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Coincidences In Hebrew, the name "Gernot Zippe" (גרנוט ציפה), the inventor of the Zippe-type centrifuge, is an anagram of the word "centrifuge" (צנטריפוגה). The anagrammer Anu Garg's name results in: "Anagram genius" = "Name is Anu Garg." Games and puzzles Anagrams are in themselves a recreational activity, but they also make up part of many other games, puzzles and game shows. The Jumble is a puzzle found in many newspapers in the United States requiring the unscrambling of letters to find the solution. Cryptic crossword puzzles frequently use anagrammatic clues, usually indicating that they are anagrams by the inclusion of a descriptive term like "confused" or "in disarray". An example would be Businessman burst into tears (9 letters). The solution, stationer, is an anagram of into tears, the letters of which have burst out of their original arrangement to form the name of a type of businessman.
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1361_11
Numerous other games and contests involve some element of anagram formation as a basic skill. Some examples: In Anagrams, players flip tiles over one at a time and race to take words. They can "steal" each other's words by rearranging the letters and extending the words. In a version of Scrabble called Clabbers, the name itself is an anagram of Scrabble. Tiles may be placed in any order on the board as long as they anagram to a valid word. On the British game show Countdown, contestants are given 30 seconds to make the longest word from nine random letters. In Boggle, players make constrained words from a grid of sixteen random letters, by joining adjacent cubes. On the British game show BrainTeaser, contestants are shown a word broken into randomly arranged segments and must announce the whole word. At the end of the game there is a "Pyramid" which starts with a three-letter word. A letter appears in the line below to which the player must add the existing letters to find a solution. The pattern continues until the player reaches the final eight-letter anagram. The player wins the game by solving all the anagrams within the allotted time. In Bananagrams, players place tiles from a pool into crossword-style word arrangements in a race to see who can finish the pool of tiles first. Ciphers Multiple anagramming is a technique used to solve some kinds of cryptograms, such as a permutation cipher, a transposition cipher, and the Jefferson disk. Solutions may be computationally found using a Jumble algorithm. Methods of construction Sometimes, it is possible to "see" anagrams in words, unaided by tools, though the more letters involved the more difficult this becomes. The difficulty is that for a word of different letters, there are (factorial of ) different permutations and so different anagrams of the word. Anagram dictionaries can also be used. Computer programs, known as "anagram search", "anagram servers", "anagram solvers", offer a much faster route to creating anagrams, and a large number of these programs are available on the Internet. Some programs use the Anatree algorithm to compute anagrams efficiently.
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1361_12
The program or server carries out an exhaustive search of a database of words, to produce a list containing every possible combination of words or phrases from the input word or phrase using a jumble algorithm. Some programs (such as Lexpert) restrict to one-word answers. Many anagram servers (for example, The Words Oracle) can control the search results, by excluding or including certain words, limiting the number or length of words in each anagram, or limiting the number of results. Anagram solvers are often banned from online anagram games. The disadvantage of computer anagram solvers, especially when applied to multi-word anagrams, is their poor understanding of the meaning of the words they are manipulating. They usually cannot filter out meaningful or appropriate anagrams from large numbers of nonsensical word combinations. Some servers attempt to improve on this using statistical techniques that try to combine only words that appear together often. This approach provides only limited success since it fails to recognize ironic and humorous combinations. Some anagrammatists indicate the method they used. Anagrams constructed without the aid of a computer are noted as having been done "manually" or "by hand"; those made by utilizing a computer may be noted "by machine" or "by computer", or may indicate the name of the computer program (using Anagram Genius). There are also a few "natural" instances: English words unconsciously created by switching letters around. The French chaise longue ("long chair") became the American "chaise lounge" by metathesis (transposition of letters and/or sounds). It has also been speculated that the English "curd" comes from the Latin crudus ("raw"). Similarly, the ancient English word for bird was "brid".
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1361_13
Prominent anagrammatists The French king Louis XIII had a man named Thomas Billon appointed as his Royal Anagrammatist with an annual salary of 1200 pounds. Among contemporary anagrammers, Anu Garg, created an Internet Anagram Server in 1994 together with the satirical anagram-based newspaper The Anagram Times. Mike Keith has anagrammed the complete text of Moby Dick. He, along with Richard Brodie, has published The Anagrammed Bible that includes anagrammed version of many books of the Bible. Popular television personality Dick Cavett is known for his anagrams of famous celebrities such as Alec Guinness and Spiro Agnew. Anagram animation An animated anagram displays the letters of a word or phrase moving into their new positions. See also Acronym Ambigram Anagrammatic poem Anagrams, a board game Ananym Blanagram Constrained writing Isogram Letter bank Lipogram List of geographic anagrams and ananyms List of taxa named by anagrams London Underground anagram map Palindrome Pangram Rebus Sator Square Spoonerism Tautonym Word play References Further reading Henry Benjamin Wheatley. Of Anagrams: A Monograph Treating of Their History from the Earliest Ages to the Present Time. Williams & Norgate, 1862. Word Ways: The Journal of Recreational Linguistics. Greenwood Periodicals et al., 1968–. . Howard W. Bergerson. Palindromes and Anagrams. Dover Publications, 1973. . External links
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1362_0
The Anadyr () is a river in the far northeast Siberia which flows into the Gulf of Anadyr of the Bering Sea and drains much of the interior of Chukotka Autonomous Okrug. Its basin corresponds to the Anadyrsky District of Chukotka. Geography The Anadyr is long and has a basin of . It is frozen from October to late May and has a maximum flow in June with the snowmelt. It is navigable in small boats for about to near Markovo. West of Markovo it is in the Anadyr Highlands (moderate mountains and valleys with a few trees) and east of Markovo it moves into the Anadyr Lowlands (very flat treeless tundra with lakes and bogs). The drop from Markovo to the sea is less than . It rises at about 67°N latitude and 171°E longitude in the Anadyr Highlands, near the headwaters of the Maly Anyuy, flows southwest receiving the waters of the rivers Yablon and Yeropol, turns east around the Shchuchy Range and passes Markvovo and the old site of Anadyrsk, turns north and east and receives the Mayn from the south, thereby encircling the Lebediny Zakaznik, turns northeast to receive the Belaya from the north in the Parapol-Belsky Lowlands, then past Ust-Belaya it turns southeast into the Anadyr Lowlands past the Ust-Tanyurer Zakaznik and receives the Tanyurer from the north. At Lake Krasnoye, it turns east and flows into the Onemen Bay of the Anadyr Estuary. If the Onemen Bay is considered part of the river, it also receives the Velikaya from the south and the Kanchalan from the north. Other important tributaries are the Yablon, Yeropol and Mamolina from the right and the Chineyveyem and Ubiyenka from the left. Its basin is surrounded by the Amguema and Palyavaam basins to the north, the Bolshoy Anyuy, Oloy and Kolyma basins to the northwest, and the Penzhina basin to the southwest.
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1362_1
History In 1648, Semyon Dezhnev reached the mouth of the Anadyr after being shipwrecked on the coast. In 1649, he went upriver and built winter quarters at Anadyrsk. For the next 100 years the Anadyr was the main route from the Arctic to the Pacific and Kamchatka. In the 18th century, the Anadyr was described by the polar explorer Dmitry Laptev. Ecology The country through which it passes is thinly populated, and is dominated by tundra, with a rich variety of plant life. Much of the region has beautiful landscapes, dominated by often spectacular, rugged mountains. For nine months of the year the ground is covered with snow, and the frozen rivers become navigable roads. George Kennan, an American working on the Western Union Telegraph Expedition in the late 1860s, found that dog sled travel on the lower Anadyr was limited by lack of firewood. Reindeer, upon which the local inhabitants subsisted, were once found in considerable numbers, but the domestic reindeer population has collapsed dramatically since the reorganization and privatization of state-run collective farms beginning in 1992. As herds of domestic reindeer have declined, herds of wild caribou have increased. There are ten species of salmon inhabiting the Anadyr river basin. Every year, on the last Sunday in April, there is an ice fishing competition in the frozen estuarine waters of the Anadyr's mouth. This festival is locally known as Korfest. The area is a summering place for a number of migratory birds including brent geese, Eurasian wigeons, and the pintails of California. See also Operation Anadyr Notes References External links "Tourist and environmental information" Chukotka Autonomous Okrug website, in English "Russia Far East: Anadyr River" Wild Salmon Center Anadyr River Watershed "Snezhnoye: a village on the Anadyr' River" Rivers of Chukotka Autonomous Okrug Drainage basins of the Bering Sea
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André-Marie Ampère (, ; ; 20 January 177510 June 1836) was a French physicist, mathematician and lay catholic who was one of the founders of the science of classical electromagnetism, which he referred to as "electrodynamics". He is also the inventor of numerous applications, such as the solenoid (a term coined by him) and the electrical telegraph. As an autodidact, Ampère was a member of the French Academy of Sciences and professor at the École polytechnique and the Collège de France. The SI unit of measurement of electric current, the ampere, is named after him. His name is also one of the 72 names inscribed on the Eiffel Tower. Early life André-Marie Ampère was born on 20 January 1775 to Jean-Jacques Ampère, a prosperous businessman, and Jeanne Antoinette Desutières-Sarcey Ampère, during the height of the French Enlightenment. He spent his childhood and adolescence at the family property at Poleymieux-au-Mont-d'Or near Lyon. Jean-Jacques Ampère, a successful merchant, was an admirer of the philosophy of Jean-Jacques Rousseau, whose theories of education (as outlined in his treatise Émile) were the basis of Ampère's education. Rousseau believed that young boys should avoid formal schooling and pursue instead an "education direct from nature." Ampère's father actualized this ideal by allowing his son to educate himself within the walls of his well-stocked library. French Enlightenment masterpieces such as Georges-Louis Leclerc, comte de Buffon's Histoire naturelle, générale et particulière (begun in 1749) and Denis Diderot and Jean le Rond d'Alembert's Encyclopédie (volumes added between 1751 and 1772) thus became Ampère's schoolmasters. The young Ampère, however, soon resumed his Latin lessons, which enabled him to master the works of Leonhard Euler and Daniel Bernoulli.
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1363_1
French Revolution In addition, Ampère used his access to the latest books to begin teaching himself advanced mathematics at age 12. In later life Ampère claimed that he knew as much about mathematics and science when he was eighteen as ever he knew, but as a polymath, his reading embraced history, travels, poetry, philosophy, and the natural sciences. His mother was a devout Catholic, so Ampère was also initiated into the Catholic faith along with Enlightenment science. The French Revolution (1789–99) that began during his youth was also influential: Ampère's father was called into public service by the new revolutionary government, becoming a justice of the peace in a small town near Lyon. When the Jacobin faction seized control of the Revolutionary government in 1792, his father Jean-Jacques Ampère resisted the new political tides, and he was guillotined on 24 November 1793, as part of the Jacobin purges of the period. In 1796, Ampère, met Julie Carron, and in 1799 they were married. Ampère took his first regular job in 1799 as a mathematics teacher, which gave him the financial security to marry Carron and father his first child, Jean-Jacques (named after his father), the next year. (Jean-Jacques Ampère eventually achieved his own fame as a scholar of languages.) Ampère's maturation corresponded with the transition to the Napoleonic regime in France, and the young father and teacher found new opportunities for success within the technocratic structures favoured by the new French First Consul. In 1802, Ampère was appointed a professor of physics and chemistry at the École Centrale in Bourg-en-Bresse, leaving his ailing wife and infant son Jean-Jacques Antoine Ampère in Lyon. He used his time in Bourg to research mathematics, producing Considérations sur la théorie mathématique de jeu (1802; "Considerations on the Mathematical Theory of Games"), a treatise on mathematical probability that he sent to the Paris Academy of Sciences in 1803. Teaching career
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1363_2
Teaching career After the death of his wife in July 1803, Ampère moved to Paris, where he began a tutoring post at the new École Polytechnique in 1804. Despite his lack of formal qualifications, Ampère was appointed a professor of mathematics at the school in 1809. As well as holding positions at this school until 1828, in 1819 and 1820 Ampère offered courses in philosophy and astronomy, respectively, at the University of Paris, and in 1824 he was elected to the prestigious chair in experimental physics at the Collège de France. In 1814, Ampère was invited to join the class of mathematicians in the new Institut Impérial, the umbrella under which the reformed state Academy of Sciences would sit. Ampère engaged in a diverse array of scientific inquiries during the years leading up to his election to the academy—writing papers and engaging in topics from mathematics and philosophy to chemistry and astronomy, which was customary among the leading scientific intellectuals of the day. Ampère claimed that "at eighteen years he found three culminating points in his life, his First Communion, the reading of Antoine Leonard Thomas's "Eulogy of Descartes", and the Taking of the Bastille. On the day of his wife's death he wrote two verses from the Psalms, and the prayer, 'O Lord, God of Mercy, unite me in Heaven with those whom you have permitted me to love on earth.' In times of duress he would take refuge in the reading of the Bible and the Fathers of the Church." For a time he took into his family the young student Frédéric Ozanam (1813–1853), one of the founders of the Conference of Charity, later known as the Society of Saint Vincent de Paul. Through Ampère, Ozanam had contact with leaders of the neo-Catholic movement, such as François-René de Chateaubriand, Jean-Baptiste Henri Lacordaire, and Charles Forbes René de Montalembert. Ozanam was beatified by Pope John Paul II in 1998. Work in electromagnetism
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1363_3
Work in electromagnetism In September 1820, Ampère's friend and eventual eulogist François Arago showed the members of the French Academy of Sciences the surprising discovery of Danish physicist Hans Christian Ørsted that a magnetic needle is deflected by an adjacent electric current. Ampère began developing a mathematical and physical theory to understand the relationship between electricity and magnetism. Furthering Ørsted's experimental work, Ampère showed that two parallel wires carrying electric currents attract or repel each other, depending on whether the currents flow in the same or opposite directions, respectively - this laid the foundation of electrodynamics. He also applied mathematics in generalizing physical laws from these experimental results. The most important of these was the principle that came to be called Ampère's law, which states that the mutual action of two lengths of current-carrying wire is proportional to their lengths and to the intensities of their currents. Ampère also applied this same principle to magnetism, showing the harmony between his law and French physicist Charles Augustin de Coulomb's law of electric action. Ampère's devotion to, and skill with, experimental techniques anchored his science within the emerging fields of experimental physics. Ampère also provided a physical understanding of the electromagnetic relationship, theorizing the existence of an "electrodynamic molecule" (the forerunner of the idea of the electron) that served as the component element of both electricity and magnetism. Using this physical explanation of electromagnetic motion, Ampère developed a physical account of electromagnetic phenomena that was both empirically demonstrable and mathematically predictive. In 1827, Ampère published his magnum opus, Mémoire sur la théorie mathématique des phénomènes électrodynamiques uniquement déduite de l’experience (Memoir on the Mathematical Theory of Electrodynamic Phenomena, Uniquely Deduced from Experience), the work that coined the name of his new science, electrodynamics, and became known ever after as its founding treatise. In 1827, Ampère was elected a Foreign Member of the Royal Society and in 1828, a foreign member of the Royal Swedish Academy of Science. Probably the highest recognition came from James Clerk Maxwell, who in his "Treatise on Electricity and Magnetism", named Ampère “the Newton of electricity”. Honours 8.10.1825: Member of the Royal Academy of Science, Letters and Fine Arts of Belgium.
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1363_4
Legacy In recognition of his contribution to the creation of modern electrical science, an international convention, signed at the 1881 International Exposition of Electricity, established the ampere as a standard unit of electrical measurement, along with the coulomb, volt, ohm, watt and farad, which are named, respectively, after Ampère's contemporaries Charles-Augustin de Coulomb of France, Alessandro Volta of Italy, Georg Ohm of Germany, James Watt of Scotland and Michael Faraday of England. Ampère's name is one of the 72 names inscribed on the Eiffel Tower. Several items are named after Ampère; many streets and squares, schools, a Lyon metro station, a graphics processing unit microarchitecture, a mountain on the moon and an electric ferry in Norway. Writings Considérations sur la théorie mathématique du jeu, Perisse, Lyon Paris 1802, online lesen im Internet-Archiv Partial translations: Magie, W.M. (1963). A Source Book in Physics. Harvard: Cambridge MA. pp. 446–460. . Complete translations: References Further reading (EPUB) External links Ampère and the history of electricity – a French-language, edited by CNRS, site with Ampère's correspondence (full text and critical edition with links to manuscripts pictures, more than 1000 letters), an Ampère bibliography, experiments, and 3D simulations Ampère Museum – a French-language site from the museum in Poleymieux-au-Mont-d'or, near Lyon, France "Société des Amis d'André-Marie Ampère", a French society dedicated to maintain the memory of André-Marie Ampère and in charge of the Ampère Museum. Catholic Encyclopedia on André Marie Ampère Electrical units history. 1775 births 1836 deaths Scientists from Lyon Electrostatics 19th-century French physicists People associated with electricity Independent scientists French Roman Catholics Collège de France faculty Foreign Members of the Royal Society Fellows of the Royal Society of Edinburgh Members of the French Academy of Sciences Members of the Royal Academy of Belgium Members of the Royal Swedish Academy of Sciences Honorary members of the Saint Petersburg Academy of Sciences Burials at Montmartre Cemetery Magneticians
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1365_0
Ammonia is a compound of nitrogen and hydrogen with the formula NH3. A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. It is a common nitrogenous waste, particularly among aquatic organisms, and it contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to 45 percent of the world's food and fertilizers. Ammonia, either directly or indirectly, is also a building block for the synthesis of many pharmaceutical products and is used in many commercial cleaning products. It is mainly collected by downward displacement of both air and water. Although common in natureboth terrestrially and in the outer planets of the Solar Systemand in wide use, ammonia is both caustic and hazardous in its concentrated form. In many countries it is classified as an extremely hazardous substance, and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities. The global industrial production of ammonia in 2018 was 175 million tonnes, with no significant change relative to the 2013 global industrial production of 175 million tonnes. Industrial ammonia is sold either as ammonia liquor (usually 28% ammonia in water) or as pressurized or refrigerated anhydrous liquid ammonia transported in tank cars or cylinders. NH3 boils at at a pressure of one atmosphere, so the liquid must be stored under pressure or at low temperature. Household ammonia or ammonium hydroxide is a solution of NH3 in water. The concentration of such solutions is measured in units of the Baumé scale (density), with 26 degrees Baumé (about 30% (by weight) ammonia at ) being the typical high-concentration commercial product. Etymology Pliny, in Book XXXI of his Natural History, refers to a salt produced in the Roman province of Cyrenaica named hammoniacum, so called because of its proximity to the nearby Temple of Jupiter Amun (Greek Ἄμμων Ammon). However, the description Pliny gives of the salt does not conform to the properties of ammonium chloride. According to Herbert Hoover's commentary in his English translation of Georgius Agricola's De re metallica, it is likely to have been common sea salt. In any case, that salt ultimately gave ammonia and ammonium compounds their name.
