the criminality involved?" "Tarun, he indeed died of liver cancer. But the problem with me is that a serious allegation has been made by Dubey's parents against Ramnath." "That's right. And now you can tell the police that Ramnath is not guilty. And you can tell them that he died of liver cancer." "Tarun, you may be surprised to know that hepatoma can be induced by a poison, especially if low quantities of it are administered to someone over a long period of time" "Really? That is most preposterous. I wouldn't believe it, if it were not coming from your mouth. Well, anyway what is that poison?" "Tarun that is a very rare poison. It is called Aflatoxin" "Aflatoxin? Never heard of that." "Really. In fact, it is one of the most talked about poisons today. Some people believe that this poison is being used by certain nations in biological warfare." "Come on doctor. It looks like we are again on to some interesting tales about poisons. Tell me about aflatoxins from the beginning" "Tarun, our story of Aflatoxin starts at the most unusual place- the church..." "The church? Come on doctor. How can the story of a poison start from such a holy place as a church?" "In churches, a device if often used for sprinkling holy water. It is swollen at one end, and this swollen end has several tiny holes in it, through which holy water can be sprinkled. This little device is called aspergillum, after the Latin word for sprinkling, which is aspergo." "I still can't make any head or tail of how this will lead us to such a deadly poison as Aflatoxin." "It so happens that there is a particular species of fungus, which under the microscope looks exactly like the aspergillum. Its strands have a tiny end and a swollen end. To many mycologists - scientists who study fungi - this appeared rather like the aspergillum used in churches, so they named it Aspergillus. Since this fungus was yellow in color, and the Latin word for yellow is flavus, they preferred to call this fungus Aspergillus flavus, which became its botanical name. In 1960, an epidemic of serious liver disease was traced to the eating of moldy peanuts. Incidentally it was nothing but Aspergillus flavus, which had affected the peanuts. It was later realized that this fungus released a poison which actually caused the serious liver disease. The toxicologists were looking for a name for this newly discovered poison, and they resorted to the botanical name of the fungus from which the poison was coming. They took the first letter from the name of the genus (i.e. "A") and the first three letters from the name of the species (i.e. "fla"). Together the four letters form the word "Afla". Since toxin is another name for poisons, they added this world to "Afla", and the name of the new poison became Aflatoxin." "Oh, that is most interesting. Doctor, you are incredible. You make things so interesting." "Tarun, Aflatoxins are powerful, tasteless, odorless and colorless mycotoxins that are chemical metabolites produced not only by Aspergillus flavus, but by certain other species of Aspergillus as well such as Aspergillus parasiticus. It is also produced by certain other fungi such as Penicillum and Rhizopus. These are all soil based fungi. Several varieties of aflatoxins are known, but the most dangerous is Aflatoxin B1, with Aflatoxin G1, coming a close second. In fact, Aflatoxin B1 is thought to be the most potent liver cancer producing chemical. Aflatoxins are mutagenic (i.e. they cause mutations), carcinogenic (i.e. they produce cancers), teratogenic (i.e. they cause deformities in the fetus, if pregnant mothers take them), and acutely toxic to most animals and humans. They can cause animals, including humans, to lose their appetites, decrease their feed efficiency and/or cause death. Aflatoxins inhibit the body's immune system and reduce the effects of vaccines. In the U.S., the aflatoxins are the only mycotoxins that are specifically regulated by the Food and Drug Administration or FDA." "Oh, I see" "Human exposure to aflatoxins may occur accidentally by the consumption of foods that have been contaminated by Aspergillus during growth, harvest or storage. Nearly all agricultural products are potentially subject to contamination with aflatoxins. Common sources include grains (e.g., corn, rice, sorghum), peanuts, oilseeds (e.g., cottonseed oil, copra), legumes (soybeans, other beans), and tree nuts (e.g., almonds, pecans, walnuts). The use of Aflatoxin-contaminated feed for domestic animals may result in secondary exposure to humans by the consumption of products such as meat, milk and cheese, and eggs that contain residues of the aflatoxins or their toxic metabolites. The FDA has established enforcement levels of 0.5 part per billion (ppb) in milk and 20 parts per billion for other food products. This means that in the United States, concentrations of up to 20 ppb are permitted in human foods and only upto 0.5 ppb in the milk. Levels of up to 200 ppb are permitted in animal feeds, although there is now a serious concern for secondary exposure to aflatoxins from the use of animal products. As I told you, Aflatoxin B1 is a potent hepatocarcinogen in experimental animals, but tumors may also occur in the colon and kidneys. In rats, tumors develop after the administration of 0.2 micrograms per day or a single dose of 0.5 mg of Aflatoxin B1; the tumor incidence is 50 per cent at 26 months after the latter treatment. There are marked differences in the susceptibility of various species to carcinogenesis by Aflatoxin B1; rats are much more susceptible than mice." "Oh, that is interesting." "Tarun, very high levels of aflatoxins occur in foods in certain regions of Africa and Asia, and people in these regions suffer a high incidence of liver cancer. Within Swaziland, Kenya, Uganda, and Thailand, where epidemiological studies have been conducted, in certain areas the climatic conditions (i.e., high temperatures and high humidity) are favorable for fungal growth; the food supply from these regions shows a relatively high Aflatoxin contamination, and the average Aflatoxin consumption exceeds 10 micrograms per kg of body weight per day. In other areas of the same countries where lower temperatures and lower humidity prevail, the food supply shows a relatively lower Aflatoxin contamination and the average human Aflatoxin consumption is less. In these areas, the incidence of liver cancer is also less. This is a fairly good evidence that aflatoxins are connected with liver cancers. Within each country, there is a direct relationship between the incidence of liver tumors (cases/100,000 people/year) and the average daily dietary intake of aflatoxins in contaminated agricultural products." "That is interesting. You were saying that aflatoxins are also used by certain nations for biological warfare" "Tarun, first of all you must know, what biological warfare is. It is the use of living organisms or their products by a nation for killing the people of its enemy nation. The earliest instance of biological warfare is provided by ancient Mayans, who used to throw deadly snakes in their enemy camps. Now the biological warfare is much more advanced and complicated. People are thinking of using aerosols of deadly bacteria and viruses to decimate their enemies. These aerosols can be released in the enemy territories in the same way that traditional bombs are dropped. On 17.10.96, Alan George of the London Observer reported some interesting facts about Iraq's weaponizing of Aflatoxin. According to him, in May 1988 Iraq began studies on Aflatoxin at its Al Salman facility where the toxin was produced by the growth of the fungus Aspergillus in 5.3-quart flasks. In 1989 Iraq moved its Aflatoxin production to a facility at Fudaliyah. In November, 1989, trials using Aflatoxin warheads (in 122 mm artillery rockets and R400 aerial bombs) were conducted. In 1990 between spring and December 1990, it produced 481 gallons of Aflatoxin in solution. Between May 1990 and August 1990, trials using Aflatoxin warheads were continued. In December 1990 large scale "weaponization" of biological agents started. In 1991 Iraq's Gulf War arsenal included sixteen R400 Aflatoxin bombs and two Aflatoxin warheads for enhanced Scud missiles. In total Iraq produced 572 gallons of concentrated Aflatoxin, of which 410.8 gallons were put into munitions. There is however no evidence that these Aflatoxin weapons were ever used. But under these circumstances, United Nations has continued its sanctions over Iraq." "That is most interesting. Coming to our original case, do you think, Ramnath was intelligent enough to mix aflatoxins in the milk, to cause liver cancer in Suman Dubey so he may die?" "I don't think so. Although there is a distinct possibility of someone doing so, if he were intelligent enough. Ramnath is an illiterate person, and I don't think, he even knows about aflatoxins. I think the rice that he was getting from his village was moldy, and he got his poisoning from that. In fact, I have examined the rice stores in Dubey's house and they are indeed moldy. I examined some of the rice grains under the microscope and I could indeed find Aspergillus in it. So that solves our case. Come, let us tell the police that Ramnath is innocent and that they should release him." "Very clever indeed. This was a most interesting discussion doctor. Without your masterly deduction, police could have unnecessarily went on harassing Ramnath. Suman Dubey's relatives and other people might have thought, it was a case of killing by Ramnath. Tell me what are you going to tell me the next time?" "Tarun, next time, I would tell you about a very interesting poison, nitric acid. "

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Forensic Toxicology THE FOLLOWING ARTICLE APPEARED IN THE JUNE 2000 ISSUE THE POISON SLEUTHS DEATH BY FLUORINE -Dr. Anil Aggrawal "Good morning doctor. Oh, my God, what are you doing today? You have the dead body of a young man today. What happened to him? Please tell me.” “Good morning Tarun. The name of this person is Ramlal and he was 26 years old. He was found dead in his room today morning. When the milkman came to deliver the milk in the morning today, Ramlal did not open the door, and he got suspicious. This was especially because Kalu, his neighbor had threatened to kill him several times.” “Who is Kalu doctor, and why did he want to kill Ramlal?” “Tarun, Kalu is a 35 year old person, who lives in the neighborhood. Kalu thought that Ramlal used to meet his wife furtively, although all the other neighbors sincerely believed that this was not the case. Many times, they even told Kalu that he was mistaken, but he did not believe anyone. Many a time, Kalu has even threatened to kill Ramlal, if he did not stop meeting his wife. Let me tell you that Kalu works in a chemical factory making all sorts of chemicals. He is a reasonably good chemist and knows a lot about various chemicals.” “So what happened when the milkman came?” “Yes, I was telling you about the events occurring in the morning today. When Ramlal did not open the door, milkman enquired from the neighbors if he had gone out for a few days, and he was informed that Ramlal was very much in town. In fact one person told, that he had seen Ramlal with Kalu only the previous night. As Ramlal always got up late, there was no question of his having got up early and going out for a walk or something. Everybody got suspicious. They called the police. When the door was forced open, everyone was stunned to see Ramlal lying dead on his cot. Everyone noticed a faint smell coming from the room, but they could not identify that smell. They said that they had never smelt anything like that.” “Perhaps Ramlal was not keeping his room tidy and hence the smell” “It was not that kind of smell. At least that is what has been informed to me by the neighbors.” “Doctor, how do you think Ramlal died?” “Tarun, this is a case which even defeated me for several hours. Since he was not admitted to a hospital, I did not have a hospital report to fall back upon. You might have noticed that many times, hospital records, such as initial symptoms etc give away the cause of death. If a poison has been administered to the individual, we can immediately know about that poison from the symptoms encountered. But in this case, there was no hospital report, and I had to rely solely on my postmortem findings. To make matters worse, there were no significant postmortem findings. The only findings which deserve mention are a reddening of his eyes, and of the mucus membranes of his respiratory tract, such as those of nose and windpipe. His lungs were very much congested with blood. His stomach showed lot of alcohol. It appears he had been drinking alcohol before his death.” “Perhaps he died by consuming too much liquor?” “I have done his blood alcohol levels. A blood alcohol level of around 600 mg% is necessary to kill a human being. But in his case, the blood level was just about 150 mg%, enough to produce a mild sensation of well-being, but not death. We enquired the neighbor - a person called Shamu - who claims having seem him with Kalu the day before. Shamu told that Kalu came to Ramlal’s house at about 9 pm the previous night. He had a big bag in his hand. Shamu knew it because at that time he was just returning to his house from his evening walk. When