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1365_1
Natural occurrence Ammonia is a chemical found in trace quantities in nature, being produced from nitrogenous animal and vegetable matter. Ammonia and ammonium salts are also found in small quantities in rainwater, whereas ammonium chloride (sal ammoniac), and ammonium sulfate are found in volcanic districts; crystals of ammonium bicarbonate have been found in Patagonia guano. The kidneys secrete ammonia to neutralize excess acid. Ammonium salts are found distributed through fertile soil and in seawater. Ammonia is also found throughout the Solar System on Mars, Jupiter, Saturn, Uranus, Neptune, and Pluto, among other places: on smaller, icy bodies such as Pluto, ammonia can act as a geologically important antifreeze, as a mixture of water and ammonia can have a melting point as low as if the ammonia concentration is high enough and thus allow such bodies to retain internal oceans and active geology at a far lower temperature than would be possible with water alone. Substances containing ammonia, or those that are similar to it, are called ammoniacal. Properties Ammonia is a colourless gas with a characteristically pungent smell. It is lighter than air, its density being 0.589 times that of air. It is easily liquefied due to the strong hydrogen bonding between molecules; the liquid boils at , and freezes to white crystals at .
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1365_2
Solid The crystal symmetry is cubic, Pearson symbol cP16, space group P213 No.198, lattice constant 0.5125 nm. Liquid Liquid ammonia possesses strong ionising powers reflecting its high ε of 22. Liquid ammonia has a very high standard enthalpy change of vaporization (23.35 kJ/mol, cf. water 40.65 kJ/mol, methane 8.19 kJ/mol, phosphine 14.6 kJ/mol) and can therefore be used in laboratories in uninsulated vessels without additional refrigeration. See liquid ammonia as a solvent. Solvent properties Ammonia readily dissolves in water. In an aqueous solution, it can be expelled by boiling. The aqueous solution of ammonia is basic. The maximum concentration of ammonia in water (a saturated solution) has a density of 0.880 g/cm3 and is often known as '.880 ammonia'. Combustion Ammonia does not burn readily or sustain combustion, except under narrow fuel-to-air mixtures of 15–25% air. When mixed with oxygen, it burns with a pale yellowish-green flame. Ignition occurs when chlorine is passed into ammonia, forming nitrogen and hydrogen chloride; if chlorine is present in excess, then the highly explosive nitrogen trichloride (NCl3) is also formed. Decomposition At high temperature and in the presence of a suitable catalyst, ammonia is decomposed into its constituent elements. Decomposition of ammonia is a slightly endothermic process requiring 23 kJ/mol (5.5 kcal/mol) of ammonia, and yields hydrogen and nitrogen gas. Ammonia can also be used as a source of hydrogen for acid fuel cells if the unreacted ammonia can be removed. Ruthenium and platinum catalysts were found to be the most active, whereas supported Ni catalysts were the less active.
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1365_3
Structure The ammonia molecule has a trigonal pyramidal shape as predicted by the valence shell electron pair repulsion theory (VSEPR theory) with an experimentally determined bond angle of 106.7°. The central nitrogen atom has five outer electrons with an additional electron from each hydrogen atom. This gives a total of eight electrons, or four electron pairs that are arranged tetrahedrally. Three of these electron pairs are used as bond pairs, which leaves one lone pair of electrons. The lone pair repels more strongly than bond pairs, therefore the bond angle is not 109.5°, as expected for a regular tetrahedral arrangement, but 106.8°. This shape gives the molecule a dipole moment and makes it polar. The molecule's polarity, and especially, its ability to form hydrogen bonds, makes ammonia highly miscible with water. The lone pair makes ammonia a base, a proton acceptor. Ammonia is moderately basic; a 1.0 M aqueous solution has a pH of 11.6, and if a strong acid is added to such a solution until the solution is neutral (pH = 7), 99.4% of the ammonia molecules are protonated. Temperature and salinity also affect the proportion of NH4+. The latter has the shape of a regular tetrahedron and is isoelectronic with methane. The ammonia molecule readily undergoes nitrogen inversion at room temperature; a useful analogy is an umbrella turning itself inside out in a strong wind. The energy barrier to this inversion is 24.7 kJ/mol, and the resonance frequency is 23.79 GHz, corresponding to microwave radiation of a wavelength of 1.260 cm. The absorption at this frequency was the first microwave spectrum to be observed and was used in the first maser. Amphotericity One of the most characteristic properties of ammonia is its basicity. Ammonia is considered to be a weak base. It combines with acids to form salts; thus with hydrochloric acid it forms ammonium chloride (sal ammoniac); with nitric acid, ammonium nitrate, etc. Perfectly dry ammonia gas will not combine with perfectly dry hydrogen chloride gas; moisture is necessary to bring about the reaction.
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1365_4
As a demonstration experiment under air with ambient moisture, opened bottles of concentrated ammonia and hydrochloric acid solutions produce a cloud of ammonium chloride, which seems to appear "out of nothing" as the salt aerosol forms where the two diffusing clouds of reagents meet between the two bottles. NH3 + HCl → NH4Cl The salts produced by the action of ammonia on acids are known as the ammonium salts and all contain the ammonium ion (NH4+). Although ammonia is well known as a weak base, it can also act as an extremely weak acid. It is a protic substance and is capable of formation of amides (which contain the NH2− ion). For example, lithium dissolves in liquid ammonia to give a blue solution (solvated electron) of lithium amide: 2 Li + 2 NH3 → 2 LiNH2 + H2 Self-dissociation Like water, liquid ammonia undergoes molecular autoionisation to form its acid and base conjugates: 2 + Ammonia often functions as a weak base, so it has some buffering ability. Shifts in pH will cause more or fewer ammonium cations () and amide anions () to be present in solution. At standard pressure and temperature, K = [] × [] = 10. Combustion The combustion of ammonia to form nitrogen and water is exothermic: 4 NH3 + 3 O2 → 2 N2 + 6 H2O (g) ΔH°r = −1267.20 kJ (or −316.8 kJ/mol if expressed per mol of NH3) The standard enthalpy change of combustion, ΔH°c, expressed per mole of ammonia and with condensation of the water formed, is −382.81 kJ/mol. Dinitrogen is the thermodynamic product of combustion: all nitrogen oxides are unstable with respect to N2 and O2, which is the principle behind the catalytic converter. Nitrogen oxides can be formed as kinetic products in the presence of appropriate catalysts, a reaction of great industrial importance in the production of nitric acid: 4 NH3 + 5 O2 → 4 NO + 6 H2O
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1365_5
A subsequent reaction leads to NO2: 2 NO + O2 → 2 NO2 The combustion of ammonia in air is very difficult in the absence of a catalyst (such as platinum gauze or warm chromium(III) oxide), due to the relatively low heat of combustion, a lower laminar burning velocity, high auto-ignition temperature, high heat of vaporization, and a narrow flammability range. However, recent studies have shown that efficient and stable combustion of ammonia can be achieved using swirl combustors, thereby rekindling research interest in ammonia as a fuel for thermal power production. The flammable range of ammonia in dry air is 15.15–27.35% and in 100% relative humidity air is 15.95–26.55%. For studying the kinetics of ammonia combustion, knowledge of a detailed reliable reaction mechanism is required, but this has been challenging to obtain. Formation of other compounds In organic chemistry, ammonia can act as a nucleophile in substitution reactions. Amines can be formed by the reaction of ammonia with alkyl halides, although the resulting −NH2 group is also nucleophilic and secondary and tertiary amines are often formed as byproducts. An excess of ammonia helps minimise multiple substitution and neutralises the hydrogen halide formed. Methylamine is prepared commercially by the reaction of ammonia with chloromethane, and the reaction of ammonia with 2-bromopropanoic acid has been used to prepare racemic alanine in 70% yield. Ethanolamine is prepared by a ring-opening reaction with ethylene oxide: the reaction is sometimes allowed to go further to produce diethanolamine and triethanolamine. Amides can be prepared by the reaction of ammonia with carboxylic acid derivatives. Acyl chlorides are the most reactive, but the ammonia must be present in at least a twofold excess to neutralise the hydrogen chloride formed. Esters and anhydrides also react with ammonia to form amides. Ammonium salts of carboxylic acids can be dehydrated to amides so long as there are no thermally sensitive groups present: temperatures of 150–200 °C are required.
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1365_6
The hydrogen in ammonia is susceptible to replacement by a myriad of substituents. When dry ammonia gas is heated with metallic sodium it converts to sodamide, NaNH2. With chlorine, monochloramine is formed. Pentavalent ammonia is known as λ5-amine or, more commonly, ammonium hydride. This crystalline solid is only stable under high pressure and decomposes back into trivalent ammonia and hydrogen gas at normal conditions. This substance was once investigated as a possible solid rocket fuel in 1966. Ammonia as a ligand Ammonia can act as a ligand in transition metal complexes. It is a pure σ-donor, in the middle of the spectrochemical series, and shows intermediate hard–soft behaviour (see also ECW model). Its relative donor strength toward a series of acids, versus other Lewis bases, can be illustrated by C-B plots. For historical reasons, ammonia is named ammine in the nomenclature of coordination compounds. Some notable ammine complexes include tetraamminediaquacopper(II) ([Cu(NH3)4(H2O)2]2+), a dark blue complex formed by adding ammonia to a solution of copper(II) salts. Tetraamminediaquacopper(II) hydroxide is known as Schweizer's reagent, and has the remarkable ability to dissolve cellulose. Diamminesilver(I) ([Ag(NH3)2]+) is the active species in Tollens' reagent. Formation of this complex can also help to distinguish between precipitates of the different silver halides: silver chloride (AgCl) is soluble in dilute (2 M) ammonia solution, silver bromide (AgBr) is only soluble in concentrated ammonia solution, whereas silver iodide (AgI) is insoluble in aqueous ammonia.
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1365_7
Ammine complexes of chromium(III) were known in the late 19th century, and formed the basis of Alfred Werner's revolutionary theory on the structure of coordination compounds. Werner noted only two isomers (fac- and mer-) of the complex [CrCl3(NH3)3] could be formed, and concluded the ligands must be arranged around the metal ion at the vertices of an octahedron. This proposal has since been confirmed by X-ray crystallography. An ammine ligand bound to a metal ion is markedly more acidic than a free ammonia molecule, although deprotonation in aqueous solution is still rare. One example is the Calomel reaction, where the resulting amidomercury(II) compound is highly insoluble. HgCl2 + 2 NH3 → HgCl(NH2) + NH4Cl Ammonia forms 1:1 adducts with a variety of Lewis acids such as I2, phenol, and Al(CH3)3. Ammonia is a hard base (HSAB theory) and its E & C parameters are EB = 2.31 and C B = 2.04. Its relative donor strength toward a series of acids, versus other Lewis bases, can be illustrated by C-B plots. Detection and determination Ammonia in solution Ammonia and ammonium salts can be readily detected, in very minute traces, by the addition of Nessler's solution, which gives a distinct yellow colouration in the presence of the slightest trace of ammonia or ammonium salts. The amount of ammonia in ammonium salts can be estimated quantitatively by distillation of the salts with sodium or potassium hydroxide, the ammonia evolved being absorbed in a known volume of standard sulfuric acid and the excess of acid then determined volumetrically; or the ammonia may be absorbed in hydrochloric acid and the ammonium chloride so formed precipitated as ammonium hexachloroplatinate, (NH4)2PtCl6.
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1365_8
Gaseous ammonia Sulfur sticks are burnt to detect small leaks in industrial ammonia refrigeration systems. Larger quantities can be detected by warming the salts with a caustic alkali or with quicklime, when the characteristic smell of ammonia will be at once apparent. Ammonia is an irritant and irritation increases with concentration; the permissible exposure limit is 25 ppm, and lethal above 500 ppm. Higher concentrations are hardly detected by conventional detectors, the type of detector is chosen according to the sensitivity required (e.g. semiconductor, catalytic, electrochemical). Holographic sensors have been proposed for detecting concentrations up to 12.5% in volume. Ammoniacal nitrogen (NH3-N) Ammoniacal nitrogen (NH3-N) is a measure commonly used for testing the quantity of ammonium ions, derived naturally from ammonia, and returned to ammonia via organic processes, in water or waste liquids. It is a measure used mainly for quantifying values in waste treatment and water purification systems, as well as a measure of the health of natural and man-made water reserves. It is measured in units of mg/L (milligram per litre). History The ancient Greek historian Herodotus mentioned that there were outcrops of salt in an area of Libya that was inhabited by a people called the "Ammonians" (now: the Siwa oasis in northwestern Egypt, where salt lakes still exist). The Greek geographer Strabo also mentioned the salt from this region. However, the ancient authors Dioscorides, Apicius, Arrian, Synesius, and Aëtius of Amida described this salt as forming clear crystals that could be used for cooking and that were essentially rock salt. Hammoniacus sal appears in the writings of Pliny, although it is not known whether the term is identical with the more modern sal ammoniac (ammonium chloride). The fermentation of urine by bacteria produces a solution of ammonia; hence fermented urine was used in Classical Antiquity to wash cloth and clothing, to remove hair from hides in preparation for tanning, to serve as a mordant in dying cloth, and to remove rust from iron.
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1365_9
In the form of sal ammoniac (نشادر, nushadir), ammonia was important to the Muslim alchemists as early as the 8th century, first mentioned by the Persian-Arab chemist Jābir ibn Hayyān, and to the European alchemists since the 13th century, being mentioned by Albertus Magnus. It was also used by dyers in the Middle Ages in the form of fermented urine to alter the colour of vegetable dyes. In the 15th century, Basilius Valentinus showed that ammonia could be obtained by the action of alkalis on sal ammoniac. At a later period, when sal ammoniac was obtained by distilling the hooves and horns of oxen and neutralizing the resulting carbonate with hydrochloric acid, the name "spirit of hartshorn" was applied to ammonia. Gaseous ammonia was first isolated by Joseph Black in 1756 by reacting sal ammoniac (ammonium chloride) with calcined magnesia (magnesium oxide). It was isolated again by Peter Woulfe in 1767, by Carl Wilhelm Scheele in 1770 and by Joseph Priestley in 1773 and was termed by him "alkaline air". Eleven years later in 1785, Claude Louis Berthollet ascertained its composition. The Haber–Bosch process to produce ammonia from the nitrogen in the air was developed by Fritz Haber and Carl Bosch in 1909 and patented in 1910. It was first used on an industrial scale in Germany during World War I, following the allied blockade that cut off the supply of nitrates from Chile. The ammonia was used to produce explosives to sustain war efforts. Before the availability of natural gas, hydrogen as a precursor to ammonia production was produced via the electrolysis of water or using the chloralkali process. With the advent of the steel industry in the 20th century, ammonia became a byproduct of the production of coking coal. Applications Solvent
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1365_10
Applications Solvent Liquid ammonia is the best-known and most widely studied nonaqueous ionising solvent. Its most conspicuous property is its ability to dissolve alkali metals to form highly coloured, electrically conductive solutions containing solvated electrons. Apart from these remarkable solutions, much of the chemistry in liquid ammonia can be classified by analogy with related reactions in aqueous solutions. Comparison of the physical properties of NH3 with those of water shows NH3 has the lower melting point, boiling point, density, viscosity, dielectric constant and electrical conductivity; this is due at least in part to the weaker hydrogen bonding in NH3 and because such bonding cannot form cross-linked networks, since each NH3 molecule has only one lone pair of electrons compared with two for each H2O moleculeGive. The ionic self-dissociation constant of liquid NH3 at −50 °C is about 10−33. Solubility of salts Liquid ammonia is an ionising solvent, although less so than water, and dissolves a range of ionic compounds, including many nitrates, nitrites, cyanides, thiocyanates, metal cyclopentadienyl complexes and metal bis(trimethylsilyl)amides. Most ammonium salts are soluble and act as acids in liquid ammonia solutions. The solubility of halide salts increases from fluoride to iodide. A saturated solution of ammonium nitrate (Divers' solution, named after Edward Divers) contains 0.83 mol solute per mole of ammonia and has a vapour pressure of less than 1 bar even at . Solutions of metals Liquid ammonia will dissolve all of the alkali metals and other electropositive metals such as Ca, Sr, Ba, Eu, and Yb (also Mg using an electrolytic process). At low concentrations (<0.06 mol/L), deep blue solutions are formed: these contain metal cations and solvated electrons, free electrons that are surrounded by a cage of ammonia molecules. These solutions are very useful as strong reducing agents. At higher concentrations, the solutions are metallic in appearance and in electrical conductivity. At low temperatures, the two types of solution can coexist as immiscible phases. Redox properties of liquid ammonia
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1365_11
Redox properties of liquid ammonia The range of thermodynamic stability of liquid ammonia solutions is very narrow, as the potential for oxidation to dinitrogen, E° (N2 + 6NH4+ + 6e− ⇌ 8NH3), is only +0.04 V. In practice, both oxidation to dinitrogen and reduction to dihydrogen are slow. This is particularly true of reducing solutions: the solutions of the alkali metals mentioned above are stable for several days, slowly decomposing to the metal amide and dihydrogen. Most studies involving liquid ammonia solutions are done in reducing conditions; although oxidation of liquid ammonia is usually slow, there is still a risk of explosion, particularly if transition metal ions are present as possible catalysts. Fertilizer In the US as of 2019, approximately 88% of ammonia was used as fertilizers either as its salts, solutions or anhydrously. When applied to soil, it helps provide increased yields of crops such as maize and wheat. 30% of agricultural nitrogen applied in the US is in the form of anhydrous ammonia and worldwide 110 million tonnes are applied each year. Precursor to nitrogenous compounds Ammonia is directly or indirectly the precursor to most nitrogen-containing compounds. Virtually all synthetic nitrogen compounds are derived from ammonia. An important derivative is nitric acid. This key material is generated via the Ostwald process by oxidation of ammonia with air over a platinum catalyst at , ≈9 atm. Nitric oxide is an intermediate in this conversion: NH3 + 2 O2 → HNO3 + H2O Nitric acid is used for the production of fertilizers, explosives, and many organonitrogen compounds. Ammonia is also used to make the following compounds: Hydrazine, in the Olin Raschig process and the peroxide process Hydrogen cyanide, in the BMA process and the Andrussow process Hydroxylamine and ammonium carbonate, in the Raschig process Phenol, in the Raschig–Hooker process Urea, in the Bosch–Meiser urea process and in Wöhler synthesis Amino acids, using Strecker amino-acid synthesis Acrylonitrile, in the Sohio process
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1365_12
Ammonia can also be used to make compounds in reactions which are not specifically named. Examples of such compounds include: ammonium perchlorate, ammonium nitrate, formamide, dinitrogen tetroxide, alprazolam, ethanolamine, ethyl carbamate, hexamethylenetetramine, and ammonium bicarbonate. Cleansing agent Household "ammonia" (also incorrectly called ammonium hydroxide) is a solution of NH3 in water, and is used as a general purpose cleaner for many surfaces. Because ammonia results in a relatively streak-free shine, one of its most common uses is to clean glass, porcelain and stainless steel. It is also frequently used for cleaning ovens and soaking items to loosen baked-on grime. Household ammonia ranges in concentration by weight from 5 to 10% ammonia. United States manufacturers of cleaning products are required to provide the product's material safety data sheet which lists the concentration used. Solutions of ammonia (5–10% by weight) are used as household cleaners, particularly for glass. These solutions are irritating to the eyes and mucous membranes (respiratory and digestive tracts), and to a lesser extent the skin. Experts advise that caution be used to ensure the substance is not mixed into any liquid containing bleach, due to the danger of toxic gas. Mixing with chlorine-containing products or strong oxidants, such as household bleach, can generate chloramines. Experts also warn not to use ammonia-based cleaners (such as glass or window cleaners) on car touchscreens, due to the risk of damage to the screen's anti-glare and anti-fingerprint coatings. Fermentation Solutions of ammonia ranging from 16% to 25% are used in the fermentation industry as a source of nitrogen for microorganisms and to adjust pH during fermentation.
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1365_13
Antimicrobial agent for food products As early as in 1895, it was known that ammonia was "strongly antiseptic ... it requires 1.4 grams per litre to preserve beef tea (broth)." In one study, anhydrous ammonia destroyed 99.999% of zoonotic bacteria in 3 types of animal feed, but not silage. Anhydrous ammonia is currently used commercially to reduce or eliminate microbial contamination of beef. Lean finely textured beef (popularly known as "pink slime") in the beef industry is made from fatty beef trimmings (c. 50–70% fat) by removing the fat using heat and centrifugation, then treating it with ammonia to kill E. coli. The process was deemed effective and safe by the US Department of Agriculture based on a study that found that the treatment reduces E. coli to undetectable levels. There have been safety concerns about the process as well as consumer complaints about the taste and smell of ammonia-treated beef. Other Fuel The raw energy density of liquid ammonia is 11.5 MJ/L, which is about a third that of diesel. There is the opportunity to convert ammonia back to hydrogen, where it can be used to power hydrogen fuel cells, or it may be used directly within high-temperature solid oxide direct ammonia fuel cells to provide efficient power sources that do not emit greenhouse gases. The conversion of ammonia to hydrogen via the sodium amide process, either for combustion or as fuel for a proton exchange membrane fuel cell, is possible. Another method is the catalytic decomposition of ammonia using solid catalysts. Conversion to hydrogen would allow the storage of hydrogen at nearly 18 wt% compared to ≈5% for gaseous hydrogen under pressure. Ammonia engines or ammonia motors, using ammonia as a working fluid, have been proposed and occasionally used. The principle is similar to that used in a fireless locomotive, but with ammonia as the working fluid, instead of steam or compressed air. Ammonia engines were used experimentally in the 19th century by Goldsworthy Gurney in the UK and the St. Charles Avenue Streetcar line in New Orleans in the 1870s and 1880s, and during World War II ammonia was used to power buses in Belgium. Ammonia is sometimes proposed as a practical alternative to fossil fuel for internal combustion engines.
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1365_14
Its high octane rating of 120 and low flame temperature allows the use of high compression ratios without a penalty of high NOx production. Since ammonia contains no carbon, its combustion cannot produce carbon dioxide, carbon monoxide, hydrocarbons, or soot. Ammonia production currently creates 1.8% of global emissions. "Green ammonia" is ammonia produced by using green hydrogen (hydrogen produced by electrolysis), whereas "blue ammonia" is ammonia produced using blue hydrogen (hydrogen produced by steam methane reforming where the carbon dioxide has been captured and stored). However, ammonia cannot be easily used in existing Otto cycle engines because of its very narrow flammability range, and there are also other barriers to widespread automobile usage. In terms of raw ammonia supplies, plants would have to be built to increase production levels, requiring significant capital and energy sources. Although it is the second most produced chemical (after sulfuric acid), the scale of ammonia production is a small fraction of world petroleum usage. It could be manufactured from renewable energy sources, as well as coal or nuclear power. The 60 MW Rjukan dam in Telemark, Norway, produced ammonia for many years from 1913, providing fertilizer for much of Europe. Despite this, several tests have been run. In 1981, a Canadian company converted a 1981 Chevrolet Impala to operate using ammonia as fuel. In 2007, a University of Michigan pickup powered by ammonia drove from Detroit to San Francisco as part of a demonstration, requiring only one fill-up in Wyoming. Compared to hydrogen as a fuel, ammonia is much more energy efficient, and could be produced, stored, and delivered at a much lower cost than hydrogen, which must be kept compressed or as a cryogenic liquid. Rocket engines have also been fueled by ammonia. The Reaction Motors XLR99 rocket engine that powered the hypersonic research aircraft used liquid ammonia. Although not as powerful as other fuels, it left no soot in the reusable rocket engine, and its density approximately matches the density of the oxidizer, liquid oxygen, which simplified the aircraft's design.
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1365_15
In early August 2018, scientists from Australia's Commonwealth Scientific and Industrial Research Organisation (CSIRO) announced the success of developing a process to release hydrogen from ammonia and harvest that at ultra-high purity as a fuel for cars. This uses a special membrane. Two demonstration fuel cell vehicles have the technology, a Hyundai Nexo and Toyota Mirai. In 2020, Saudi Arabia shipped forty metric tons of liquid "blue ammonia" to Japan for use as a fuel. It was produced as a by-product by petrochemical industries, and can be burned without giving off greenhouse gases. Its energy density by volume is nearly double that of liquid hydrogen. If the process of creating it can be scaled up via purely renewable resources, producing green ammonia, it could make a major difference in avoiding climate change. The company ACWA Power and the city of Neom have announced the construction of a green hydrogen and ammonia plant in 2020. Green ammonia is considered as a potential fuel for future container ships. In 2020, the companies DSME and MAN Energy Solutions announced the construction of an ammonia-based ship, DSME plans to commercialize it by 2025. Japan is targeting to bring forward a plan to develop ammonia co-firing technology that can increase the use of ammonia in power generation, as part of efforts to assist domestic and other Asian utilities to accelerate their transition to carbon neutrality. In October 2021, the first International Conference on Fuel Ammonia (ICFA2021) was held. Remediation of gaseous emissions Ammonia is used to scrub SO2 from the burning of fossil fuels, and the resulting product is converted to ammonium sulfate for use as fertilizer. Ammonia neutralises the nitrogen oxide (NOx) pollutants emitted by diesel engines. This technology, called SCR (selective catalytic reduction), relies on a vanadia-based catalyst. Ammonia may be used to mitigate gaseous spills of phosgene. As a hydrogen carrier Due to its attributes, being liquid at ambient temperature under its own vapour pressure and having high volumetric and gravimetric energy density, ammonia is considered a suitable carrier for hydrogen, and may be cheaper than direct transport of liquid hydrogen.
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1365_16
Refrigeration – R717 Because of ammonia's vaporization properties, it is a useful refrigerant. It was commonly used before the popularisation of chlorofluorocarbons (Freons). Anhydrous ammonia is widely used in industrial refrigeration applications and hockey rinks because of its high energy efficiency and low cost. It suffers from the disadvantage of toxicity, and requiring corrosion resistant components, which restricts its domestic and small-scale use. Along with its use in modern vapor-compression refrigeration it is used in a mixture along with hydrogen and water in absorption refrigerators. The Kalina cycle, which is of growing importance to geothermal power plants, depends on the wide boiling range of the ammonia–water mixture. Ammonia coolant is also used in the S1 radiator aboard the International Space Station in two loops which are used to regulate the internal temperature and enable temperature dependent experiments. The potential importance of ammonia as a refrigerant has increased with the discovery that vented CFCs and HFCs are extremely potent and stable greenhouse gases. Stimulant Ammonia, as the vapor released by smelling salts, has found significant use as a respiratory stimulant. Ammonia is commonly used in the illegal manufacture of methamphetamine through a Birch reduction. The Birch method of making methamphetamine is dangerous because the alkali metal and liquid ammonia are both extremely reactive, and the temperature of liquid ammonia makes it susceptible to explosive boiling when reactants are added. Textile Liquid ammonia is used for treatment of cotton materials, giving properties like mercerisation, using alkalis. In particular, it is used for prewashing of wool. Lifting gas At standard temperature and pressure, ammonia is less dense than atmosphere and has approximately 45–48% of the lifting power of hydrogen or helium. Ammonia has sometimes been used to fill balloons as a lifting gas. Because of its relatively high boiling point (compared to helium and hydrogen), ammonia could potentially be refrigerated and liquefied aboard an airship to reduce lift and add ballast (and returned to a gas to add lift and reduce ballast). Fuming
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1365_17
Fuming Ammonia has been used to darken quartersawn white oak in Arts & Crafts and Mission-style furniture. Ammonia fumes react with the natural tannins in the wood and cause it to change colours. Safety The U.S. Occupational Safety and Health Administration (OSHA) has set a 15-minute exposure limit for gaseous ammonia of 35 ppm by volume in the environmental air and an 8-hour exposure limit of 25 ppm by volume. The National Institute for Occupational Safety and Health (NIOSH) recently reduced the IDLH (Immediately Dangerous to Life and Health, the level to which a healthy worker can be exposed for 30 minutes without suffering irreversible health effects) from 500 to 300 based on recent more conservative interpretations of original research in 1943. Other organizations have varying exposure levels. U.S. Navy Standards [U.S. Bureau of Ships 1962] maximum allowable concentrations (MACs): continuous exposure (60 days): 25 ppm / 1 hour: 400 ppm. Ammonia vapour has a sharp, irritating, pungent odour that acts as a warning of potentially dangerous exposure. The average odour threshold is 5 ppm, well below any danger or damage. Exposure to very high concentrations of gaseous ammonia can result in lung damage and death. Ammonia is regulated in the United States as a non-flammable gas, but it meets the definition of a material that is toxic by inhalation and requires a hazardous safety permit when transported in quantities greater than 13,248 L (3,500 gallons). Liquid ammonia is dangerous because it is hygroscopic and because it can cause caustic burns. See for more information. Toxicity The toxicity of ammonia solutions does not usually cause problems for humans and other mammals, as a specific mechanism exists to prevent its build-up in the bloodstream. Ammonia is converted to carbamoyl phosphate by the enzyme carbamoyl phosphate synthetase, and then enters the urea cycle to be either incorporated into amino acids or excreted in the urine. Fish and amphibians lack this mechanism, as they can usually eliminate ammonia from their bodies by direct excretion. Ammonia even at dilute concentrations is highly toxic to aquatic animals, and for this reason it is classified as dangerous for the environment. Atmospheric ammonia plays a key role in the formation of fine particulate matter.
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1365_18
Ammonia is a constituent of tobacco smoke. Coking wastewater Ammonia is present in coking wastewater streams, as a liquid by-product of the production of coke from coal. In some cases, the ammonia is discharged to the marine environment where it acts as a pollutant. The Whyalla steelworks in South Australia is one example of a coke-producing facility which discharges ammonia into marine waters. Aquaculture Ammonia toxicity is believed to be a cause of otherwise unexplained losses in fish hatcheries. Excess ammonia may accumulate and cause alteration of metabolism or increases in the body pH of the exposed organism. Tolerance varies among fish species. At lower concentrations, around 0.05 mg/L, un-ionised ammonia is harmful to fish species and can result in poor growth and feed conversion rates, reduced fecundity and fertility and increase stress and susceptibility to bacterial infections and diseases. Exposed to excess ammonia, fish may suffer loss of equilibrium, hyper-excitability, increased respiratory activity and oxygen uptake and increased heart rate. At concentrations exceeding 2.0 mg/L, ammonia causes gill and tissue damage, extreme lethargy, convulsions, coma, and death. Experiments have shown that the lethal concentration for a variety of fish species ranges from 0.2 to 2.0 mg/l. During winter, when reduced feeds are administered to aquaculture stock, ammonia levels can be higher. Lower ambient temperatures reduce the rate of algal photosynthesis so less ammonia is removed by any algae present. Within an aquaculture environment, especially at large scale, there is no fast-acting remedy to elevated ammonia levels. Prevention rather than correction is recommended to reduce harm to farmed fish and in open water systems, the surrounding environment. Storage information Similar to propane, anhydrous ammonia boils below room temperature when at atmospheric pressure. A storage vessel capable of is suitable to contain the liquid. Ammonia is used in numerous different industrial application requiring carbon or stainless steel storage vessels. Ammonia with at least 0.2 percent by weight water content is not corrosive to carbon steel. NH3 carbon steel construction storage tanks with 0.2 percent by weight or more of water could last more than 50 years in service. Experts warn that ammonium compounds not be allowed to come in contact with bases (unless in an intended and contained reaction), as dangerous quantities of ammonia gas could be released.
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1365_19
Laboratory The hazards of ammonia solutions depend on the concentration: "dilute" ammonia solutions are usually 5–10% by weight (<5.62 mol/L); "concentrated" solutions are usually prepared at >25% by weight. A 25% (by weight) solution has a density of 0.907 g/cm3, and a solution that has a lower density will be more concentrated. The European Union classification of ammonia solutions is given in the table. The ammonia vapour from concentrated ammonia solutions is severely irritating to the eyes and the respiratory tract, and experts warn that these solutions only be handled in a fume hood. Saturated ("0.880" – see #Properties) solutions can develop a significant pressure inside a closed bottle in warm weather, and experts also warn that the bottle be opened with care; this is not usually a problem for 25% ("0.900") solutions. Experts warn that ammonia solutions not be mixed with halogens, as toxic and/or explosive products are formed. Experts also warn that prolonged contact of ammonia solutions with silver, mercury or iodide salts can also lead to explosive products: such mixtures are often formed in qualitative inorganic analysis, and that it needs to be lightly acidified but not concentrated (<6% w/v) before disposal once the test is completed. Laboratory use of anhydrous ammonia (gas or liquid) Anhydrous ammonia is classified as toxic (T) and dangerous for the environment (N). The gas is flammable (autoignition temperature: 651 °C) and can form explosive mixtures with air (16–25%). The permissible exposure limit (PEL) in the United States is 50 ppm (35 mg/m3), while the IDLH concentration is estimated at 300 ppm. Repeated exposure to ammonia lowers the sensitivity to the smell of the gas: normally the odour is detectable at concentrations of less than 50 ppm, but desensitised individuals may not detect it even at concentrations of 100 ppm. Anhydrous ammonia corrodes copper- and zinc-containing alloys which makes brass fittings not appropriate for handling the gas. Liquid ammonia can also attack rubber and certain plastics.
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1365_20
Ammonia reacts violently with the halogens. Nitrogen triiodide, a primary high explosive, is formed when ammonia comes in contact with iodine. Ammonia causes the explosive polymerisation of ethylene oxide. It also forms explosive fulminating compounds with compounds of gold, silver, mercury, germanium or tellurium, and with stibine. Violent reactions have also been reported with acetaldehyde, hypochlorite solutions, potassium ferricyanide and peroxides. Ammonia adsorption followed by FTIR as well as temperature programmed desorption of ammonia (NH3-TPD) are very valuable methods to characterize acid-base properties of heterogeneous catalysts. Production Ammonia is one of the most produced inorganic chemicals, with global production reported at 175 million tonnes in 2018. China accounted for 28.5% of that, followed by Russia at 10.3%, the United States at 9.1%, and India at 6.7%. Before the start of World War I, most ammonia was obtained by the dry distillation of nitrogenous vegetable and animal waste products, including camel dung, where it was distilled by the reduction of nitrous acid and nitrites with hydrogen; in addition, it was produced by the distillation of coal, and also by the decomposition of ammonium salts by alkaline hydroxides such as quicklime: 2 NH4Cl + 2 CaO → CaCl2 + Ca(OH)2 + 2 NH3(g) For small scale laboratory synthesis, one can heat urea and calcium hydroxide: (NH2)2CO + Ca(OH)2 → CaCO3 + 2 NH3 Haber–Bosch Mass production uses the Haber–Bosch process, a gas phase reaction between hydrogen (H2) and nitrogen (N2) at a moderately-elevated temperature (450 °C) and high pressure ():
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1365_21
This reaction is exothermic and results in decreased entropy, meaning that the reaction is favoured at lower temperatures and higher pressures. It is difficult and expensive to achieve, as lower temperatures result in slower reaction kinetics (hence a slower reaction rate) and high pressure requires high-strength pressure vessels that are not weakened by hydrogen embrittlement. Diatomic nitrogen is bound together by a triple bond, which makes it rather inert. Yield and efficiency are low, meaning that the output must be continuously separated and extracted for the reaction to proceed at an acceptable pace. Combined with the energy needed to produce hydrogen and purified atmospheric nitrogen, ammonia production is energy-intensive, accounting for 1 to 2% of global energy consumption, 3% of global carbon emissions, and 3 to 5% of natural gas consumption. Electrochemical Ammonia can be synthesized electrochemically. The only required inputs are sources of nitrogen (potentially atmospheric) and hydrogen (water), allowing generation at the point of use. The availability of renewable energy creates the possibility of zero emission production. In 2012, Hideo Hosono's group found that Ru-loaded Electride works well as a catalyst and pursued more efficient formation. This method is implemented in a small plant for ammonia synthesis in Japan. In 2019, Hosono's group found another catalyst, a novel perovskite oxynitride-hydride BaCe, that works at lower temperature and without costly Ruthenium. Another electrochemical synthesis mode involves the reductive formation of lithium nitride, which can be protonated to ammonia, given a proton source. Ethanol has been used as such a source, although it may degrade. One study used lithium electrodeposition in tetrahydrofuran. In 2021, Suryanto et al. replaced ethanol with a tetraalkyl phosphonium salt. This cation can stably undergo deprotonation–reprotonation cycles, while it enhances the medium's ionic conductivity. The study observed production rates of 53 ± nanomoles/s/cm2 at 69 ± 1% faradaic efficiency experiments under 0.5-bar hydrogen and 19.5-bar nitrogen partial pressure at ambient temperature. Role in biological systems and human disease
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1365_22
Role in biological systems and human disease Ammonia is both a metabolic waste and a metabolic input throughout the biosphere. It is an important source of nitrogen for living systems. Although atmospheric nitrogen abounds (more than 75%), few living creatures are capable of using this atmospheric nitrogen in its diatomic form, N2 gas. Therefore, nitrogen fixation is required for the synthesis of amino acids, which are the building blocks of protein. Some plants rely on ammonia and other nitrogenous wastes incorporated into the soil by decaying matter. Others, such as nitrogen-fixing legumes, benefit from symbiotic relationships with rhizobia that create ammonia from atmospheric nitrogen. Biosynthesis In certain organisms, ammonia is produced from atmospheric nitrogen by enzymes called nitrogenases. The overall process is called nitrogen fixation. Intense effort has been directed toward understanding the mechanism of biological nitrogen fixation; the scientific interest in this problem is motivated by the unusual structure of the active site of the enzyme, which consists of an Fe7MoS9 ensemble. Ammonia is also a metabolic product of amino acid deamination catalyzed by enzymes such as glutamate dehydrogenase 1. Ammonia excretion is common in aquatic animals. In humans, it is quickly converted to urea, which is much less toxic, particularly less basic. This urea is a major component of the dry weight of urine. Most reptiles, birds, insects, and snails excrete uric acid solely as nitrogenous waste. Physiology Ammonia also plays a role in both normal and abnormal animal physiology. It is biosynthesised through normal amino acid metabolism and is toxic in high concentrations. The liver converts ammonia to urea through a series of reactions known as the urea cycle. Liver dysfunction, such as that seen in cirrhosis, may lead to elevated amounts of ammonia in the blood (hyperammonemia). Likewise, defects in the enzymes responsible for the urea cycle, such as ornithine transcarbamylase, lead to hyperammonemia. Hyperammonemia contributes to the confusion and coma of hepatic encephalopathy, as well as the neurologic disease common in people with urea cycle defects and organic acidurias.