Shamu asked what he was doing there, initially Kalu looked nonplussed but very soon, he regained his composure. He told that that he wanted to bury the hatchet with Ramlal, and was going to his house to have a friendship drink. He even opened the bag and showed him a bottle of Rum which he had with him.” “Then how are you going to find out how he died?” “Tarun. I had just three abnormal and suspicious looking pieces in the whole story. One that Kalu his neighbor who was his enemy, showed a suspicious behavior the previous night, and two that Kalu works in a chemical factory. Add to this the third factor that the neighbors noticed some strange smell coming out from the house when they opened the door, and my mind immediately turned towards some poisonous gas as the possible killing agent. Still I was in the dark because there are so many gases which can kill a person. I had no way but to perform a chemical test on his lungs, and guess what I found - fluorine! Ramlal has died because of fluorine” “Come on doctor. We have never heard of a person dying from fluorine. He must have died some other way.” “Tarun, I am very sure Ramlal died of fluorine. In fact the circumstances which Kalu created were perfect for a killing with fluorine. He first made Ramlal tipsy with alcohol and then released fluorine which he had brought with him in his bag. He had this gas in a pressurized container, which the police has seized from a half opened almirah. Of course they would never have looked for it, had I not told them about it. I went to Ramlal’s house and did some tests on the air in his room. Although much of the fluorine had diffused out of Ramlal’s room, yet I could demonstrate a significant amount of fluorine in his room.” “Doctor, it appears we are on to some other good of your stories. Please tell me something about fluorine first, so I can follow you better.” “Tarun, fluorine (F), is the most reactive chemical element, and the lightest member of the halogen elements, or Group VIIa of the periodic table. Its atomic number is 9, atomic weight 18.9984, melting point -219.62° C (-363.32° F), boiling point -188° C (-306° F), and density at 1 atm, and 0° C about 1.696 g/litre. Under ordinary conditions fluorine is a gas a little heavier than air, with a pale yellow colour; inhalation except in very low concentrations is dangerous. Upon cooling, fluorine becomes a yellow liquid. Fluorine occurs combined in the widely distributed mineral fluorite ( calcium fluoride, fluorspar), its chief source, in the minerals cryolite and fluorapatite, and in small amounts in seawater, bones, and teeth. Not a rare element, it makes up about 0.065 percent of the Earth's crust. Only one isotope occurs in nature, stable fluorine-19. Let me tell you that Fluorine is difficult to isolate from its compounds, and in fact it is impossible to free it by chemical means. No other element is powerful enough, as an oxidizing agent, to replace it.” “Doctor since when do we know about fluorine?” “Tarun, the French chemist Henri Moissan first isolated fluorine in 1886 by electrolysis of anhydrous hydrogen fluoride (HF), in which potassium hydrogen fluoride (KHF2) had been dissolved to make it conduct a current. Elemental fluorine of high purity is prepared commercially by Moissan's procedure. The elemental gas is used as an oxidizer in rocket fuels and to prepare fluorides. Fluorine, composed of two-atom molecules (F2), is so reactive that it combines with all other elements except helium, neon, and argon to form ionic or covalent fluorides. Its chemical activity can be attributed to its extreme ability to attract electrons (in fact, it is the most electronegative element) and to the small size of its atoms. The oxidation state of -1 is the only one observed in fluorine compounds. Because of the small size of the fluoride ion (F-), it forms many stable complexes with positive ions; for example, hexafluorosilicate(IV) (SiF62-) and hexafluoroaluminate(III) (AlF63-). One of the principal industrial compounds of fluorine is hydrogen fluoride, obtained by treating fluorite with sulfuric acid. It is employed in the preparation of numerous inorganic and organic fluorine compounds of commercial importance, e.g., sodium aluminum fluoride (Na3AlF6), used as an electrolyte in the electrolytic smelting of aluminum metal; and uranium hexafluoride (UF6), utilized in the gaseous diffusion process of separating uranium-235 from uranium-238 for reactor fuel. A solution of hydrogen fluoride gas in water is called hydrofluoric acid, large quantities of which are consumed in industry for cleaning metals and for polishing, frosting, and etching glass. Boron trifluoride (BF3) and antimony trifluoride (SbF3), like hydrogen fluoride, are important catalysts for organic reactions; cobalt trifluoride (CoF3) and chlorine trifluoride (ClF3) are useful fluorinating agents; and sulfur hexafluoride (SF6) is used as a gaseous electrical insulator. Sodium fluoride (NaF) is used to treat dental caries and is often added in small amounts to fluoride-deficient water supplies (fluoridation) to reduce tooth decay. Elemental fluorine, often diluted with nitrogen, reacts with hydrocarbons to form corresponding fluorocarbons in which some or all hydrogen has been replaced by fluorine. The resulting compounds are usually characterized by great stability, chemical inertness, high electrical resistance, and other valuable physical and chemical properties. This fluorination may be accomplished also by treating organic compounds with cobaltic fluoride or by electrolyzing their solutions in anhydrous hydrogen fluoride. Useful plastics with non-sticking qualities, such as polytetrafluoroethylene ([CF2CF2)x]; known by the commercial name Teflon), are readily made from unsaturated fluorocarbons. Organic compounds containing chlorine, bromine, or iodine are fluorinated to produce compounds such as dichlorodifluoromethane (Cl2CF2), the coolant used in most household refrigerators and air conditioners." “Doctor, what is the color of this gas? And how does it smell?” “Fluorine is a yellow gas that does not occur free in nature because of its great reactivity. Before World War II it was generated only in gram quantities, but the need for stable fluorocarbons in the atomic energy program stimulated the chemical industry to devise electrolyte cells for the preparation of elemental fluorine. The present availability of the compressed gas in nickel or steel cylinders has led to its use for the preparation of a host of new organic fluorine compounds, many of them of commercial value. The gas can be liquefied at low temperatures. Its odor differs from that of chlorine. It is rather difficult