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1365_23
Ammonia is important for normal animal acid/base balance. After formation of ammonium from glutamine, α-ketoglutarate may be degraded to produce two bicarbonate ions, which are then available as buffers for dietary acids. Ammonium is excreted in the urine, resulting in net acid loss. Ammonia may itself diffuse across the renal tubules, combine with a hydrogen ion, and thus allow for further acid excretion. Excretion Ammonium ions are a toxic waste product of metabolism in animals. In fish and aquatic invertebrates, it is excreted directly into the water. In mammals, sharks, and amphibians, it is converted in the urea cycle to urea, which is less toxic and can be stored more efficiently. In birds, reptiles, and terrestrial snails, metabolic ammonium is converted into uric acid, which is solid and can therefore be excreted with minimal water loss. Beyond Earth Ammonia has been detected in the atmospheres of the giant planets, including Jupiter, along with other gases such as methane, hydrogen, and helium. The interior of Saturn may include frozen ammonia crystals. It is found on Deimos and Phobos – the two moons of Mars. Interstellar space Ammonia was first detected in interstellar space in 1968, based on microwave emissions from the direction of the galactic core. This was the first polyatomic molecule to be so detected. The sensitivity of the molecule to a broad range of excitations and the ease with which it can be observed in a number of regions has made ammonia one of the most important molecules for studies of molecular clouds. The relative intensity of the ammonia lines can be used to measure the temperature of the emitting medium. The following isotopic species of ammonia have been detected: NH3, 15NH3, NH2D, NHD2, and ND3 The detection of triply deuterated ammonia was considered a surprise as deuterium is relatively scarce. It is thought that the low-temperature conditions allow this molecule to survive and accumulate.
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1365_24
Since its interstellar discovery, NH3 has proved to be an invaluable spectroscopic tool in the study of the interstellar medium. With a large number of transitions sensitive to a wide range of excitation conditions, NH3 has been widely astronomically detected – its detection has been reported in hundreds of journal articles. Listed below is a sample of journal articles that highlights the range of detectors that have been used to identify ammonia. The study of interstellar ammonia has been important to a number of areas of research in the last few decades. Some of these are delineated below and primarily involve using ammonia as an interstellar thermometer. Interstellar formation mechanisms The interstellar abundance for ammonia has been measured for a variety of environments. The [NH3]/[H2] ratio has been estimated to range from 10−7 in small dark clouds up to 10−5 in the dense core of the Orion Molecular Cloud Complex. Although a total of 18 total production routes have been proposed, the principal formation mechanism for interstellar NH3 is the reaction: NH4+ + e− → NH3 + H· The rate constant, k, of this reaction depends on the temperature of the environment, with a value of 5.2×10−6 at 10 K. The rate constant was calculated from the formula . For the primary formation reaction, and . Assuming an NH4+ abundance of 3×10−7 and an electron abundance of 10−7 typical of molecular clouds, the formation will proceed at a rate of in a molecular cloud of total density . All other proposed formation reactions have rate constants of between 2 and 13 orders of magnitude smaller, making their contribution to the abundance of ammonia relatively insignificant. As an example of the minor contribution other formation reactions play, the reaction: H2 + NH2 → NH3 + H has a rate constant of 2.2. Assuming H2 densities of 105 and [NH2]/[H2] ratio of 10−7, this reaction proceeds at a rate of 2.2, more than 3 orders of magnitude slower than the primary reaction above. Some of the other possible formation reactions are: H− + NH4+ → NH3 + H2 PNH3+ + e− → P + NH3
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1365_25
Interstellar destruction mechanisms There are 113 total proposed reactions leading to the destruction of NH3. Of these, 39 were tabulated in extensive tables of the chemistry among C, N, and O compounds. A review of interstellar ammonia cites the following reactions as the principal dissociation mechanisms: with rate constants of 4.39×10−9 and 2.2×10−9, respectively. The above equations (, ) run at a rate of 8.8×10−9 and 4.4×10−13, respectively. These calculations assumed the given rate constants and abundances of [NH3]/[H2] = 10−5, [H3+]/[H2] = 2×10−5, [HCO+]/[H2] = 2×10−9, and total densities of n = 105, typical of cold, dense, molecular clouds. Clearly, between these two primary reactions, equation () is the dominant destruction reaction, with a rate ≈10,000 times faster than equation (). This is due to the relatively high abundance of H3+. Single antenna detections Radio observations of NH3 from the Effelsberg 100-m Radio Telescope reveal that the ammonia line is separated into two components – a background ridge and an unresolved core. The background corresponds well with the locations previously detected CO. The 25 m Chilbolton telescope in England detected radio signatures of ammonia in H II regions, HNH2O masers, H-H objects, and other objects associated with star formation. A comparison of emission line widths indicates that turbulent or systematic velocities do not increase in the central cores of molecular clouds. Microwave radiation from ammonia was observed in several galactic objects including W3(OH), Orion A, W43, W51, and five sources in the galactic centre. The high detection rate indicates that this is a common molecule in the interstellar medium and that high-density regions are common in the galaxy.
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1365_26
Interferometric studies VLA observations of NH3 in seven regions with high-velocity gaseous outflows revealed condensations of less than 0.1 pc in L1551, S140, and Cepheus A. Three individual condensations were detected in Cepheus A, one of them with a highly elongated shape. They may play an important role in creating the bipolar outflow in the region. Extragalactic ammonia was imaged using the VLA in IC 342. The hot gas has temperatures above 70 K, which was inferred from ammonia line ratios and appears to be closely associated with the innermost portions of the nuclear bar seen in CO. NH3 was also monitored by VLA toward a sample of four galactic ultracompact HII regions: G9.62+0.19, G10.47+0.03, G29.96-0.02, and G31.41+0.31. Based upon temperature and density diagnostics, it is concluded that in general such clumps are probably the sites of massive star formation in an early evolutionary phase prior to the development of an ultracompact HII region. Infrared detections Absorption at 2.97 micrometres due to solid ammonia was recorded from interstellar grains in the Becklin-Neugebauer Object and probably in NGC 2264-IR as well. This detection helped explain the physical shape of previously poorly understood and related ice absorption lines. A spectrum of the disk of Jupiter was obtained from the Kuiper Airborne Observatory, covering the 100 to 300 cm−1 spectral range. Analysis of the spectrum provides information on global mean properties of ammonia gas and an ammonia ice haze. A total of 149 dark cloud positions were surveyed for evidence of 'dense cores' by using the (J,K) = (1,1) rotating inversion line of NH3. In general, the cores are not spherically shaped, with aspect ratios ranging from 1.1 to 4.4. It is also found that cores with stars have broader lines than cores without stars. Ammonia has been detected in the Draco Nebula and in one or possibly two molecular clouds, which are associated with the high-latitude galactic infrared cirrus. The finding is significant because they may represent the birthplaces for the Population I metallicity B-type stars in the galactic halo that could have been borne in the galactic disk.
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1365_27
Observations of nearby dark clouds By balancing and stimulated emission with spontaneous emission, it is possible to construct a relation between excitation temperature and density. Moreover, since the transitional levels of ammonia can be approximated by a 2-level system at low temperatures, this calculation is fairly simple. This premise can be applied to dark clouds, regions suspected of having extremely low temperatures and possible sites for future star formation. Detections of ammonia in dark clouds show very narrow linesindicative not only of low temperatures, but also of a low level of inner-cloud turbulence. Line ratio calculations provide a measurement of cloud temperature that is independent of previous CO observations. The ammonia observations were consistent with CO measurements of rotation temperatures of ≈10 K. With this, densities can be determined, and have been calculated to range between 104 and 105 cm−3 in dark clouds. Mapping of NH3 gives typical clouds sizes of 0.1 pc and masses near 1 solar mass. These cold, dense cores are the sites of future star formation. UC HII regions Ultra-compact HII regions are among the best tracers of high-mass star formation. The dense material surrounding UCHII regions is likely primarily molecular. Since a complete study of massive star formation necessarily involves the cloud from which the star formed, ammonia is an invaluable tool in understanding this surrounding molecular material. Since this molecular material can be spatially resolved, it is possible to constrain the heating/ionising sources, temperatures, masses, and sizes of the regions. Doppler-shifted velocity components allow for the separation of distinct regions of molecular gas that can trace outflows and hot cores originating from forming stars. Extragalactic detection Ammonia has been detected in external galaxies, and by simultaneously measuring several lines, it is possible to directly measure the gas temperature in these galaxies. Line ratios imply that gas temperatures are warm (≈50 K), originating from dense clouds with sizes of tens of pc. This picture is consistent with the picture within our Milky Way galaxyhot dense molecular cores form around newly forming stars embedded in larger clouds of molecular material on the scale of several hundred pc (giant molecular clouds; GMCs). See also Notes References Works Cited Further reading External links
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Works Cited Further reading External links International Chemical Safety Card 0414 (anhydrous ammonia), ilo.org. International Chemical Safety Card 0215 (aqueous solutions), ilo.org. Emergency Response to Ammonia Fertilizer Releases (Spills) for the Minnesota Department of Agriculture.ammoniaspills.org National Institute for Occupational Safety and Health – Ammonia Page, cdc.gov NIOSH Pocket Guide to Chemical Hazards – Ammonia, cdc.gov Ammonia, video Bases (chemistry) Foul-smelling chemicals Gaseous signaling molecules Household chemicals Industrial gases Inorganic solvents Nitrogen cycle Nitrogen hydrides Nitrogen(−III) compounds Refrigerants Toxicology
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1366_0
Amethyst is a violet variety of quartz. The name comes from the Koine Greek αμέθυστος amethystos from α- a-, "not" and μεθύσκω (Ancient Greek) / μεθώ (Modern Greek), "intoxicate", a reference to the belief that the stone protected its owner from drunkenness. Ancient Greeks wore amethyst and carved drinking vessels from it in the belief that it would prevent intoxication. Amethyst, a semiprecious stone, is often used in jewelry and is the traditional birthstone for February. Structure Amethyst is a purple variety of quartz (SiO2) and owes its violet color to irradiation, impurities of iron and in some cases other transition metals, and the presence of other trace elements, which result in complex crystal lattice substitutions. The hardness of the mineral is the same as quartz, thus making it suitable for use in jewelry. Hue and tone Amethyst occurs in primary hues from a light lavender or pale violet, to a deep purple. Amethyst may exhibit one or both secondary hues, red and blue. High quality amethyst can be found in Siberia, Sri Lanka, Brazil, Uruguay, and the Far East. The ideal grade is called "Deep Siberian" and has a primary purple hue of around 75–80%, with 15–20% blue and (depending on the light source) red secondary hues. ‘Rose de France’ is defined by its markedly light shade of the purple, reminiscent of a lavender/lilac shade. These pale colors were once considered undesirable, but have recently become popular due to intensive marketing. Green quartz is sometimes incorrectly called green amethyst, which is a misnomer and not an appropriate name for the material, as the proper terminology is prasiolite. Other names for green quartz are vermarine or lime citrine.
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1366_1
Amethyst frequently shows color zoning, with the most intense color typically found at the crystal terminations. It is the most prized variety of quartz. One of a gem cutter’s tasks is to make a finished product with even color. Sometimes, only a thin layer of a natural, uncut amethyst is violet colored, or the color is very uneven. The uncut gem may have only a small portion that is suitable for faceting. The color of amethyst has been demonstrated to result from substitution by irradiation of trivalent iron (Fe3+) for silicon in the structure, in the presence of trace elements of large ionic radius, and to a certain extent, the amethyst color can naturally result from displacement of transition elements even if the iron concentration is low. Natural amethyst is dichroic in reddish violet and bluish violet, but when heated, turns yellow-orange, yellow-brown, or dark brownish and may resemble citrine, but loses its dichroism, unlike genuine citrine. When partially heated, amethyst can result in ametrine. Amethyst can fade in tone if overexposed to light sources and can be artificially darkened with adequate irradiation. It does not fluoresce under either short-wave or long-wave UV light. Geographic distribution Amethyst is found in many locations around the world. Between 2000 and 2010, the greatest production was from Marabá and Pau d'Arco, Pará, and the Paraná Basin, Rio Grande do Sul, Brazil; Sandoval, Santa Cruz, Bolivia; Artigas, Uruguay; Kalomo, Zambia; and Thunder Bay, Ontario. Lesser amounts are found in many other locations in Africa, Brazil, Spain, Argentina, Russia, Afghanistan, South Korea, Mexico, and the United States. Amethyst is produced in abundance from the state of Rio Grande do Sul in Brazil where it occurs in large geodes within volcanic rocks. Many of the hollow agates of southwestern Brazil and Uruguay contain a crop of amethyst crystals in the interior. Artigas, Uruguay and neighboring Brazilian state Rio Grande do Sul are large world producers, with lesser quantities mined in Minas Gerais and Bahia states.
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1366_2
Amethyst is also found and mined in South Korea. The large opencast amethyst vein at Maissau, Lower Austria, was historically important, but is no longer included among significant producers. Much fine amethyst comes from Russia, especially from near Mursinka in the Ekaterinburg district, where it occurs in drusy cavities in granitic rocks. Amethyst was historically mined in many localities in south India, though these are no longer significant producers. One of the largest global amethyst producers is Zambia in southern Africa with an annual production of about 1000 tons. Amethyst occurs at many localities in the United States. The most important production is at Four Peaks, Gila and Maricopa Counties, Arizona, and Jackson's Crossroads, Wilkes County, Georgia. Smaller occurrences have been reported in the Red Feather Lakes, near Fort Collins, Colorado; Amethyst Mountain, Texas; Yellowstone National Park; Delaware County, Pennsylvania; Haywood County, North Carolina; Deer Hill and Stow, Maine and in the Lake Superior region of Minnesota, Wisconsin and Michigan. Amethyst is relatively common in the Canadian provinces of Ontario and Nova Scotia. The largest amethyst mine in North America is located in Thunder Bay, Ontario. Amethyst is the official state gemstone of South Carolina. Several South Carolina amethysts are on display at the Smithsonian Museum of Natural History. History Amethyst was used as a gemstone by the ancient Egyptians and was largely employed in antiquity for intaglio engraved gems. The Greeks believed amethyst gems could prevent intoxication, while medieval European soldiers wore amethyst amulets as protection in battle in the belief that amethysts heal people and keep them cool-headed. Beads of amethyst were found in Anglo-Saxon graves in England. Anglican bishops wear an episcopal ring often set with an amethyst, an allusion to the description of the Apostles as "not drunk" at Pentecost in Acts 2:15. A large geode, or "amethyst-grotto", from near Santa Cruz in southern Brazil was presented at a 1902 exhibition in Düsseldorf, Germany.
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1366_3
The meaning of amethyst varies from time to time and culture, which is why amethyst has different meanings in Feng Shui and focuses on increasing wealth. In ancient China, it was also used as a powerful tool to remove negative energies and drive away the hazards of daily life. Synthetic amethyst Synthetic (laboratory-grown) amethyst is produced by a synthesis method called hydrothermal growth, which grows the crystals inside a high-pressure autoclave. Synthetic amethyst is made to imitate the best quality amethyst. Its chemical and physical properties are the same as that of natural amethyst and it can not be differentiated with absolute certainty without advanced gemmological testing (which is often cost-prohibitive). One test based on "Brazil law twinning" (a form of quartz twinning where right and left hand quartz structures are combined in a single crystal) can be used to identify most synthetic amethyst rather easily. Synthesizing twinned amethyst is possible, but this type is not available in large quantities in the market. Treated amethyst is produced by gamma ray, X-ray, or electron-beam irradiation of clear quartz (rock crystal), which has been first doped with ferric impurities. Exposure to heat partially cancels the irradiation effects and amethyst generally becomes yellow or even green. Much of the citrine, cairngorm, or yellow quartz of jewelry is said to be merely "burnt amethyst". Cultural history
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1366_4
Cultural history Ancient Greece The Greek word "amethystos" may be translated as "not drunken", from Greek a-, "not" + , "intoxicated". Amethyst was considered to be a strong antidote against drunkenness, which is why wine goblets were often carved from it. In his poem "L'Amethyste, ou les Amours de Bacchus et d'Amethyste" (Amethyst or the loves of Bacchus and Amethyste), the French poet Remy Belleau (1528–1577) invented a myth in which Bacchus, the god of intoxication, of wine, and grapes was pursuing a maiden named Amethyste, who refused his affections. Amethyste prayed to the gods to remain chaste, a prayer which the chaste goddess Diana answered, transforming her into a white stone. Humbled by Amethyste's desire to remain chaste, Bacchus poured wine over the stone as an offering, dyeing the crystals purple. Variations of the story include that Dionysus had been insulted by a mortal and swore to slay the next mortal who crossed his path, creating fierce tigers to carry out his wrath. The mortal turned out to be a beautiful young woman, Amethystos, who was on her way to pay tribute to Artemis. Her life was spared by Artemis, who transformed the maiden into a statue of pure crystalline quartz to protect her from the brutal claws. Dionysus wept tears of wine in remorse for his action at the sight of the beautiful statue. The god's tears then stained the quartz purple. This myth and its variations are not found in classical sources. However, the goddess Rhea does present Dionysus with an amethyst stone to preserve the wine-drinker's sanity in historical text. Other cultural associations Tibetans consider amethyst sacred to the Buddha and make prayer beads from it. Amethyst is considered the birthstone of February. In the Middle Ages, it was considered a symbol of royalty and used to decorate English regalia. In the Old World, amethyst was considered one of the Cardinal gems, in that it was one of the five gemstones considered precious above all others, until large deposits were found in Brazil.