to describe, but it can be compared to that of relatively concentrated ozone. It can be piped through standard steel pipe or copper tubing equipped with Monel metal…” “Sorry to disturb you doctor, but what is Monel metal?” “Tarun, fluorine is a very reactive gas, and thus it can only be piped through certain very resistant metals. Monel is any of a group of nickel-copper alloys, first developed in 1905, containing about 66 percent nickel and 31.5 percent copper, with small amounts of iron, manganese, carbon, and silicon. Stronger than pure nickel, Monel alloys are resistant to corrosion by many agents, including fluorine and rapidly flowing seawater, both of which can be very very corrosive to metals. They can be fabricated readily by hot- and cold-working, machining, and welding. Monel is a registered trademark of the International Nickel Company. So I was telling you, how the gas can be piped. Well, it can be piped also through nickel valves with Teflon packing. With metals, fluorine reacts only slowly, except at sufficiently elevated temperatures. Under suitable conditions, it reacts spontaneously with most materials at room temperature except the inert gases, metal fluorides in their highest valence states, and carbon tetrachloride. Under some conditions, fluorine at atmospheric pressure can burn even steel equipment. For reasons unknown, fluorine does not always react with water, but at times the reaction may occur explosively. With the moisture of the air, it forms hydrogen fluoride and, possibly, oxygen fluoride, OF2." “Doctor, how does fluorine kill a person? Have scientists done some studies on how fluorine kills a man?” “Tarun, the only studies of the effects of exposure of animals to metered dilutions of fluorine in nitrogen were those made at the University of Rochester by a team led by Stokinger in 1949. They did a number of experiments on various animals, and let me tell you what they found. The gas was uniformly fatal to rabbits, guinea pigs, rats, and mice in exposures ranging from 5 minutes at a concentration of 10,000 parts per million (p.p.m.) to 3 hours at 200 p.p.m. Guinea pigs survived an exposure of 7 hours to 100 p.p.m., but the over-all mortality among the various species was 60 per cent. Respiratory damage, with swelling of the lungs - technically called pulmonary edema-, was the cause of death. More prolonged exposure, up to 35 days, was made to lesser concentrations. Irritation of the eyes and nasal and mouth mucosal lining was noted at concentrations of 5 to 10 p.p.m., and dogs exhibited irrational seizures, many of which were fatal. Moderate to severe lung irritation occurred at all levels down to 3 mg./cu. meter, and rats showed also a high degree of destruction of their testes at 25-mg. level. The tolerated exposure was taken as 1 p.p.m. (1.7 mg./cu. meter),and hydrogen fluoride and fluorine were regarded as independently toxic. The Rochester group also exposed the skin of the back of anesthetised rabbits for periods of 0.2 to 0.6 sec. at a distance of 1 in. to fluorine under 40 lb. pressure. The briefest exposure led to the appearance of a small area devoid of blood about 1/4 inch in diameter, surrounded by an reddened area. This became a superficial eschar that sloughed off by the fourth day, disclosing normal epidermis. The longer exposures were accompanied by a flash of flame, burning the hair and causing a special type of destruction - technically known as coagulation necrosis - of the burned area and charring of the epidermis. The thermal flash burns resembled those induced by an oxyacetylene flame.” “Sounds like a really dangerous gas. Doctor, you told me that Kalu worked in a factory from where he might have smuggled a canister of fluorine. Surely if Kalu works in a factory, he himself might be exposed to it. Has the government set up any regulations regarding it?” “No, to the best of my knowledge, there are no governmental regulations on the allowable concentrations of fluorine. But the American Conference of Governmental Industrial Hygienists (1961) has recommended 0.1 p.p.m. as the threshold limit for fluorine. Apparently if the concentration increases beyond it, there is danger to one’s health.” “Doctor, now I know reasonably enough about fluorine. Please tell me how Kalu killed Ramlal with Fluorine” “Tarun, it was a very devilish plan. Kalu stole a canister of fluorine from where he was working. He was working in a chemical factory, and it was not difficult for him to do that. He knew about the killing potential of fluorine as he had studied chemistry upto college level and was reasonably conversant with all the chemicals, and their effects on the human body. He knew that if he released the gas in Ramlal’s house he would recognize the smell and would throw open the doors and windows of his house. So he decided to first lull his senses. For this purpose he came to Ramlal’s house along with a bottle of liquor. Did you notice that Shamu told us he had a big bag with him, and from it he took out a bottle of liquor to show him. I am sure that the canister of fluorine was also in the very same bag, but he did not take it out to show to Shamu. At Ramlal’s house, he said that he wanted friendship. Ramlal was also tired of day-to-day bickerings and he readily agreed for a drink. After two or three pegs, when Ramlal was quite tipsy, Kalu got up on the pretext of going to the bathroom. He furtively opened a nearby almirah, put the canister inside it, and slightly unscrewed its cap, so the gas could leak slowly into the room. After this he went to the bathroom. When he came back, he found Ramlal lying lazily in his bed, with his eyes closed. Kalu took leave of him, and came back to his house. Ramlal closed the door behind him, and came back to his bed to sleep. By this time, enough gas had not come out of the canister to arouse Ramlal’s suspicions. Anyway, Ramlal was drunk, and he was not in a position to recognize the special odor of fluorine. Soon he fell asleep. The concentration of fluorine increased in the house, and killed him in his sleep. Ramu did one mistake in his whole episode. He left the canister in the almirah. He never thought that our investigation can be so thorough. Anyway, this was the only way, he could ensure a gradual build-up of the gas in Ramlal’s house. Come, let us tell the police that Kalu has killed Ramlal, and that he should be caught” “That is very clever of you doctor. Without your clever deduction it would have been impossible to say how Ramlal died and Kalu may have gone scot-free. What are you going to tell me next time?” “Tarun, next time, I would tell you about a very interesting poison - Potassium Bromate."