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1366_5
Value Until the 18th century, amethyst was included in the cardinal, or most valuable, gemstones (along with diamond, sapphire, ruby, and emerald), but since the discovery of extensive deposits in locations such as Brazil, it has lost most of its value. It is now considered a semiprecious stone. Collectors look for depth of color; possibly with red flashes if cut conventionally. As amethyst is readily available in large structures, the value of the gem is not primarily defined by carat weight. This is different from most gemstones, since the carat weight typically exponentially increases the value of the stone. The biggest factor in the value of amethyst is the color displayed. The highest-grade amethyst (called "Deep Russian") is exceptionally rare. When one is found, its value is dependent on the demand of collectors. The highest-grade sapphires or rubies are still orders of magnitude more expensive than amethyst. Handling and care The most suitable setting for gem amethyst is a prong or a bezel setting. The channel method must be used with caution. Amethyst has a good hardness, and handling it with proper care will prevent any damage to the stone. Amethyst is sensitive to strong heat and may lose or change its colour when exposed to prolonged heat or light. Polishing the stone or cleaning it by ultrasonic or steamer must be done with caution. See also Ametrine List of minerals Specimen Ridge References Quartz gemstones Provincial symbols of Ontario Trigonal minerals Minerals in space group 152 or 154
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1367_0
Albertosaurus (; meaning "Alberta lizard") is a genus of tyrannosaurid theropod dinosaurs that lived in western North America during the Late Cretaceous Period, about 71 million years ago. The type species, A. sarcophagus, was apparently restricted in range to the modern-day Canadian province of Alberta, after which the genus is named, although an indeterminate species ("cf. Albertosaurus sp.") has been discovered in the Corral de Enmedio and Packard Formations in Mexico. Scientists disagree on the content of the genus, with some recognizing Gorgosaurus libratus as a second species. As a tyrannosaurid, Albertosaurus was a bipedal predator with tiny, two-fingered hands and a massive head that had dozens of large, sharp teeth. It may have been at the top of the food chain in its local ecosystem. While Albertosaurus was large for a theropod, it was much smaller than its larger and more famous relative Tyrannosaurus rex, growing and possibly weighing to 4 tonnes (4.4 short tons) Since the first discovery in 1884, fossils of more than 30 individuals have been recovered, providing scientists with a more detailed knowledge of Albertosaurus anatomy than is available for most other tyrannosaurids. The discovery of 26 individuals at one site provides evidence of pack behaviour and allows studies of ontogeny and population biology, which are impossible with lesser-known dinosaurs due to their remains being rarer and more fragmentary compared to those of Albertosaurus. History of discovery Naming Albertosaurus was named by Henry Fairfield Osborn in a one-page note at the end of his 1905 description of Tyrannosaurus rex. The name honours Alberta, the Canadian province established the same year, in which the first remains were found. The generic name also incorporates the Greek term /sauros ("lizard"), the most common suffix in dinosaur names. The type species is Albertosaurus sarcophagus; the specific name is derived from Ancient Greek σαρκοφάγος () meaning "flesh-eating" and having the same etymology as the funeral container with which it shares its name: a combination of the Greek words σαρξ/ ("flesh") and / ("to eat"). More than 30 specimens of all ages are known to science. Early discoveries
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1367_1
Early discoveries The type specimen is a partial skull, collected in the summer of 1884 from an outcrop of the Horseshoe Canyon Formation alongside the Red Deer River, in Alberta. This specimen, found on June 9, 1884, was recovered by an expedition of the Geological Survey of Canada, led by the famous geologist Joseph Burr Tyrrell. Due to a lack of specialised equipment the almost complete skull could only be partially secured. In 1889, Tyrrell's colleague Thomas Chesmer Weston found an incomplete smaller skull associated with some skeletal material at a location nearby. The two skulls were assigned to the preexisting species Laelaps incrassatus by Edward Drinker Cope in 1892, although the name Laelaps was preoccupied by a genus of mite and had been changed to Dryptosaurus in 1877 by Othniel Charles Marsh. Cope refused to recognize the new name created by his archrival Marsh. However, Lawrence Lambe used the name Dryptosaurus incrassatus instead of Laelaps incrassatus when he described the remains in detail in 1903 and 1904, a combination first coined by Oliver Perry Hay in 1902. Shortly later, Osborn pointed out that D. incrassatus was based on generic tyrannosaurid teeth, so the two Horseshoe Canyon skulls could not be confidently referred to that species. The Horseshoe Canyon skulls also differed markedly from the remains of D. aquilunguis, type species of Dryptosaurus, so Osborn created the new name Albertosaurus sarcophagus for them in 1905. He did not describe the remains in any great detail, citing Lambe's complete description the year before. Both specimens (the holotype CMN 5600 and the paratype CMN 5601) are stored in the Canadian Museum of Nature in Ottawa. By the early twenty-first century, some concerns had arisen that, due to the damaged state of the holotype, Albertosaurus might be a nomen dubium, a "dubious name" that could only be used for the type specimen itself because other fossils could not reliably be assigned to it. However, in 2010, Thomas Carr established that the holotype, the paratype and comparable later finds all shared a single common unique trait or autapomorphy: the possession of an enlarged pneumatic opening in the back rim of the side of the palatine bone, proving that Albertosaurus was a valid taxon.
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1367_2
Dry Island bone bed On 11 August 1910, American paleontologist Barnum Brown discovered the remains of a large group of Albertosaurus at another quarry alongside the Red Deer River. Because of the large number of bones and the limited time available, Brown's party did not collect every specimen, but made sure to collect remains from all of the individuals that they could identify in the bone bed. Among the bones deposited in the American Museum of Natural History collections in New York City are seven sets of right metatarsals, along with two isolated toe bones that did not match any of the metatarsals in size. This indicated the presence of at least nine individuals in the quarry. Palaeontologist Philip J. Currie of the Royal Tyrrell Museum of Palaeontology rediscovered the bonebed in 1997 and resumed fieldwork at the site, which is now located inside Dry Island Buffalo Jump Provincial Park. Further excavation from 1997 to 2005 turned up the remains of 13 more individuals of various ages, including a diminutive two-year-old and a very old individual estimated at over in length. None of these individuals are known from complete skeletons, and most are represented by remains in both museums. Excavations continued until 2008, when the minimum number of individuals present had been established at 12, on the basis of preserved elements that occur only once in a skeleton, and at 26 if mirrored elements were counted when differing in size due to ontogeny. A total of 1,128 Albertosaurus bones had been secured, the largest concentration of large theropod fossils known from the Cretaceous. Other discoveries In 1911, Barnum Brown, during the second year of American Museum of Natural History operations in Alberta, uncovered a fragmentary partial Albertosaurus skull at the Red Deer River near Tolman Bridge, specimen AMNH 5222. William Parks described a new species in 1928, Albertosaurus arctunguis, based on a partial skeleton lacking the skull excavated by Gus Lindblad and Ralph Hornell near the Red Deer River in 1923, but this species has been considered identical to A. sarcophagus since 1970. Parks' specimen (ROM 807) is housed in the Royal Ontario Museum in Toronto.
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1367_3
Between 1926 and 1972, no Albertosaurus fossils were found at all; but, since the seventies, there has been a steady increase in the known material. Apart from the Dry Island bonebed, six more skulls and skeletons have since been discovered in Alberta and are housed in various Canadian museums: specimens RTMP 81.010.001, found in 1978 by amateur paleontologist Maurice Stefanuk; RTMP 85.098.001, found by Stefanuk on 16 June 1985; RTMP 86.64.001 (December 1985); RTMP 86.205.001 (1986); RTMP 97.058.0001 (1996); and CMN 11315. However, due to vandalism and accidents, no undamaged and complete skulls could be secured among these finds. Fossils have also been reported from the American states of Montana, New Mexico, Wyoming, and Missouri, but these probably do not represent A. sarcophagus and may not even belong to the genus Albertosaurus. Two specimens from ("cf Albertosaurus ".sp") have been found in Mexico (Packard Formation and Corral de Enmedio Formation). Gorgosaurus libratus In 1913, paleontologist Charles H. Sternberg recovered another tyrannosaurid skeleton from the slightly older Dinosaur Park Formation in Alberta. Lawrence Lambe named this dinosaur Gorgosaurus libratus in 1914. Other specimens were later found in Alberta and the US state of Montana. Finding, largely due to a lack of good Albertosaurus skull material, no significant differences to separate the two taxa, Dale Russell declared the name Gorgosaurus a junior synonym of Albertosaurus, which had been named first, and G. libratus was renamed Albertosaurus libratus in 1970. A species distinction was maintained because of the age difference. This addition extended the temporal range of the genus Albertosaurus backwards by several million years and its geographic range southwards by hundreds of kilometres.
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1367_4
In 2003, Philip J. Currie, benefiting from much more extensive finds and a general increase in anatomical knowledge of theropods, compared several tyrannosaurid skulls and came to the conclusion that the two species are more distinct than previously thought. The decision to use one or two genera is rather arbitrary, as the two species are sister taxa, more closely related to each other than to any other species. Recognizing this, Currie nevertheless recommended that Albertosaurus and Gorgosaurus be retained as separate genera, as he concluded that they were no more similar than Daspletosaurus and Tyrannosaurus, which are almost always separated. In addition, several albertosaurine specimens have been recovered from Alaska and New Mexico, and Currie suggested that the Albertosaurus-Gorgosaurus situation may be clarified once these are described fully. Most authors have followed Currie's recommendation, but some have not. Other species Apart from A. sarcophagus, A. arctunguis and A. libratus, several other species of Albertosaurus have been named. All of these are today seen as younger synonyms of other species or as nomina dubia, and are not assigned to Albertosaurus.
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1367_5
In 1930, Anatoly Nikolaevich Riabinin named Albertosaurus pericolosus based on a tooth from China, that probably belonged to Tarbosaurus. In 1932, Friedrich von Huene renamed Dryptosaurus incrassatus, not considered a nomen dubium by him, to Albertosaurus incrassatus. Because he had identified Gorgosaurus with Albertosaurus, in 1970, Russell also renamed Gorgosaurus sternbergi (Matthew & Brown 1922) into Albertosaurus sternbergi and Gorgosaurus lancensis (Gilmore 1946) into Albertosaurus lancensis. The former species is today seen as a juvenile form of Gorgosaurus libratus, the latter as either identical to Tyrannosaurus or representing a separate genus Nanotyrannus. In 1988, Gregory S. Paul based Albertosaurus megagracilis on a small tyrannosaurid skeleton, specimen LACM 28345, from the Hell Creek Formation of Montana. It was renamed Dinotyrannus in 1995, but is now thought to represent a juvenile Tyrannosaurus rex. Also in 1988, Paul renamed Alectrosaurus olseni (Gilmore 1933) into Albertosaurus olseni; this has found no general acceptance. In 1989, Gorgosaurus novojilovi (Maleev 1955) was renamed by Bryn Mader and Robert Bradley as Albertosaurus novojilovi; today this is seen as a synonym of Tarbosaurus. On two occasions, species based on valid Albertosaurus material were reassigned to a different genus: in 1922 William Diller Matthew renamed A. sarcophagus into Deinodon sarcophagus and in 1939 German paleontologist Oskar Kuhn renamed A. arctunguis into Deinodon arctunguis. Description Albertosaurus was a large bipedal predator but smaller than Tarbosaurus and Tyrannosaurus rex. Typical Albertosaurus adults measured up to long, while rare individuals of great age could grow to be over long. Several independent mass estimates, obtained by different methods, suggest that an adult Albertosaurus weighed between . In 2016, Molina-Pérez and Larramendi estimated the largest specimen (CMN 5600) at 9.6 meters (31 ft) and 4 tonnes (4.4 short tons).
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1367_6
Albertosaurus shared a similar body appearance with all other tyrannosaurids. Typically for a theropod, Albertosaurus was bipedal and balanced the heavy head and torso with a long tail. However, tyrannosaurid forelimbs were extremely small for their body size and retained only two digits. The hind limbs were long and ended in a four-toed foot on which the first digit, called the hallux, was short and did not reach the ground. The third digit was longer than the rest. Albertosaurus may have been able to reach walking speeds of 14–21 km/hour (8–13 mi/hour). At least for the younger individuals, a high running speed is plausible. Two skin impressions from Albertosaurus are known, both showing scales. One patch is found with some gastralic ribs and the impression of a long, unknown bone, indicating that the patch is from the belly. The scales are pebbly and gradually become larger and somewhat hexagonal in shape. Also preserved are two larger feature scales, placed 4.5 cm apart from each other. Another skin impression is from an unknown part of the body. These scales are small, diamond-shaped and arranged in rows. Skull and teeth
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1367_7
Skull and teeth The massive skull of Albertosaurus, which was perched on a short, S-shaped neck, was about long in the largest adults. Wide openings in the skull (fenestrae) reduced the weight of the head while also providing space for muscle attachment and sensory organs. Its long jaws contained, both sides combined, 58 or more banana-shaped teeth; larger tyrannosaurids possessed fewer teeth; Gorgosaurus had more at 62. Unlike most theropods, Albertosaurus and other tyrannosaurids were heterodont, with teeth of different forms depending on their position in the mouth. The premaxillary teeth at the tip of the upper jaw, four per side, were much smaller than the rest, more closely packed, and D-shaped in cross section. Like with Tyrannosaurus, the maxillary (cheek) teeth of Albertosaurus were adapted in general form to resist lateral forces exerted by a struggling prey. The bite force of Albertosaurus was less formidable, however, with the maximum force, by the hind teeth, reaching 3,413 Newtons. Above the eyes were short bony crests that may have been brightly coloured in life and used in courtship to attract a mate.
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1367_8
William Abler observed in 2001 that Albertosaurus tooth serrations resemble a crack in the tooth ending in a round void called an ampulla. Tyrannosaurid teeth were used as holdfasts for pulling flesh off a body, so when a tyrannosaur pulled back on a piece of meat, the tension could cause a purely crack-like serration to spread through the tooth. However, the presence of the ampulla distributed these forces over a larger surface area, and lessened the risk of damage to the tooth under strain. The presence of incisions ending in voids has parallels in human engineering. Guitar makers use incisions ending in voids to, as Abler describes, "impart alternating regions of flexibility and rigidity" to wood they work. The use of a drill to create an "ampulla" of sorts and prevent the propagation of cracks through material is also used to protect aircraft surfaces. Abler demonstrated that a plexiglass bar with incisions called "kerfs" and drilled holes was more than 25% stronger than one with only regularly placed incisions. Unlike tyrannosaurs, ancient predators like phytosaurs and Dimetrodon had no adaptations to prevent the crack-like serrations of their teeth from spreading when subjected to the forces of feeding. Classification and systematics Albertosaurus is a member of the theropod family Tyrannosauridae, in the subfamily Albertosaurinae. Its closest relative is the slightly older Gorgosaurus libratus (sometimes called Albertosaurus libratus; see below). These two species are the only described albertosaurines; other undescribed species may exist. Thomas Holtz found Appalachiosaurus to be an albertosaurine in 2004, but his more recent unpublished work locates it just outside Tyrannosauridae, in agreement with other authors. The other major subfamily of tyrannosaurids is the Tyrannosaurinae, which includes Daspletosaurus, Tarbosaurus and Tyrannosaurus. Compared with these robust tyrannosaurines, albertosaurines had slender builds, with proportionately smaller skulls and longer bones of the lower leg (tibia) and feet (metatarsals and phalanges). Below is the cladogram of the Tyrannosauridae based on the phylogenetic analysis conducted by Loewen et al. in 2013.
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1367_9
Palaeobiology Growth pattern Most age categories of Albertosaurus are represented in the fossil record. Using bone histology, the age of an individual animal at the time of death can often be determined, allowing growth rates to be estimated and compared with other species. The youngest known Albertosaurus is a two-year-old discovered in the Dry Island bonebed, which would have weighed about 50 kilograms (110 lb) and measured slightly more than in length. The specimen from the same quarry is the oldest and largest known, at 28 years of age. When specimens of intermediate age and size are plotted on a graph, an S-shaped growth curve results, with the most rapid growth occurring in a four-year period ending around the sixteenth year of life, a pattern also seen in other tyrannosaurids. The growth rate during this phase was per year, based on an adult 1.3 tonnes. Other studies have suggested higher adult weights; this would affect the magnitude of the growth rate, but not the overall pattern. Tyrannosaurids similar in size to Albertosaurus had similar growth rates, although the much larger Tyrannosaurus rex grew at almost five times this rate ( per year) at its peak. The end of the rapid growth phase suggests the onset of sexual maturity in Albertosaurus, although growth continued at a slower rate throughout the animals' lives. Sexual maturation while still actively growing appears to be a shared trait among small and large dinosaurs as well as in large mammals such as humans and elephants. This pattern of relatively early sexual maturation differs strikingly from the pattern in birds, which delay their sexual maturity until after they have finished growing. During growth, through thickening the tooth morphology changed so much that, had the association of young and adult skeletons on the Dry Island bonebed not proven they belonged to the same taxon, the teeth of juveniles would likely have been identified by statistical analysis as those of a different species.
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1367_10
Life history Most known Albertosaurus individuals were aged 14 years or more at the time of death. Juvenile animals are rarely found as fossils for several reasons, mainly preservation bias, where the smaller bones of younger animals were less likely to be preserved by fossilization than the larger bones of adults, and collection bias, where smaller fossils are less likely to be noticed by collectors in the field. Young Albertosaurus are relatively large for juvenile animals, but their remains are still rare in the fossil record compared with adults. It has been suggested that this phenomenon is a consequence of life history, rather than bias, and that fossils of juvenile Albertosaurus are rare because they simply did not die as often as adults did. A hypothesis of Albertosaurus life history postulates that hatchlings died in large numbers, but have not been preserved in the fossil record due to their small size and fragile construction. After just two years, juveniles were larger than any other predator in the region aside from adult Albertosaurus, and more fleet of foot than most of their prey animals. This resulted in a dramatic decrease in their mortality rate and a corresponding rarity of fossil remains. Mortality rates doubled at age twelve, perhaps the result of the physiological demands of the rapid growth phase, and then doubled again with the onset of sexual maturity between the ages of fourteen and sixteen. This elevated mortality rate continued throughout adulthood, perhaps due to the high physiological demands of procreation, including stress and injuries received during intraspecific competition for mates and resources, and eventually, the ever-increasing effects of senescence. The higher mortality rate in adults may explain their more common preservation. Very large animals were rare because few individuals survived long enough to attain such sizes. High infant mortality rates, followed by reduced mortality among juveniles and a sudden increase in mortality after sexual maturity, with very few animals reaching maximum size, is a pattern observed in many modern large mammals, including elephants, African buffalo, and rhinoceros. The same pattern is also seen in other tyrannosaurids. The comparison with modern animals and other tyrannosaurids lends support to this life history hypothesis, but bias in the fossil record may still play a large role, especially since more than two-thirds of all Albertosaurus specimens are known from one locality. Pack behaviour
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1367_11
Pack behaviour The Dry Island bonebed discovered by Barnum Brown and his crew contains the remains of 26 Albertosaurus, the most individuals found in one locality of any large Cretaceous theropod, and the second-most of any large theropod dinosaur behind the Allosaurus assemblage at the Cleveland-Lloyd Dinosaur Quarry in Utah. The group seems to be composed of one very old adult; eight adults between 17 and 23 years old; seven sub-adults undergoing their rapid growth phases at between 12 and 16 years old; and six juveniles between the ages of 2 and 11 years, who had not yet reached the growth phase. The near-absence of herbivore remains and the similar state of preservation common to the many individuals at the Albertosaurus bonebed quarry led Currie to conclude that the locality was not a predator trap like the La Brea Tar Pits in California, and that all of the preserved animals died at the same time. Currie claims this as evidence of pack behaviour. Other scientists are skeptical, observing that the animals may have been driven together by drought, flood or for other reasons. There is plentiful evidence for gregarious behaviour among herbivorous dinosaurs, including ceratopsians and hadrosaurs. However, only rarely are so many dinosaurian predators found at the same site. Small theropods like Deinonychus and Coelophysis have been found in aggregations, as have larger predators like Allosaurus and Mapusaurus. There is some evidence of gregarious behaviour in other tyrannosaurids as well. Fragmentary remains of smaller individuals were found alongside "Sue", the Tyrannosaurus mounted in the Field Museum of Natural History in Chicago, and a bonebed in the Two Medicine Formation of Montana contains at least three specimens of Daspletosaurus, preserved alongside several hadrosaurs. These findings may corroborate the evidence for social behaviour in Albertosaurus, although some or all of the above localities may represent temporary or unnatural aggregations. Others have speculated that instead of social groups, at least some of these finds represent Komodo dragon-like mobbing of carcasses, where aggressive competition leads to some of the predators being killed and cannibalized.
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1367_12
Currie has also speculated on the pack-hunting habits of Albertosaurus. The leg proportions of the smaller individuals were comparable to those of ornithomimids, which were probably among the fastest dinosaurs. Younger Albertosaurus were probably equally fleet-footed, or at least faster than their prey. Currie hypothesized that the younger members of the pack may have been responsible for driving their prey towards the adults, who were larger and more powerful, but also slower. Juveniles may also have had different lifestyles than adults, filling predator niches between the enormous adults and the smaller contemporaneous theropods, the largest of which were two orders of magnitude smaller than adult Albertosaurus in mass. A similar situation is observed in modern Komodo dragons, with hatchlings beginning life as small insectivores before growing to become the dominant predators on their islands. However, as the preservation of behaviour in the fossil record is exceedingly rare, these ideas cannot readily be tested. In 2010, Currie, though still favouring the hunting pack hypothesis, admitted that the concentration could have been brought about by other causes, such as a slowly rising water level during an extended flood. Palaeopathology In 2009, researchers hypothesized that smooth-edged holes found in the fossil jaws of tyrannosaurid dinosaurs such as Albertosaurus were caused by a parasite similar to Trichomonas gallinae, which infects birds. They suggested that tyrannosaurids transmitted the infection by biting each other, and that the infection impaired their ability to eat food.
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1367_13
In 2001, Bruce Rothschild and others published a study examining evidence for stress fractures and tendon avulsions in theropod dinosaurs and the implications for their behavior. They found that only one of the 319 Albertosaurus foot bones checked for stress fractures actually had them and none of the four hand bones did. The scientists found that stress fractures were "significantly" less common in Albertosaurus than in the carnosaur Allosaurus. ROM 807, the holotype of A. arctunguis (now referred to A. sarcophagus), had a deep hole in the iliac blade, although the describer of the species did not recognize this as pathological. The specimen also contains some exostosis on the fourth left metatarsal. In 1970, two of the five Albertosaurus sarcophagus specimens with humeri were reported by Dale Russel as having pathological damage to them. In 2010, the health of the Dry Island Albertosaurus assembly was reported upon. Most specimens showed no sign of disease. On three phalanges of the foot strange bony spurs, consisting of abnormal ossifications of the tendons, so-called enthesophytes, were present, their cause unknown. Two ribs and a belly-rib showed signs of breaking and healing. One adult specimen had a left lower jaw showing a puncture wound and both healed and unhealed bite marks. The low number of abnormalities compares favourably with the health condition of a Majungasaurus population of which it in 2007 was established that 19% of individuals showed bone pathologies. Palaeoecology
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1367_14
Palaeoecology Most fossils of Albertosaurus sarcophagus are known from the upper Horseshoe Canyon Formation in Alberta. These younger units of this geologic formation date to the early Maastrichtian stage of the Late Cretaceous Period, 70 to 68 Ma (million years ago). Immediately below this formation is the Bearpaw Shale, a marine formation representing a section of the Western Interior Seaway. The seaway was receding as the climate cooled and sea levels subsided towards the end of the Cretaceous, exposing land that had previously been underwater. It was not a smooth process, however, and the seaway would periodically rise to cover parts of the region throughout Horseshoe Canyon before finally receding altogether in the years after. Due to the changing sea levels, many different environments are represented in the Horseshoe Canyon Formation, including offshore and near-shore marine habitats and coastal habitats like lagoons, estuaries and tidal flats. Numerous coal seams represent ancient peat swamps. Like most of the other vertebrate fossils from the formation, Albertosaurus remains are found in deposits laid down in the deltas and floodplains of large rivers during the later half of Horseshoe Canyon times.
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1367_15
The fauna of the Horseshoe Canyon Formation is well-known, as vertebrate fossils, including those of dinosaurs, are quite common. Sharks, rays, sturgeons, bowfins, gars and the gar-like Aspidorhynchus made up the fish fauna. Mammals included multituberculates and the marsupial Didelphodon. The saltwater plesiosaur Leurospondylus has been found in marine sediments in the Horseshoe Canyon, while freshwater environments were populated by turtles, Champsosaurus, and crocodilians like Leidyosuchus and Stangerochampsa. Dinosaurs dominate the fauna, especially hadrosaurs, which make up half of all dinosaurs known, including the genera Edmontosaurus, Saurolophus and Hypacrosaurus. Ceratopsians and ornithomimids were also very common, together making up another third of the known fauna. Along with much rarer ankylosaurians and pachycephalosaurs, all of these animals would have been prey for a diverse array of carnivorous theropods, including troodontids, dromaeosaurids, and caenagnathids. Intermingled with the Albertosaurus remains of the Dry Island bonebed, the bones of the small theropod Albertonykus were found. Adult Albertosaurus were the apex predators in this environment, with intermediate niches possibly filled by juvenile albertosaurs. See also Timeline of tyrannosaur research References External links Late Cretaceous dinosaurs of North America Tyrannosaurids Fossil taxa described in 1905 Taxa named by Henry Fairfield Osborn Maastrichtian life Paleontology in Alberta Maastrichtian genus first appearances Maastrichtian genus extinctions Horseshoe Canyon fauna
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1368_0
In computer programming, assembly language (or assembler language), sometimes abbreviated asm, is any low-level programming language in which there is a very strong correspondence between the instructions in the language and the architecture's machine code instructions. Assembly language usually has one statement per machine instruction (1:1), but constants, comments, assembler directives, symbolic labels of, e.g., memory locations, registers, and macros are generally also supported. Assembly code is converted into executable machine code by a utility program referred to as an assembler. The term "assembler" is generally attributed to Wilkes, Wheeler and Gill in their 1951 book The Preparation of Programs for an Electronic Digital Computer, who, however, used the term to mean "a program that assembles another program consisting of several sections into a single program". The conversion process is referred to as assembly, as in assembling the source code. The computational step when an assembler is processing a program is called assembly time. Assembly language may also be called symbolic machine code. Because assembly depends on the machine code instructions, each assembly language is specific to a particular computer architecture. Sometimes there is more than one assembler for the same architecture, and sometimes an assembler is specific to an operating system or to particular operating systems. Most assembly languages do not provide specific syntax for operating system calls, and most assembly languages can be used universally with any operating system, as the language provides access to all the real capabilities of the processor, upon which all system call mechanisms ultimately rest. In contrast to assembly languages, most high-level programming languages are generally portable across multiple architectures but require interpreting or compiling, a much more complicated task than assembling.
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1368_1
Assembly language syntax Assembly language uses a mnemonic to represent, e.g., each low-level machine instruction or opcode, each directive, typically also each architectural register, flag, etc. Some of the mnemonics may be built in and some user defined. Many operations require one or more operands in order to form a complete instruction. Most assemblers permit named constants, registers, and labels for program and memory locations, and can calculate expressions for operands. Thus, programmers are freed from tedious repetitive calculations and assembler programs are much more readable than machine code. Depending on the architecture, these elements may also be combined for specific instructions or addressing modes using offsets or other data as well as fixed addresses. Many assemblers offer additional mechanisms to facilitate program development, to control the assembly process, and to aid debugging. Some are column oriented, with specific fields in specific columns; this was very common for machines using punched cards in the 1950s and early 1960s. Some assemblers have free-form syntax, with fields separated by delimiters, e.g., punctuation, white space. Some assemblers are hybrid, with, e.g., labels, in a specific column and other fields separated by delimiters; this became more common than column oriented syntax in the 1960s. IBM System/360 All of the IBM assemblers for System/360, by default, have a label in column 1, fields separated by delimiters in columns 2-71, a continuation indicator in column 72 and a sequence number in columns 73-80. The delimiter for label, opcode, operands and comments is spaces, while individual operands are separated by commas and parentheses.
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1368_2
Terminology A macro assembler is an assembler that includes a macroinstruction facility so that (parameterized) assembly language text can be represented by a name, and that name can be used to insert the expanded text into other code. Open code refers to any assembler input outside of a macro definition. A cross assembler (see also cross compiler) is an assembler that is run on a computer or operating system (the host system) of a different type from the system on which the resulting code is to run (the target system). Cross-assembling facilitates the development of programs for systems that do not have the resources to support software development, such as an embedded system or a microcontroller. In such a case, the resulting object code must be transferred to the target system, via read-only memory (ROM, EPROM, etc.), a programmer (when the read-only memory is integrated in the device, as in microcontrollers), or a data link using either an exact bit-by-bit copy of the object code or a text-based representation of that code (such as Intel hex or Motorola S-record). A high-level assembler is a program that provides language abstractions more often associated with high-level languages, such as advanced control structures (IF/THEN/ELSE, DO CASE, etc.) and high-level abstract data types, including structures/records, unions, classes, and sets. A microassembler is a program that helps prepare a microprogram, called firmware, to control the low level operation of a computer. A meta-assembler is "a program that accepts the syntactic and semantic description of an assembly language, and generates an assembler for that language", or that accepts an assembler source file along with such a description and assembles the source file in accordance with that description. "Meta-Symbol" assemblers for the SDS 9 Series and SDS Sigma series of computers are meta-assemblers. Sperry Univac also provided a Meta-Assembler for the UNIVAC 1100/2200 series. inline assembler (or embedded assembler) is assembler code contained within a high-level language program. This is most often used in systems programs which need direct access to the hardware. Key concepts
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1368_3
Key concepts Assembler An assembler program creates object code by translating combinations of mnemonics and syntax for operations and addressing modes into their numerical equivalents. This representation typically includes an operation code ("opcode") as well as other control bits and data. The assembler also calculates constant expressions and resolves symbolic names for memory locations and other entities. The use of symbolic references is a key feature of assemblers, saving tedious calculations and manual address updates after program modifications. Most assemblers also include macro facilities for performing textual substitution – e.g., to generate common short sequences of instructions as inline, instead of called subroutines. Some assemblers may also be able to perform some simple types of instruction set-specific optimizations. One concrete example of this may be the ubiquitous x86 assemblers from various vendors. Called jump-sizing, most of them are able to perform jump-instruction replacements (long jumps replaced by short or relative jumps) in any number of passes, on request. Others may even do simple rearrangement or insertion of instructions, such as some assemblers for RISC architectures that can help optimize a sensible instruction scheduling to exploit the CPU pipeline as efficiently as possible. Assemblers have been available since the 1950s, as the first step above machine language and before high-level programming languages such as Fortran, Algol, COBOL and Lisp. There have also been several classes of translators and semi-automatic code generators with properties similar to both assembly and high-level languages, with Speedcode as perhaps one of the better-known examples. There may be several assemblers with different syntax for a particular CPU or instruction set architecture. For instance, an instruction to add memory data to a register in a x86-family processor might be add eax,[ebx], in original Intel syntax, whereas this would be written addl (%ebx),%eax in the AT&T syntax used by the GNU Assembler. Despite different appearances, different syntactic forms generally generate the same numeric machine code. A single assembler may also have different modes in order to support variations in syntactic forms as well as their exact semantic interpretations (such as FASM-syntax, TASM-syntax, ideal mode, etc., in the special case of x86 assembly programming).
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1368_4
Number of passes There are two types of assemblers based on how many passes through the source are needed (how many times the assembler reads the source) to produce the object file. One-pass assemblers go through the source code once. Any symbol used before it is defined will require "errata" at the end of the object code (or, at least, no earlier than the point where the symbol is defined) telling the linker or the loader to "go back" and overwrite a placeholder which had been left where the as yet undefined symbol was used. Multi-pass assemblers create a table with all symbols and their values in the first passes, then use the table in later passes to generate code. In both cases, the assembler must be able to determine the size of each instruction on the initial passes in order to calculate the addresses of subsequent symbols. This means that if the size of an operation referring to an operand defined later depends on the type or distance of the operand, the assembler will make a pessimistic estimate when first encountering the operation, and if necessary, pad it with one or more "no-operation" instructions in a later pass or the errata. In an assembler with peephole optimization, addresses may be recalculated between passes to allow replacing pessimistic code with code tailored to the exact distance from the target. The original reason for the use of one-pass assemblers was memory size and speed of assembly – often a second pass would require storing the symbol table in memory (to handle forward references), rewinding and rereading the program source on tape, or rereading a deck of cards or punched paper tape. Later computers with much larger memories (especially disc storage), had the space to perform all necessary processing without such re-reading. The advantage of the multi-pass assembler is that the absence of errata makes the linking process (or the program load if the assembler directly produces executable code) faster.
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1368_5
Example: in the following code snippet, a one-pass assembler would be able to determine the address of the backward reference BKWD when assembling statement S2, but would not be able to determine the address of the forward reference FWD when assembling the branch statement S1; indeed, FWD may be undefined. A two-pass assembler would determine both addresses in pass 1, so they would be known when generating code in pass 2. B ... EQU * ... EQU * ... B High-level assemblers More sophisticated high-level assemblers provide language abstractions such as: High-level procedure/function declarations and invocations Advanced control structures (IF/THEN/ELSE, SWITCH) High-level abstract data types, including structures/records, unions, classes, and sets Sophisticated macro processing (although available on ordinary assemblers since the late 1950s for, e.g., the IBM 700 series and IBM 7000 series, and since the 1960s for IBM System/360 (S/360), amongst other machines) Object-oriented programming features such as classes, objects, abstraction, polymorphism, and inheritance See Language design below for more details. Assembly language A program written in assembly language consists of a series of mnemonic processor instructions and meta-statements (known variously as declarative operations, directives, pseudo-instructions, pseudo-operations and pseudo-ops), comments and data. Assembly language instructions usually consist of an opcode mnemonic followed by an operand, which might be a list of data, arguments or parameters. Some instructions may be "implied," which means the data upon which the instruction operates is implicitly defined by the instruction itself—such an instruction does not take an operand. The resulting statement is translated by an assembler into machine language instructions that can be loaded into memory and executed.
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1368_6
For example, the instruction below tells an x86/IA-32 processor to move an immediate 8-bit value into a register. The binary code for this instruction is 10110 followed by a 3-bit identifier for which register to use. The identifier for the AL register is 000, so the following machine code loads the AL register with the data 01100001. 10110000 01100001 This binary computer code can be made more human-readable by expressing it in hexadecimal as follows. B0 61 Here, B0 means 'Move a copy of the following value into AL, and 61 is a hexadecimal representation of the value 01100001, which is 97 in decimal. Assembly language for the 8086 family provides the mnemonic MOV (an abbreviation of move) for instructions such as this, so the machine code above can be written as follows in assembly language, complete with an explanatory comment if required, after the semicolon. This is much easier to read and to remember. MOV AL, 61h ; Load AL with 97 decimal (61 hex) In some assembly languages (including this one) the same mnemonic, such as MOV, may be used for a family of related instructions for loading, copying and moving data, whether these are immediate values, values in registers, or memory locations pointed to by values in registers or by immediate (a.k.a direct) addresses. Other assemblers may use separate opcode mnemonics such as L for "move memory to register", ST for "move register to memory", LR for "move register to register", MVI for "move immediate operand to memory", etc.
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1368_7
If the same mnemonic is used for different instructions, that means that the mnemonic corresponds to several different binary instruction codes, excluding data (e.g. the 61h in this example), depending on the operands that follow the mnemonic. For example, for the x86/IA-32 CPUs, the Intel assembly language syntax MOV AL, AH represents an instruction that moves the contents of register AH into register AL. The hexadecimal form of this instruction is: 88 E0 The first byte, 88h, identifies a move between a byte-sized register and either another register or memory, and the second byte, E0h, is encoded (with three bit-fields) to specify that both operands are registers, the source is AH, and the destination is AL. In a case like this where the same mnemonic can represent more than one binary instruction, the assembler determines which instruction to generate by examining the operands. In the first example, the operand 61h is a valid hexadecimal numeric constant and is not a valid register name, so only the B0 instruction can be applicable. In the second example, the operand AH is a valid register name and not a valid numeric constant (hexadecimal, decimal, octal, or binary), so only the 88 instruction can be applicable. Assembly languages are always designed so that this sort of unambiguousness is universally enforced by their syntax. For example, in the Intel x86 assembly language, a hexadecimal constant must start with a numeral digit, so that the hexadecimal number 'A' (equal to decimal ten) would be written as 0Ah or 0AH, not AH, specifically so that it cannot appear to be the name of register AH. (The same rule also prevents ambiguity with the names of registers BH, CH, and DH, as well as with any user-defined symbol that ends with the letter H and otherwise contains only characters that are hexadecimal digits, such as the word "BEACH".)
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1368_8
Returning to the original example, while the x86 opcode 10110000 (B0) copies an 8-bit value into the AL register, 10110001 (B1) moves it into CL and 10110010 (B2) does so into DL. Assembly language examples for these follow. MOV AL, 1h ; Load AL with immediate value 1 MOV CL, 2h ; Load CL with immediate value 2 MOV DL, 3h ; Load DL with immediate value 3 The syntax of MOV can also be more complex as the following examples show. MOV EAX, [EBX] ; Move the 4 bytes in memory at the address contained in EBX into EAX MOV [ESI+EAX], CL ; Move the contents of CL into the byte at address ESI+EAX MOV DS, DX ; Move the contents of DX into segment register DS In each case, the MOV mnemonic is translated directly into one of the opcodes 88-8C, 8E, A0-A3, B0-BF, C6 or C7 by an assembler, and the programmer normally does not have to know or remember which.
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1368_9
Transforming assembly language into machine code is the job of an assembler, and the reverse can at least partially be achieved by a disassembler. Unlike high-level languages, there is a one-to-one correspondence between many simple assembly statements and machine language instructions. However, in some cases, an assembler may provide pseudoinstructions (essentially macros) which expand into several machine language instructions to provide commonly needed functionality. For example, for a machine that lacks a "branch if greater or equal" instruction, an assembler may provide a pseudoinstruction that expands to the machine's "set if less than" and "branch if zero (on the result of the set instruction)". Most full-featured assemblers also provide a rich macro language (discussed below) which is used by vendors and programmers to generate more complex code and data sequences. Since the information about pseudoinstructions and macros defined in the assembler environment is not present in the object program, a disassembler cannot reconstruct the macro and pseudoinstruction invocations but can only disassemble the actual machine instructions that the assembler generated from those abstract assembly-language entities. Likewise, since comments in the assembly language source file are ignored by the assembler and have no effect on the object code it generates, a disassembler is always completely unable to recover source comments. Each computer architecture has its own machine language. Computers differ in the number and type of operations they support, in the different sizes and numbers of registers, and in the representations of data in storage. While most general-purpose computers are able to carry out essentially the same functionality, the ways they do so differ; the corresponding assembly languages reflect these differences. Multiple sets of mnemonics or assembly-language syntax may exist for a single instruction set, typically instantiated in different assembler programs. In these cases, the most popular one is usually that supplied by the CPU manufacturer and used in its documentation.