Forensic Toxicology Anil Aggrawal's Science Reporter's Articles on Forensic Toxicology Hi, I am Professor Anil Aggrawal from India. I am working as a Professor of Forensic Medicine at the Maulana Azad Medical College, New Delhi-110002, India. I love to exchange ideas on Forensic Medicine, Forensic Pathology and Forensic Toxicology. I love writing books on science, and have published nine books so far. I love reading and writing science fiction, especially that related to forensic medicine. Anyone wishing to exchange ideas with me on forensic medicine, science, and science fiction is welcome. I have been writing popular articles on Forensic Medicine, Forensic Pathology and Forensic Toxicology in some of the most popular magazines and periodicals in India. I love talking to young intelligent students on matters of forensic science. One of my most memorable experiences was when I talked on "Forensic Engineering" to a group of highly intelligent students at IIT, Bombay in February 2002. The students were fantastic; I thoroughly enjoyed being with them and talking to them on this confluence of the two specialties. The students appeared to enjoy my slides and animations too. S cience Reporter is a monthly science magazine, which gives articles of scientific interest on a variety of subjects. This magazine was started in post independent India in 1952 and is published uninterrupted since then. It is published by the National Institute of Science Communication, New Delhi. The full address of the magazine is: THE EDITOR SCIENCE REPORTER National Institute of Science Communication (CSIR) Dr. K.S. Krishnan Marg New Delhi-110 012 INDIA F rom January 1997, I started a new series, POISON SLEUTHS which appeared as a monthly column from January 1997 till April 2001. It proved highly popular among lay people and scientists alike. It was in the form of a dialogue between an intelligent and curious 15 year old, and an expert forensic pathologist. IMPORTANT NOTE: THIS MATERIAL IS COPYRIGHTED BY THE AUTHOR AND MAY NOT BE REPOSTED, REPRINTED OR OTHERWISE USED IN ANY MANNER WITHOUT THE WRITTEN PERMISSION OF THE AUTHOR Anil Aggrawal's Science Reporter's 1997 Articles on Forensic Toxicology Poisons, antidotes & anecdotes (January 1997) Arsenic: The king of Poisons (February 1997) The myth of the Spanish Fly (March 1997) Boron Poisoning (April 1997) Silver Poisoning (June 1997) Vanadium Poisoning (July 1997) Methyl Bromide Poisoning (August 1997) Poisoning by Ratti Seeds (September 1997) Poisoning by Thallium (October 1997) Poisoning by Capsaicin (November 1997) Death by Lysol (December 1997) Anil Aggrawal's Science Reporter's 1998 Articles on Forensic Toxicology Death by Phosgene (January 1998) Death by SMFA (February 1998) Common Salt (March 1998) Iodine (April 1998) Barium (May 1998) Selenium (June 1998) Death by DNOC (July 1998) Death by Cadmium (August 1998) Death by Aluminium Phosphide (October 1998) Argemone mexicana (November 1998) Death by Sodium chlorate (December 1998) Death by Argemone Oil Anil Aggrawal's Science Reporter's 1999 Articles on Forensic Toxicology Death by Sodium Nitrite (January 1999) Death by Potassium Permanganate (February 1999) Death by Diesel fumes (March 1999) Death by Arsine gas (April 1999) Death by Alfatoxin (May 1999) Death by Nitric Acid (June 1999) Death by Oxalic Acid (July 1999) Death by Digitalis (August 1999) Death by Yellow Kaner (September 1999) Death by Vitamin A (October 1999) Death by Cicutoxin (November 1999) Death by Brodifacoum (December 1999) Anil Aggrawal's Science Reporter's 2000 Articles on Forensic Toxicology Death by Succinylcholine (January 2000) Death by Gold (February 2000) Death by Radon (March 2000) Death by Hydrogen Peroxide (April 2000) Death by Hydrogen Fluoride (May 2000) Death by Fluorine (June 2000) Potassium Bromate (July 2000) Ethylene Glycol (August 2000) Botulinum Toxin (September 2000) General quiz on Forensic Toxicology Arsenic: The king of poisons Silver Death BY SMFA Death by Cadmium Death by Aflatoxins Death by Arsine gas Death by Nitric Acid Picture quiz on Forensic Toxicology Death by Digitalis Death by Oxalic Acid Quiz Index: Anil Aggrawal's Forensic Toxicology Page Arsenic: The king of poisons Methyl bromide Death by DNOC

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Forensic Toxicology THE FOLLOWING ARTICLE APPEARED IN THE JULY 2000 ISSUE THE POISON SLEUTHS DEATH BY POTASSIUM BROMATE -Dr. Anil Aggrawal "Good morning doctor. Oh, my God, what are you doing today? You have the dead body of a young child today. What happened to him? Please tell me.” “Good morning Tarun. The name of this young child is Nitya, and he is four years old. He was the only son of his parents. Till yesterday evening he was alright. He was playing in front of his house quite cheerfully. After sometime, he started vomiting and felt very restless. His parents noted that he vomited some blood too. They became very afraid, and took the child immediately to the doctors. The doctors took it to be a case of gastroenteritis and started treating him along those lines. However the child failed to show any improvement and died today morning. Now the police has brought his body to me. My job of course is to tell them, how Nitya has died.” “But surely Nitya has died due to some natural disease. We don’t really need a post-mortem in this case, do we?” “Tarun, the doctors at the hospital where he was being treated have refused to give any cause of death. They say, that they just did not have the time to diagnose his disease. For all we know this could very well be a case of poisoning too.” “Really? Have the parents of Nitya given some hint in this direction?” “Police has made some enquiries and have come up with some interesting results. Ramlal, the father of Nitya was not going along well with his neighbor Raghav. Both Ramlal and Raghav claimed a hundred square yard plot somewhere in Ghaziabad. A court case was also dragging on in this connection for quite sometime. Recently there had been indications that Ramlal would ultimately win the case. Raghav had become very restless after that. He had sworn several times before neighbors that he would teach a good lesson to Ramlal. It is quite probable that Raghav gave some kind of poison to Nitya to get even with Ramlal.” “What do you think Doctor?” “Tarun, the first thing I did was to ask the police what Raghav does. They told me that he works at a modern hair saloon called “Hairwaves”. Now “Hairwaves” is really a very modern and posh hair saloon offering all kinds of hair treatments to their customers. The moment I heard this, I immediately became attentive, because a chemical potassium bromate usually found at hair saloons usually produces the kind of symptoms Nitya showed. Come to think of it, I think Nitya in fact has been poisoned by Potassium Bromate.” “But doctor how can you be so sure?” “Potassium bromate seems the most likely candidate Tarun. Now let me tell you that in Japan, in the 1960s and 1970s there were about 20 cases of suicides by hair dressers. And do you know which chemical they used for self-poisoning? All of them used potassium bromate, because this is so easily available to hair dressers.” “Doctor, it looks like we are on to one of your great stories. Why don’t you tell me about potassium bromate from the beginning?” “Tarun, the chemical formula of potassium bromate is KBrO3. Both Potassium and sodium bromate (NaBrO3) have no medicinal use. They are used solely as flour bleaches and as “neutralizers” in cold wave hair permanent kits, which can contain either 2% potassium bromate or 10% sodium bromate.......” “Sorry to interrupt you doctor, but what are flour bleaches and how are they used?” “Tarun, flour that we get from wheat has to be “treated” with the use of “improvers”. These “improvers” are nothing but oxidizing substances which enhance the baking quality of flour, allowing production of better and larger loaves. Relatively small amounts of these “improvers” are required, generally a few parts per million. Similarly to reduce the yellowness of the flour, bleaching agents may also be required. Although such improvers and the bleaching agents used to rectify excessive yellowness in flour are permitted in most countries, the processes are not universal. Improvers include bromates, chlorine dioxide (in gaseous form), and azodicarbonamide. The most popular bleacher used is benzoyl peroxide. But in many places potassium bromate is still used.” “Oh, I see. You used another word ‘neutralizers’. What are these?” “Tarun, there was a time when making the hairs wavy had become a fashion. In the late 1940s and during whole of 50s, it was fashionable to make the hair wavy. To do this, the hair was first treated with a milky waving lotion, the active ingredient of which was ammonium thioglycollate. At the appropriate time its effects were arrested by applying a neutralizer, i.e. a solution of potassium bromate, prepared from a small packet of the crystals. Outfits for permanent waving of hair by a cold process in the home became available in the UK round about 1950 and a little earlier in the United States. In the US in the late 1940s and early 1950s, home kits for making hair wavy were easily available, resulting in several cases of bromate poisonings, primarily in children under the age of 4. As I told you earlier, in Japan several cases were reported where hair dressers had apparently taken potassium bromate as a suicidal agent.” “Oh, that is most interesting. So this chemical is so dangerous that it can kill too?” “Yeah, and what makes it still more dangerous is that it is colourless, odourless and tasteless too, thus making it a very good candidate as a homicidal poison. A substance which is colourless, odourless and tasteless can be very easily administered to a victim mixed in his food, without him knowing anything about it. For the same reason, it can be taken by mistake too, especially if left in a cup or milk bottle. Cases have been reported in medical literature about the death of children who have ingested hair neutralizer accidentally. Many toxicologists in fact have talked about the possible danger of the ‘home perm’ outfits.” “Doctor, what are the other circumstances in which potassium bromate may be ingested by a human being?” “The majority of cases of poisoning are of course the result of accidents. A case has been described in the medical literature of the accidental poisoning of four adults who drank coffee prepared with fluid which proved to be hair neutralizer placed in an empty milk bottle. Except that they had thought the coffee tasted salty they were unaware of its nature until, half an hour later, they were seized with abdominal cramps and vomiting and, at the end of an hour, abdominal pain of a griping nature and diarrhoea. Fortunately all four made a complete recovery at the end of 24 hours. Hair neutralizer was administered by a woman to members of her family, apparently to enable her to enjoy the company of another man. She put some in her husband’s tea, and in orange squash which she gave to her daughters. The husband had abdominal pain which was ascribed to dysentery contracted while absent on military service. When the others became ill, the doctor suspected poisoning. The woman was later convicted of administering poison with intent to injure and was sentenced to 18 months imprisonment.” “Oh, that is quite interesting. What are the symptoms after ingesting this poison?” “Tarun, this compound is absorbed almost unchanged in the gastrointestinal tract. A very slow reduction of bromate to bromide may occur in the body, which can minimally elevate bromide levels in the blood. Potassium bromate causes gastrointestinal irritation and kidney damage as its principal effects and there may be incidental damage to the liver. Unlike potassium chlorate, however, potassium bromate does not break RBCs, a process known as haemolysis. The gastrointestinal symptoms are non-specific. Within half an hour the patient has nausea and vomits and this may be accompanied by epigastric cramps. Vomiting is repeated and may continue for a few days. There may be blood in the vomit. Within about an hour there is abdominal colic and diarrhoea. Some toxicologists think that the stomach and intestinal complaints are due to the caustic hydrobromic acid produced when bromate reacts with gastric juice. I may tell you that in Potassium chlorate poisoning, a special compound is formed in the blood. This is known as methemoglobin, and is chocolate brown in color. This feature has not been detected in humans with bromate poisoning. Fall in blood pressure may or may not occur. Severe poisoning leads to damage of kidneys and in consequence there is decrease in the formation of urine, coming to a complete halt after some time. This causes a rise in the blood urea concentration. In some cases generalized seizures are seen. It has been estimated that the fatal dose of potassium bromate is about 240-500 mg/Kg. If 300 mg/Kg is taken as the average fatal dose, then about 18 g would be required to kill a 60 kg man. The weight of Nitya is about 14 kg. So only about 4-5 g of potassium bromate must have been needed in this case. If you look under the microscope you would find that the kidneys of Nitya are damaged. Technically this change is known as renal tubular necrosis. Similarly I am also finding damage to his liver and heart, both of which are seen in potassium bromate poisoning. I have also recovered potassium bromate from Nitya’s stomach and have chemically identified it. There seems little doubt now that he was poisoned. And Raghav is indeed the poisoner. It was only he who had access to this dangerous chemical. He must have been taught during the course of his profession that this is a dangerous chemical. He somehow was able to smuggle some amount of Potassium bromate from his work place to his home. When Nitya was playing in the evening, he must have approached him with some kind of drink, may be a sherbet, in which he must have mixed potassium bromate. He wanted to kill Nitya, which was his way of getting even with Ramlal. Come let us tell the police who the culprit is. They will search his house, and if any of the remaining chemical is found in his house, everything would become very clear.” “That is very clever of you doctor. Without your clever deduction it would have been impossible to say how Nitya died and Raghav may have gone scot-free. What are you going to tell me next time?” “Tarun, next time, I would tell you about a very interesting poison - Ethylene Glycol."