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1368_10
Two examples of CPUs that have two different sets of mnemonics are the Intel 8080 family and the Intel 8086/8088. Because Intel claimed copyright on its assembly language mnemonics (on each page of their documentation published in the 1970s and early 1980s, at least), some companies that independently produced CPUs compatible with Intel instruction sets invented their own mnemonics. The Zilog Z80 CPU, an enhancement of the Intel 8080A, supports all the 8080A instructions plus many more; Zilog invented an entirely new assembly language, not only for the new instructions but also for all of the 8080A instructions. For example, where Intel uses the mnemonics MOV, MVI, LDA, STA, LXI, LDAX, STAX, LHLD, and SHLD for various data transfer instructions, the Z80 assembly language uses the mnemonic LD for all of them. A similar case is the NEC V20 and V30 CPUs, enhanced copies of the Intel 8086 and 8088, respectively. Like Zilog with the Z80, NEC invented new mnemonics for all of the 8086 and 8088 instructions, to avoid accusations of infringement of Intel's copyright. (It is questionable whether such copyrights can be valid, and later CPU companies such as AMD and Cyrix republished Intel's x86/IA-32 instruction mnemonics exactly with neither permission nor legal penalty.) It is doubtful whether in practice many people who programmed the V20 and V30 actually wrote in NEC's assembly language rather than Intel's; since any two assembly languages for the same instruction set architecture are isomorphic (somewhat like English and Pig Latin), there is no requirement to use a manufacturer's own published assembly language with that manufacturer's products. Language design Basic elements There is a large degree of diversity in the way the authors of assemblers categorize statements and in the nomenclature that they use. In particular, some describe anything other than a machine mnemonic or extended mnemonic as a pseudo-operation (pseudo-op). A typical assembly language consists of 3 types of instruction statements that are used to define program operations: Opcode mnemonics Data definitions Assembly directives
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1368_11
Opcode mnemonics Data definitions Assembly directives Opcode mnemonics and extended mnemonics Instructions (statements) in assembly language are generally very simple, unlike those in high-level languages. Generally, a mnemonic is a symbolic name for a single executable machine language instruction (an opcode), and there is at least one opcode mnemonic defined for each machine language instruction. Each instruction typically consists of an operation or opcode plus zero or more operands. Most instructions refer to a single value or a pair of values. Operands can be immediate (value coded in the instruction itself), registers specified in the instruction or implied, or the addresses of data located elsewhere in storage. This is determined by the underlying processor architecture: the assembler merely reflects how this architecture works. Extended mnemonics are often used to specify a combination of an opcode with a specific operand, e.g., the System/360 assemblers use as an extended mnemonic for with a mask of 15 and ("NO OPeration" – do nothing for one step) for with a mask of 0. Extended mnemonics are often used to support specialized uses of instructions, often for purposes not obvious from the instruction name. For example, many CPU's do not have an explicit NOP instruction, but do have instructions that can be used for the purpose. In 8086 CPUs the instruction is used for , with being a pseudo-opcode to encode the instruction . Some disassemblers recognize this and will decode the instruction as . Similarly, IBM assemblers for System/360 and System/370 use the extended mnemonics and for and with zero masks. For the SPARC architecture, these are known as synthetic instructions. Some assemblers also support simple built-in macro-instructions that generate two or more machine instructions. For instance, with some Z80 assemblers the instruction is recognized to generate followed by . These are sometimes known as pseudo-opcodes. Mnemonics are arbitrary symbols; in 1985 the IEEE published Standard 694 for a uniform set of mnemonics to be used by all assemblers. The standard has since been withdrawn.
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1368_12
Data directives There are instructions used to define data elements to hold data and variables. They define the type of data, the length and the alignment of data. These instructions can also define whether the data is available to outside programs (programs assembled separately) or only to the program in which the data section is defined. Some assemblers classify these as pseudo-ops. Assembly directives Assembly directives, also called pseudo-opcodes, pseudo-operations or pseudo-ops, are commands given to an assembler "directing it to perform operations other than assembling instructions". Directives affect how the assembler operates and "may affect the object code, the symbol table, the listing file, and the values of internal assembler parameters". Sometimes the term pseudo-opcode is reserved for directives that generate object code, such as those that generate data. The names of pseudo-ops often start with a dot to distinguish them from machine instructions. Pseudo-ops can make the assembly of the program dependent on parameters input by a programmer, so that one program can be assembled in different ways, perhaps for different applications. Or, a pseudo-op can be used to manipulate presentation of a program to make it easier to read and maintain. Another common use of pseudo-ops is to reserve storage areas for run-time data and optionally initialize their contents to known values. Symbolic assemblers let programmers associate arbitrary names (labels or symbols) with memory locations and various constants. Usually, every constant and variable is given a name so instructions can reference those locations by name, thus promoting self-documenting code. In executable code, the name of each subroutine is associated with its entry point, so any calls to a subroutine can use its name. Inside subroutines, GOTO destinations are given labels. Some assemblers support local symbols which are often lexically distinct from normal symbols (e.g., the use of "10$" as a GOTO destination). Some assemblers, such as NASM, provide flexible symbol management, letting programmers manage different namespaces, automatically calculate offsets within data structures, and assign labels that refer to literal values or the result of simple computations performed by the assembler. Labels can also be used to initialize constants and variables with relocatable addresses.
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1368_13
Assembly languages, like most other computer languages, allow comments to be added to program source code that will be ignored during assembly. Judicious commenting is essential in assembly language programs, as the meaning and purpose of a sequence of binary machine instructions can be difficult to determine. The "raw" (uncommented) assembly language generated by compilers or disassemblers is quite difficult to read when changes must be made. Macros Many assemblers support predefined macros, and others support programmer-defined (and repeatedly re-definable) macros involving sequences of text lines in which variables and constants are embedded. The macro definition is most commonly a mixture of assembler statements, e.g., directives, symbolic machine instructions, and templates for assembler statements. This sequence of text lines may include opcodes or directives. Once a macro has been defined its name may be used in place of a mnemonic. When the assembler processes such a statement, it replaces the statement with the text lines associated with that macro, then processes them as if they existed in the source code file (including, in some assemblers, expansion of any macros existing in the replacement text). Macros in this sense date to IBM autocoders of the 1950s. Macro assemblers typically have directives to, e.g., define macros, define variables, set variables to the result of an arithmetic, logical or string expression, iterate, conditionally generate code. Some of those directives may be restricted to use within a macro definition, e.g., MEXIT in HLASM, while others may be permitted within open code (outside macro definitions), e.g., AIF and COPY in HLASM. In assembly language, the term "macro" represents a more comprehensive concept than it does in some other contexts, such as the pre-processor in the C programming language, where its #define directive typically is used to create short single line macros. Assembler macro instructions, like macros in PL/I and some other languages, can be lengthy "programs" by themselves, executed by interpretation by the assembler during assembly.
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1368_14
Since macros can have 'short' names but expand to several or indeed many lines of code, they can be used to make assembly language programs appear to be far shorter, requiring fewer lines of source code, as with higher level languages. They can also be used to add higher levels of structure to assembly programs, optionally introduce embedded debugging code via parameters and other similar features. Macro assemblers often allow macros to take parameters. Some assemblers include quite sophisticated macro languages, incorporating such high-level language elements as optional parameters, symbolic variables, conditionals, string manipulation, and arithmetic operations, all usable during the execution of a given macro, and allowing macros to save context or exchange information. Thus a macro might generate numerous assembly language instructions or data definitions, based on the macro arguments. This could be used to generate record-style data structures or "unrolled" loops, for example, or could generate entire algorithms based on complex parameters. For instance, a "sort" macro could accept the specification of a complex sort key and generate code crafted for that specific key, not needing the run-time tests that would be required for a general procedure interpreting the specification. An organization using assembly language that has been heavily extended using such a macro suite can be considered to be working in a higher-level language since such programmers are not working with a computer's lowest-level conceptual elements. Underlining this point, macros were used to implement an early virtual machine in SNOBOL4 (1967), which was written in the SNOBOL Implementation Language (SIL), an assembly language for a virtual machine. The target machine would translate this to its native code using a macro assembler. This allowed a high degree of portability for the time. Macros were used to customize large scale software systems for specific customers in the mainframe era and were also used by customer personnel to satisfy their employers' needs by making specific versions of manufacturer operating systems. This was done, for example, by systems programmers working with IBM's Conversational Monitor System / Virtual Machine (VM/CMS) and with IBM's "real time transaction processing" add-ons, Customer Information Control System CICS, and ACP/TPF, the airline/financial system that began in the 1970s and still runs many large computer reservation systems (CRS) and credit card systems today.
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1368_15
It is also possible to use solely the macro processing abilities of an assembler to generate code written in completely different languages, for example, to generate a version of a program in COBOL using a pure macro assembler program containing lines of COBOL code inside assembly time operators instructing the assembler to generate arbitrary code. IBM OS/360 uses macros to perform system generation. The user specifies options by coding a series of assembler macros. Assembling these macros generates a job stream to build the system, including job control language and utility control statements. This is because, as was realized in the 1960s, the concept of "macro processing" is independent of the concept of "assembly", the former being in modern terms more word processing, text processing, than generating object code. The concept of macro processing appeared, and appears, in the C programming language, which supports "preprocessor instructions" to set variables, and make conditional tests on their values. Unlike certain previous macro processors inside assemblers, the C preprocessor is not Turing-complete because it lacks the ability to either loop or "go to", the latter allowing programs to loop. Despite the power of macro processing, it fell into disuse in many high level languages (major exceptions being C, C++ and PL/I) while remaining a perennial for assemblers. Macro parameter substitution is strictly by name: at macro processing time, the value of a parameter is textually substituted for its name. The most famous class of bugs resulting was the use of a parameter that itself was an expression and not a simple name when the macro writer expected a name. In the macro: foo: macro a load a*b the intention was that the caller would provide the name of a variable, and the "global" variable or constant b would be used to multiply "a". If foo is called with the parameter a-c, the macro expansion of load a-c*b occurs. To avoid any possible ambiguity, users of macro processors can parenthesize formal parameters inside macro definitions, or callers can parenthesize the input parameters. Support for structured programming
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1368_16
Support for structured programming Packages of macros have been written providing structured programming elements to encode execution flow. The earliest example of this approach was in the Concept-14 macro set, originally proposed by Harlan Mills (March 1970), and implemented by Marvin Kessler at IBM's Federal Systems Division, which provided IF/ELSE/ENDIF and similar control flow blocks for OS/360 assembler programs. This was a way to reduce or eliminate the use of GOTO operations in assembly code, one of the main factors causing spaghetti code in assembly language. This approach was widely accepted in the early 1980s (the latter days of large-scale assembly language use). IBM's High Level Assembler Toolkit includes such a macro package. A curious design was A-natural, a "stream-oriented" assembler for 8080/Z80, processors from Whitesmiths Ltd. (developers of the Unix-like Idris operating system, and what was reported to be the first commercial C compiler). The language was classified as an assembler because it worked with raw machine elements such as opcodes, registers, and memory references; but it incorporated an expression syntax to indicate execution order. Parentheses and other special symbols, along with block-oriented structured programming constructs, controlled the sequence of the generated instructions. A-natural was built as the object language of a C compiler, rather than for hand-coding, but its logical syntax won some fans. There has been little apparent demand for more sophisticated assemblers since the decline of large-scale assembly language development. In spite of that, they are still being developed and applied in cases where resource constraints or peculiarities in the target system's architecture prevent the effective use of higher-level languages. Assemblers with a strong macro engine allow structured programming via macros, such as the switch macro provided with the Masm32 package (this code is a complete program): include \masm32\include\masm32rt.inc ; use the Masm32 library
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1368_17
.code demomain: REPEAT 20 switch rv(nrandom, 9) ; generate a number between 0 and 8 mov ecx, 7 case 0 print "case 0" case ecx ; in contrast to most other programming languages, print "case 7" ; the Masm32 switch allows "variable cases" case 1 .. 3 .if eax==1 print "case 1" .elseif eax==2 print "case 2" .else print "cases 1 to 3: other" .endif case 4, 6, 8 print "cases 4, 6 or 8" default mov ebx, 19 ; print 20 stars .Repeat print "*" dec ebx .Until Sign? ; loop until the sign flag is set endsw print chr$(13, 10) ENDM exit end demomain Use of assembly language Historical perspective Assembly languages were not available at the time when the stored-program computer was introduced. Kathleen Booth "is credited with inventing assembly language" based on theoretical work she began in 1947, while working on the ARC2 at Birkbeck, University of London following consultation by Andrew Booth (later her husband) with mathematician John von Neumann and physicist Herman Goldstine at the Institute for Advanced Study. In late 1948, the Electronic Delay Storage Automatic Calculator (EDSAC) had an assembler (named "initial orders") integrated into its bootstrap program. It used one-letter mnemonics developed by David Wheeler, who is credited by the IEEE Computer Society as the creator of the first "assembler". Reports on the EDSAC introduced the term "assembly" for the process of combining fields into an instruction word. SOAP (Symbolic Optimal Assembly Program) was an assembly language for the IBM 650 computer written by Stan Poley in 1955. Assembly languages eliminate much of the error-prone, tedious, and time-consuming first-generation programming needed with the earliest computers, freeing programmers from tedium such as remembering numeric codes and calculating addresses.
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1368_18
Assembly languages were once widely used for all sorts of programming. However, by the 1980s (1990s on microcomputers), their use had largely been supplanted by higher-level languages, in the search for improved programming productivity. Today, assembly language is still used for direct hardware manipulation, access to specialized processor instructions, or to address critical performance issues. Typical uses are device drivers, low-level embedded systems, and real-time systems. Historically, numerous programs have been written entirely in assembly language. The Burroughs MCP (1961) was the first computer for which an operating system was not developed entirely in assembly language; it was written in Executive Systems Problem Oriented Language (ESPOL), an Algol dialect. Many commercial applications were written in assembly language as well, including a large amount of the IBM mainframe software written by large corporations. COBOL, FORTRAN and some PL/I eventually displaced much of this work, although a number of large organizations retained assembly-language application infrastructures well into the 1990s. Most early microcomputers relied on hand-coded assembly language, including most operating systems and large applications. This was because these systems had severe resource constraints, imposed idiosyncratic memory and display architectures, and provided limited, buggy system services. Perhaps more important was the lack of first-class high-level language compilers suitable for microcomputer use. A psychological factor may have also played a role: the first generation of microcomputer programmers retained a hobbyist, "wires and pliers" attitude. In a more commercial context, the biggest reasons for using assembly language were minimal bloat (size), minimal overhead, greater speed, and reliability. Typical examples of large assembly language programs from this time are IBM PC DOS operating systems, the Turbo Pascal compiler and early applications such as the spreadsheet program Lotus 1-2-3. Assembly language was used to get the best performance out of the Sega Saturn, a console that was notoriously challenging to develop and program games for. The 1993 arcade game NBA Jam is another example.
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1368_19
Assembly language has long been the primary development language for many popular home computers of the 1980s and 1990s (such as the MSX, Sinclair ZX Spectrum, Commodore 64, Commodore Amiga, and Atari ST). This was in large part because interpreted BASIC dialects on these systems offered insufficient execution speed, as well as insufficient facilities to take full advantage of the available hardware on these systems. Some systems even have an integrated development environment (IDE) with highly advanced debugging and macro facilities. Some compilers available for the Radio Shack TRS-80 and its successors had the capability to combine inline assembly source with high-level program statements. Upon compilation, a built-in assembler produced inline machine code. Current usage There have always been debates over the usefulness and performance of assembly language relative to high-level languages. Although assembly language has specific niche uses where it is important (see below), there are other tools for optimization. , the TIOBE index of programming language popularity ranks assembly language at 11, ahead of Visual Basic, for example. Assembler can be used to optimize for speed or optimize for size. In the case of speed optimization, modern optimizing compilers are claimed to render high-level languages into code that can run as fast as hand-written assembly, despite the counter-examples that can be found. The complexity of modern processors and memory sub-systems makes effective optimization increasingly difficult for compilers, as well as for assembly programmers. Moreover, increasing processor performance has meant that most CPUs sit idle most of the time, with delays caused by predictable bottlenecks such as cache misses, I/O operations and paging. This has made raw code execution speed a non-issue for many programmers. There are some situations in which developers might choose to use assembly language:
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1368_20
Writing code for systems with that have limited high-level language options such as the Atari 2600, Commodore 64, and graphing calculators. Programs for these computers of 1970s and 1980s are often written in the context of demoscene or retrogaming subcultures. Code that must interact directly with the hardware, for example in device drivers and interrupt handlers. In an embedded processor or DSP, high-repetition interrupts require the shortest number of cycles per interrupt, such as an interrupt that occurs 1000 or 10000 times a second. Programs that need to use processor-specific instructions not implemented in a compiler. A common example is the bitwise rotation instruction at the core of many encryption algorithms, as well as querying the parity of a byte or the 4-bit carry of an addition. A stand-alone executable of compact size is required that must execute without recourse to the run-time components or libraries associated with a high-level language. Examples have included firmware for telephones, automobile fuel and ignition systems, air-conditioning control systems, security systems, and sensors. Programs with performance-sensitive inner loops, where assembly language provides optimization opportunities that are difficult to achieve in a high-level language. For example, linear algebra with BLAS or discrete cosine transformation (e.g. SIMD assembly version from x264). Programs that create vectorized functions for programs in higher-level languages such as C. In the higher-level language this is sometimes aided by compiler intrinsic functions which map directly to SIMD mnemonics, but nevertheless result in a one-to-one assembly conversion specific for the given vector processor. Real-time programs such as simulations, flight navigation systems, and medical equipment. For example, in a fly-by-wire system, telemetry must be interpreted and acted upon within strict time constraints. Such systems must eliminate sources of unpredictable delays, which may be created by (some) interpreted languages, automatic garbage collection, paging operations, or preemptive multitasking. However, some higher-level languages incorporate run-time components and operating system interfaces that can introduce such delays. Choosing assembly or lower level languages for such systems gives programmers greater visibility and control over processing details.
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1368_21
Cryptographic algorithms that must always take strictly the same time to execute, preventing timing attacks. Modify and extend legacy code written for IBM mainframe computers. Situations where complete control over the environment is required, in extremely high-security situations where nothing can be taken for granted. Computer viruses, bootloaders, certain device drivers, or other items very close to the hardware or low-level operating system. Instruction set simulators for monitoring, tracing and debugging where additional overhead is kept to a minimum. Situations where no high-level language exists, on a new or specialized processor for which no cross compiler is available. Reverse-engineering and modifying program files such as: existing binaries that may or may not have originally been written in a high-level language, for example when trying to recreate programs for which source code is not available or has been lost, or cracking copy protection of proprietary software. Video games (also termed ROM hacking), which is possible via several methods. The most widely employed method is altering program code at the assembly language level.
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1368_22
Assembly language is still taught in most computer science and electronic engineering programs. Although few programmers today regularly work with assembly language as a tool, the underlying concepts remain important. Such fundamental topics as binary arithmetic, memory allocation, stack processing, character set encoding, interrupt processing, and compiler design would be hard to study in detail without a grasp of how a computer operates at the hardware level. Since a computer's behavior is fundamentally defined by its instruction set, the logical way to learn such concepts is to study an assembly language. Most modern computers have similar instruction sets. Therefore, studying a single assembly language is sufficient to learn: I) the basic concepts; II) to recognize situations where the use of assembly language might be appropriate; and III) to see how efficient executable code can be created from high-level languages.