Forensic Toxicology THE FOLLOWING ARTICLE APPEARED IN THE JANUARY 1998 ISSUE THE POISON SLEUTHS DEATH BY PHOSGENE -Dr. Anil Aggrawal "Good morning doctor. Oh, my God, what are you doing today? You have the dead body of a young man today. His eyes look suffused. What happened to him? Please tell me." "Good morning Tarun. The name of this 36 year old man is Manhar. He is a welder by profession and was working for the last five years as a welder in Messers Arihant Welders Ltd. Welders as you know work with hot torches, and seal metallic objects. He used to weld metallic pipes in a small confined space in basement. Yesterday he was suffering from common cold, but he reached his workplace at 9 am as usual and started welding pipes in the basement. After sometime, a cup of tea and some snacks were sent to him by the management as he was having common cold. This was not a usual practice, but as he was ill and the management wanted quick work on that day, this sympathetic gesture was made. He took tea and snacks and got back to work. Soon he started feeling as if his throat was dry and burning. His eyes began itching, and there was a copious outflow of tears. He took it merely to be an aggravation of his common cold symptoms, and kept on working. Soon however he started coughing violently. Still he did not take things seriously. He took some water to soothe his throat and continued working. When the cough became unbearable, he came up and told about this experience to the manager on duty. He asked him to relax on a side chair. Soon thereafter he died." "Oh, sure enough this is a mysterious death. What do you think happened in this case?" "A few facts about Manhar would be in order before I proceed with this story. Manhar was a Union leader, and for the last three months was fighting with the management for better working conditions and salary. I have talked to the Union and its other leaders. They all hold Manhar in great respect. They have come out with a most outrageous suggestion, and in fact that is part of the reason, why his body is with me today." "What have they suggested doctor? Please let me know." "Well, the Union leaders think that the management has secretly poisoned Manhar. There is no secret of the fact that the management did want to sack Manhar, the moment he took up the cause of workers. But they couldn't do so, because the Union threatened to go on strike. Since then the Management was thinking of various ways and means of doing away with him. The Union leaders- as well as the family members -think that the management sent poisonous tea and snacks to Manhar on that fateful day. Manhar was naive enough to think that the Management was being friendly to him, and took the tea. The fact that Manhar started having symptoms of throat irritation, redness of eyes and coughing immediately thereafter has lent strength to their suspicion." "Well come to think of doctor, even I think that he might have been poisoned." "Tarun, I have made a habit of examining the scene of crime always before starting the autopsy. So before starting the autopsy on this case, I asked police to take me to the place where he was working. I was surprised to find that he was working in a really cramped place in the basement. The place had a rather musty odour. "Perhaps you are suggesting that he died of suffocation. But he was working there daily for the last five years, and nothing happened to him!" "Yes that's right. But I looked around and found some strange looking cans there. I enquired about these cans and was told by the Management staff, that they contained dry-cleaning fluid. They were soon going to expand into dry-cleaning business and for this purpose had bought dry-cleaning fluid and had stored the cans there. Some of the cans were lying open...." "Sorry to interrupt you doctor, but is this observation of any help in this murder investigation?" "Oh yes, surely it is. When you look at all the facts, you can pinpoint the probable cause of his death." "Sorry doctor. I can't make any head or tail of the facts you have just mentioned." "Tarun dry-cleaning fluid usually contain chlorinated solvents, such as carbon tetrachloride or tricholoroethylene. I investigated about the contents of that dry cleaning fluid and found out that it contained tricholoroethylene. It is a well known fact that welding in a poorly ventilated, confined space in the presence of chlorinated solvents can cause phosgene to form rapidly in lethal concentrations. After I found the dry cleaning cans there, and saw how cramped the place was, I immediately came to the conclusion that Manhar must have died of phosgene poisoning. There were some additional pointers to my hunch. In the first place the place had a musty odour much like the actual smell of phosgene...." "But Manhar never noticed the smell. If phosgene was forming, he must have noticed it." "Phosgene is not a particularly offensive smelling gas. Its odour has been described as musty, resembling that of fresh mown hay or green corn. Of course, in high concentrations phosgene is rather pungent and mildly irritating, but Manhar was having severe cold on that day and it is quite possible that he couldn't notice the smell because of his cold. In addition to the smell, the other things, that go in favor of phosgene poisoning are the peculiar symptoms that he displayed...." "Oh, well, I am getting the idea. You certainly are a clever doctor. But let us begin from the beginning. Tell me something about phosgene first, so I could follow you better" "Tarun, Phosgene is a colorless gas, about 3.43 times heavier than air. It liquefies at 80 C. Phosgene is an acidic chloride and its chemical formula is COCl2 . It is known by several other names. Some of these are Carbonic dichloride, carbonyl chloride, carbon oxychloride, and chloroformyl chloride. It has a musty odor resembling fresh mown hay or green corn as I have already told you. Because of these peculiar properties, and especially the fact that it is heavier than air, it was used extensively in gas warfare in World War I, and caused 80 per cent of the deaths by gas in that conflict. Fortunately, gas warfare was sparingly used in World War II, otherwise the casualties could have been much more. A curious fact is that smokers report a flat, metallic taste when smoking in the presence of phosgene. Phosgene does not occur naturally and was first synthesized by Sir Humphry Davy in 1812 by means of passing carbon monoxide and chlorine through charcoal. It was quite natural for a curious mind to do such an experiment, because these two were the most poisonous gases known at that time, and one would have thought, he could perhaps create a deadlier gas by mixing the two chemically. In a way, he succeeded too, because phosgene is in fact deadlier than both the other gases. According to most estimates, Carbon monoxide can prove fatal if inhaled in a concentration of 1000 ppm for sometime....." "Sorry to interrupt you doctor, but would you tell me the meaning of ppm?" "Sure, ppm is an abbreviation of parts per million. When we talk of the toxicity of gases, we usually talk in terms of ppm. If I mix 1 cc of a poisonous gas with ordinary air in such a way that the final volume of the mixture turns out to be 1 million cc, the concentration of the poisonous gas in that mixture would be referred to as 1 ppm. Of course you can understand that to make the final mixture to be 1 million cc, I would have to use 999,999 cc of ordinary air. Similarly if I mix 1000 cc of a poisonous gas with 999,000 cc of air, the resulting mixture would measure 1 million cc and the concentration of poisonous gas in that mixture would be 1000 ppm." "Oh, that is quite clear doctor. So you were telling me about the lethality of certain gases." "Yes, I told you about the lethality of Carbon monoxide. For chlorine the fatal concentration has been estimated to be somewhat lesser; about 400 ppm, but phosgene kills rapidly in as low concentration as 50 ppm. Its lethality is compounded by the fact, that it is not a particularly irritating gas, being only mildly irritating and that too in high concentrations. Because of this curious fact, the victim does not make any attempt to run away from the gas, as he would do if he were exposed to, say, chlorine. This is what happened in Manhar's case. In fact phosgene is such a dangerous gas that cylinders of phosgene are not normally supplied by the manufacturers unless they have satisfied themselves that the purchaser and his premises are satisfactory." "But why would anyone want to buy such a deadly gas doctor?" "Tarun, Phosgene is an important industrial chemical being used in the synthesis or manufacture of isocyanates, polyurethane, polycarbonate resins, aniline dyes, pharmaceuticals, plastics, and insecticides. It is also used in the "Uranium enrichment" process. Because of its wide use in industry, there is always a danger of workers getting dangerously exposed to it. Currently it is generally agreed that a Maximum Allowable Concentration (MAC) of phosgene should be 1.0 ppm of gas, which means that during a 10 hour continuous working period, there should be no more than 0.1 ppm of the gas in the environment (0.1 ppm x 10 hours = 1 ppm). Phosgene can form by burning of several compounds, most important of which is polyurethane. This is the chemical with which furniture upholsteries are made. In December, 1987, in Tampa, Florida, an individual was filling an air mattress with a hair dryer when the mattress exploded, burned and released phosgene into the apartment. This occurred because the mattress was made of polyurethane. This gas represents one of the many hazards to fire-fighting personnel and fire victims for similar reasons. Welding in a poorly ventilated, confined space in the presence of chlorinated solvents or other halides can cause phosgene to form rapidly in lethal concentrations as I have already told you. You would be surprised to know that phosgene was also implicated in the Bhopal tragedy that occurred in our country in December 1984..." "Yes, that certainly surprises me doctor. Because I was under the impression that the gas responsible for the tragedy was Methyl Isocyanate (MIC)." "Oh, sure it was. But that was just one of the main gases involved. MIC in turn is made from phosgene and methylamine and is used as an intermediate product in the manufacture of carbamate insecticide Carbaryl, or Sevin, the chemical which Union Carbide used to make. On that fateful day nearly 50,000 pounds of stored MIC was released in vapor and liquid forms over a period of 2 hours. Because of the hypothesized reactions that took place within the storage tank and in the surrounding atmosphere, it is thought that MIC, phosgene, and hydrogen cyanide all played a significant role in this disaster." "That's certainly a good addition to my knowledge doctor. Tell me doctor, how does phosgene kill?" "Tarun, phosgene damages the body in several ways. It slowly hydrolyzes in mucus membrane water to produce carbon dioxide and hydrochloric acid. Because this hydrolysis tends to occur slowly, phosgene is less irritating to the mucous membrane of the upper airway and eyes and therefore penetrates more deeply into the lungs. Formation of hydrochloric acid within the lungs causes damage to lung cells. This causes water to ooze out of the blood into the lungs. This in turn causes lungs to become water logged, a condition medically known as pulmonary edema. This is a very important and conspicuous finding in deaths due to phosgene. I have examined Manhar's lungs, and they are severely water logged. Hydrochloric acid can also cause red blood cells to break down, a process medically known as hemolysis. This usually occurs at high concentrations. There are other complex reactions too, which cause severe kidney and liver damage." "Doctor, earlier you said that Manhar's symptoms also led you to conclude phosgene poisoning. Can you tell me what are the symptoms experienced in phosgene poisoning." "Oh sure. In concentrations of 3 ppm, phosgene causes dryness and burning of the throat. At 4 ppm, it causes eye irritation, redness of eyes, and watering of eyes. At 5-10 ppm, it causes coughing. Exposure to 25 ppm for 30 minutes is very dangerous, and even brief exposures to 50 ppm or greater is rapidly fatal. You will remember that Manhar displayed roughly the same symptoms. 80% of mortalities occur within 48 hours of the initial exposure, which may be considered as its fatal period. There are no specific diagnostic tests for phosgene exposure. A detailed and meticulous history and crime scene examination is the only likey thing to help. And that certainly has helped me. Come let us tell the police that the management is innocent. They have not given any poison to Manhar. But certainly they were careless to keep those cans in the basement. The management may be charged for being careless, but certainly the charge of murder can not be proved." "Oh, how very clever of you doctor. This was a most interesting discussion. Tell me what are you going to tell me the next time?" "Tarun, next time, I would tell you about a very deadly poison- Sodium Monofluoroacetate, commonly known as SMFA."