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1368_23
Typical applications Assembly language is typically used in a system's boot code, the low-level code that initializes and tests the system hardware prior to booting the operating system and is often stored in ROM. (BIOS on IBM-compatible PC systems and CP/M is an example.) Assembly language is often used for low-level code, for instance for operating system kernels, which cannot rely on the availability of pre-existing system calls and must indeed implement them for the particular processor architecture on which the system will be running. Some compilers translate high-level languages into assembly first before fully compiling, allowing the assembly code to be viewed for debugging and optimization purposes. Some compilers for relatively low-level languages, such as Pascal or C, allow the programmer to embed assembly language directly in the source code (so called inline assembly). Programs using such facilities can then construct abstractions using different assembly language on each hardware platform. The system's portable code can then use these processor-specific components through a uniform interface. Assembly language is useful in reverse engineering. Many programs are distributed only in machine code form which is straightforward to translate into assembly language by a disassembler, but more difficult to translate into a higher-level language through a decompiler. Tools such as the Interactive Disassembler make extensive use of disassembly for such a purpose. This technique is used by hackers to crack commercial software, and competitors to produce software with similar results from competing companies. Assembly language is used to enhance speed of execution, especially in early personal computers with limited processing power and RAM. Assemblers can be used to generate blocks of data, with no high-level language overhead, from formatted and commented source code, to be used by other code. See also Compiler Comparison of assemblers Disassembler Hexadecimal Instruction set architecture Little man computer – an educational computer model with a base-10 assembly language Nibble Typed assembly language Notes References Further reading (2+xiv+270+6 pages) Kann, Charles W. (2021). "Introduction to Assembly Language Programming: From Soup to Nuts: ARM Edition" ("An online book full of helpful ASM info, tutorials and code examples" by the ASM Community, archived at the internet archive.) External links
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1368_24
External links Unix Assembly Language Programming Linux Assembly PPR: Learning Assembly Language NASM – The Netwide Assembler (a popular assembly language) Assembly Language Programming Examples Authoring Windows Applications In Assembly Language Assembly Optimization Tips by Mark Larson The table for assembly language to machine code Assembly language Computer-related introductions in 1949 Embedded systems Low-level programming languages Programming language implementation Programming languages created in 1949
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1369_0
In the ancient Greek myths, ambrosia (, ) is the food or drink of the Greek gods, often depicted as conferring longevity or immortality upon whoever consumed it. It was brought to the gods in Olympus by doves and served by either Hebe or Ganymede at the heavenly feast. Ambrosia is sometimes depicted in ancient art as distributed by a nymph labeled with that name and a nurse of Dionysus. Definition Ambrosia is very closely related to the gods' other form of sustenance, nectar. The two terms may not have originally been distinguished; though in Homer's poems nectar is usually the drink and ambrosia the food of the gods; it was with ambrosia Hera "cleansed all defilement from her lovely flesh", and with ambrosia Athena prepared Penelope in her sleep, so that when she appeared for the final time before her suitors, the effects of years had been stripped away, and they were inflamed with passion at the sight of her. On the other hand, in Alcman, nectar is the food, and in Sappho and Anaxandrides, ambrosia is the drink. A character in Aristophanes' Knights says, "I dreamed the goddess poured ambrosia over your head—out of a ladle." Both descriptions could be correct, as ambrosia could be a liquid considered a food (such as honey). The consumption of ambrosia was typically reserved for divine beings. Upon his assumption into immortality on Olympus, Heracles is given ambrosia by Athena, while the hero Tydeus is denied the same thing when the goddess discovers him eating human brains. In one version of the myth of Tantalus, part of Tantalus' crime is that after tasting ambrosia himself, he attempts to steal some to give to other mortals. Those who consume ambrosia typically have ichor, not blood, in their veins.
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1369_1
Both nectar and ambrosia are fragrant, and may be used as perfume: in the Odyssey Menelaus and his men are disguised as seals in untanned seal skins, "...and the deadly smell of the seal skins vexed us sore; but the goddess saved us; she brought ambrosia and put it under our nostrils." Homer speaks of ambrosial raiment, ambrosial locks of hair, even the gods' ambrosial sandals. Among later writers, ambrosia has been so often used with generic meanings of "delightful liquid" that such late writers as Athenaeus, Paulus and Dioscurides employ it as a technical terms in contexts of cookery, medicine, and botany. Pliny used the term in connection with different plants, as did early herbalists. Additionally, some modern ethnomycologists, such as Danny Staples, identify ambrosia with the hallucinogenic mushroom Amanita muscaria: "...it was the food of the gods, their ambrosia, and nectar was the pressed sap of its juices", Staples asserts. W. H. Roscher thinks that both nectar and ambrosia were kinds of honey, in which case their power of conferring immortality would be due to the supposed healing and cleansing powers of honey, and because fermented honey (mead) preceded wine as an entheogen in the Aegean world; on some Minoan seals, goddesses were represented with bee faces (compare Merope and Melissa).
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1369_2
Etymology The concept of an immortality drink is attested in at least two ancient Indo-European languages: Greek and Sanskrit. The Greek ἀμβροσία (ambrosia) is semantically linked to the Sanskrit (amṛta) as both words denote a drink or food that gods use to achieve immortality. The two words appear to be derived from the same Indo-European form *ṇ-mṛ-tós, "un-dying" (n-: negative prefix from which the prefix a- in both Greek and Sanskrit are derived; mṛ: zero grade of *mer-, "to die"; and -to-: adjectival suffix). A semantically similar etymology exists for nectar, the beverage of the gods (Greek: νέκταρ néktar) presumed to be a compound of the PIE roots *nek-, "death", and -*tar, "overcoming". Other examples in mythology
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1369_3
Other examples in mythology In one version of the story of the birth of Achilles, Thetis anoints the infant with ambrosia and passes the child through the fire to make him immortal but Peleus, appalled, stops her, leaving only his heel unimmortalised (Argonautica 4.869–879). In the Iliad xvi, Apollo washes the black blood from the corpse of Sarpedon and anoints it with ambrosia, readying it for its dreamlike return to Sarpedon's native Lycia. Similarly, Thetis anoints the corpse of Patroclus in order to preserve it. Ambrosia and nectar are depicted as unguents (xiv. 170; xix. 38). In the Odyssey, Calypso is described as having "spread a table with ambrosia and set it by Hermes, and mixed the rosy-red nectar." It is ambiguous whether he means the ambrosia itself is rosy-red, or if he is describing a rosy-red nectar Hermes drinks along with the ambrosia. Later, Circe mentions to Odysseus that a flock of doves are the bringers of ambrosia to Olympus. In the Odyssey (ix.345–359), Polyphemus likens the wine given to him by Odysseus to ambrosia and nectar. One of the impieties of Tantalus, according to Pindar, was that he offered to his guests the ambrosia of the Deathless Ones, a theft akin to that of Prometheus, Karl Kerenyi noted (in Heroes of the Greeks). In the Homeric hymn to Aphrodite, the goddess uses "ambrosial bridal oil that she had ready perfumed." In the story of Eros and Psyche as told by Apuleius, Psyche is given ambrosia upon her completion of the quests set by Aphrodite and her acceptance on Olympus. After she partakes, she and Eros are wed as gods. In the Aeneid, Aeneas encounters his mother in an alternate, or illusory form. When she became her godly form "Her hair's ambrosia breathed a holy fragrance." Lycurgus of Thrace and Ambrosia
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1369_4
Lycurgus of Thrace and Ambrosia Lycurgus, king of Thrace, forbade the cult of Dionysus, whom he drove from Thrace, and attacked the gods' entourage when they celebrated the god. Among them was Ambrosia, who turned herself into a grapevine to hide from his wrath. Dionysus, enraged by the king's actions, drove him mad. In his fit of insanity he killed his son, whom he mistook for a stock of ivy, and then himself. See also Elixir of life, a potion sought by alchemy to produce immortality Ichor, blood of the Greek gods, related to ambrosia Iðunn's apples in Norse mythology Manna, food given by God to the Israelites Peaches of Immortality in Chinese mythology Pill of Immortality Silphium Soma (drink), a ritual drink of importance among the early Vedic peoples and Indo-Iranians. References Sources Clay, Jenny Strauss, "Immortal and ageless forever", The Classical Journal 77.2 (December 1981:pp. 112–117). Ruck, Carl A.P. and Danny Staples, The World of Classical Myth 1994, p. 26 et seq. Wright, F. A., "The Food of the Gods", The Classical Review 31.1, (February 1917:4–6). External links Ancient Greek cuisine Fictional food and drink Mount Olympus Mythological medicines and drugs Mythological food and drink
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1370_0
Ambrose of Milan (; ), venerated as Saint Ambrose, was the Bishop of Milan, a theologian and statesman. He expressed himself prominently as a public figure, fiercely promoting the Latin Church against Arianism and paganism. He left a substantial collection of writings, of which the best known include the ethical commentary De officiis ministrorum (377–391), and the exegetical (386–390). His preachings, his actions and his literary works, in addition to his innovative musical hymnography, made him one of the most influential ecclesiastical figures of the 4th century. Ambrose was serving as the Roman governor of Aemilia-Liguria in Milan when he was unexpectedly made Bishop of Milan in 374 by popular acclamation. As bishop, he took a firm position against Arianism and attempted to mediate the conflict between the emperors Theodosius I and Magnus Maximus. Tradition credits Ambrose with developing an antiphonal chant, known as Ambrosian chant, and for composing the "Te Deum" hymn, though modern scholars now reject both of these attributions. Ambrose's authorship on at least four hymns, including the well-known "Veni redemptor gentium", is secure; they form the core of the Ambrosian hymns, which includes others that are sometimes attributed to him. He also had notable influence on Augustine of Hippo (354–430), particularly in converting him to Christianity. Before the 16th century, Western Christianity identified Ambrose as one of its four traditional Doctors of the Church. He is considered a saint by the Catholic Church, Eastern Orthodox Church, Anglican Communion, and various Lutheran denominations, and venerated as the patron saint of Milan and beekeepers. Life and background Legends about Ambrose had spread through the empire long before his biography was written, making it difficult for modern historians to understand his true character and fairly place his behavior within the context of antiquity. Most agree he was the personification of his era. As such, Ambrose was a genuinely spiritual man who spoke up and defended his faith against opponents, an aristocrat who retained many of the attitudes and practices of a Roman governor, while also being an ascetic who served the poor. Early life
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1370_1
Early life Ambrose was born into a Roman Christian family in the year 339. Ambrose himself wrote that he was 53 years old in his letter number 49 which has been dated to 392. He began life in Augusta Trevorum (modern Trier) the capitol of the Roman province of Gallia Belgica in what was then northeastern Gaul and is now modern Germany. Who exactly his father was is disagreed upon by scholars. His father is sometimes identified with Aurelius Ambrosius, a praetorian prefect of Gaul; but some scholars identify his father as an official named Uranius who received an imperial constitution dated 3 February 339 (addressed in a brief extract from one of the three emperors ruling in 339, Constantine II, Constantius II, or Constans, in the Codex Theodosianus, book XI.5). What does seem certain is that Ambrose was born in Trier and his father was either the praetorian prefect or part of his administration. There is a legend about Ambrose as an infant contending that a swarm of bees settled on his face while he lay in his cradle, leaving behind a drop of honey. His father is said to have considered this a sign of his future eloquence and honeyed tongue. For this reason, bees and beehives often appear in the saint's symbology. Ambrose' mother was a woman of intellect and piety. It is probable she was a member of the Roman family Aurelii Symmachi, and thus Ambrose was cousin of the orator Quintus Aurelius Symmachus. The family had produced one martyr (the virgin Soteris) in its history. Ambrose was the youngest of three children. His siblings were Satyrus, the subject of Ambrose's De excessu fratris Satyri, and Marcellina, who made a profession of virginity sometime between 352 and 355; Pope Liberius himself conferred the veil upon her. Both Ambrose's siblings also became venerated as saints.
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1370_2
Some time early in the life of Ambrose, his father died, and at an unknown later date, his mother fled Trier with her three children, whereupon the family moved to Rome. There Ambrose studied literature, law, and rhetoric. He then followed in his father's footsteps and entered public service. Praetorian Prefect Sextus Claudius Petronius Probus first gave him a place as his council, and then in about 372 made him governor of Liguria and Emilia, with headquarters at Milan. Bishop of Milan In 374 the bishop of Milan, Auxentius, an Arian, died, and the Arians challenged the succession. Ambrose went to the church where the election was to take place to prevent an uproar which was probable in this crisis. His address was interrupted by a call, "Ambrose, bishop!", which was taken up by the whole assembly. Ambrose was known to be Nicene Christian in belief, but he was considered acceptable to Arians due to the charity he had shown in theological matters in this regard. At first he energetically refused the office, for which he felt he was in no way prepared: Ambrose was a relatively new Christian who was not yet baptized nor formally trained in theology. Ambrose fled to a colleague's home seeking to hide. Upon receiving a letter from the Emperor Gratian praising the appropriateness of Rome appointing individuals worthy of holy positions, Ambrose's host gave him up. Within a week, he was baptized, ordained and duly consecrated as the next bishop of Milan. This was the first time in the West that a member of the upper class of high officials had accepted the office of bishop. As bishop, he immediately adopted an ascetic lifestyle, apportioned his money to the poor, donating all of his land, making only provision for his sister Marcellina. This raised his popularity even further; it was his popularity with the people that gave him considerable political leverage throughout his career. Upon the unexpected appointment of Ambrose to the episcopate, his brother Satyrus resigned a prefecture in order to move to Milan, where he took over managing the diocese's temporal affairs.
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1370_3
Arianism Arius was a Christian priest who asserted (around the year 300) that God the Father must have created the Son, making the Son a lesser being who was not eternal and of a different "essence" than God the Father was. This Christology was contrary to tradition, yet it quickly spread through Egypt and Libya and the other Roman provinces. Bishops engaged in "wordy warfare," and the people divided into parties, sometimes demonstrating in the streets in support of one side or the other. Arianism appealed to many high level leaders and clergy in both the Western and Eastern empires. Although the western Emperor Gratian supported orthodoxy, the younger Valentinian II, who became his colleague in the Empire, adhered to the Arian creed. Ambrose sought to theologically refute Arian propositions, but Ambrose did not sway the young prince's position. In the East, Emperor Theodosius I likewise professed the Nicene creed; but there were many adherents of Arianism throughout his dominions, especially among the higher clergy. In this state of religious ferment, two leaders of the Arians, bishops Palladius of Ratiaria and Secundianus of Singidunum, confident of numbers, prevailed upon Gratian to call a general council from all parts of the empire. This request appeared so equitable that he complied without hesitation. However, Ambrose feared the consequences and prevailed upon the emperor to have the matter determined by a council of the Western bishops. Accordingly, a synod composed of thirty-two bishops was held at Aquileia in the year 381. Ambrose was elected president and Palladius, being called upon to defend his opinions, declined. A vote was then taken and Palladius and his associate Secundianus were deposed from their episcopal offices. Ambrose struggled with Arianism for over half of his life in the episcopate. Unifying the church was important to the church, but it was no less important to the state, and as a Roman, Ambrose felt strongly about that. Judaism was more attractive for those seeking conversion than previous scholars have realized, and pagans were still in the majority, so the edition of heresy created an age of religious ferment comparable to the Reformation of the fourteenth and fifteenth centuries. Orthodox Christianity was determining how to define itself as it faced multiple challenges on both a theological and a practical level, and Ambrose is seen as a crucial influence at a crucial time.
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1370_4
Imperial relations Ambrose had good relations and varying levels of influence with the Roman emperors Gratian, Valentinian II and Theodosius I, but exactly how much influence, what kind of influence, and in what ways, when, has been debated in the scholarship of the late twentieth and early twenty-first centuries. Gratian It has long been convention to see Gratian and Ambrose as having a personal friendship, putting Ambrose in the dominant role of spiritual guide, but modern scholars now find this view hard to support in the sources. The ancient Christian historian Sozomen is the only ancient source that shows Ambrose and Gratian together in any personal interaction. In that interaction, Sozomen relates that, in the last year of Gratian's reign, Ambrose crashed Gratian's private hunting party in order to appeal on behalf of a pagan senator sentenced to die. After years of acquaintance, this indicates Ambrose could not take for granted that Gratian would see him, so instead, Ambrose had to resort to such maneuverings to make his appeal. Gratian was personally devout long before meeting Ambrose. Modern scholarship indicates Gratian's religious policies do not evidence capitulation to Ambrose more than they evidence Gratian's own views. Gratian's devotion did lead Ambrose to write a large number of books and letters of theology and spiritual commentary dedicated to the emperor. The sheer volume of these writings and the effusive praise they contain has led many historians to conclude that Gratian was dominated by Ambrose, and it was that dominance that produced Gratian's anti-pagan actions. McLynn asserts that effusive praises were common in everyone's correspondence with the crown. He adds that Gratian's actions were determined by the constraints of the system as much as "by his own initiatives or Ambrose's influence".
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1370_5
McLynn asserts that the largest influence on Gratian's policy was the profound change in political circumstances produced by the battle of Adrianople in 378. Gratian had become involved in fighting the Goths the previous year and had been on his way to the Balkans when his Uncle and the "cream of the eastern army" were destroyed at Adrianople. Gratian withdrew to Sirmium and set up his court there. Several rival groups, including the Arians, sought to secure benefits from the government at Sirmium. In an Arian attempt to undermine Ambrose, whom Gratian had not yet met, Gratian was 'warned' that Ambrose' faith was suspect. Gratian took steps to investigate by writing Ambrose and asking him to explain his faith. Ambrose and Gratian first met, after this, in 379 during a visit to Milan. The bishop made a good impression on Gratian and his court which was pervasively Christian and aristocratic much like Ambrose himself. The emperor returned to Milan in 380 to find that Ambrose had complied with his request for a statement of his faith – in two volumes – known as De Fide: a statement of orthodoxy, Ambrose' political theology, and a polemic against the Arian heresy intended for public discussion. The emperor had not asked to be instructed by Ambrose, and in De Fide Ambrose states this clearly. Nor was he asked to refute the Arians. He was asked to justify his own position, but in the end, he did all three. By 382, it seems clear that Ambrose had replaced Ausonius to become a major influence in Gratian's court. Ambrose had not yet become the "conscience" of kings he would in the later 380's, but he did speak out against reinstating the Altar of Victory. In 382, Gratian was the first to divert public financial subsidies that had previously supported Rome's cults. Before that year, contributions in support of the ancient customs had continued unchallenged by the state.
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1370_6
Valentinian II Gratian, who was childless, had treated his younger brother Valentinian II like a son. Ambrose, on the other hand, had incurred the lasting enmity of Valentinian II's mother, the Empress Justina, in the winter of 379 by helping to appoint a Nicene bishop in Sirmium. Not long after this, Valentinian II, his mother, and the court left Sirmium; Sirmium had come under Theodosius' control, so they went to Milan which was ruled by Gratian. In 383 Gratian was assassinated at Lyon, in Gaul (France) by Magnus Maximus. Valentinian was twelve years old, and it left his mother, Justina, in a position of something akin to a regent. In 385 (or 386) the emperor Valentinian II and his mother Justina, along with a considerable number of clergy, the laity, and the military, professed Arianism. Conflict between Ambrose and Justina soon followed. The Arians demanded that Valentinian allocate to them two churches in Milan: one in the city (the Basilica of the Apostles), the other in the suburbs (St Victor's). Ambrose refused to surrender the churches. He answered by saying that "What belongs to God, is outside the emperor's power". In this, Ambrose called on an ancient Roman principle: a temple set apart to a god became the property of that god. Ambrose now applied this ancient legal principle to the Christian churches, and the bishop, as his representative, was guardian of his god's property. Subsequently, while Ambrose was performing the Liturgy of the Hours in the basilica, the prefect of the city came to persuade him to give it up the to the Arians. Ambrose again refused. Certain deans (officers of the court) were sent to take possession of the basilica by hanging upon it imperial escutcheons. Instead, soldiers from the ranks the emperor had placed around the basilica began pouring into the church assuring Ambrose of their fidelity. The escutcheons outside the church were removed, and legend says the children tore them to shreds.
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1370_7
Ambrose refused to surrender the basilica, and sent sharp answers back to his emperor: "If you demand my person, I am ready to submit: carry me to prison or to death, I will not resist; but I will never betray the church of Christ. I will not call upon the people to succour me; I will die at the foot of the altar rather than desert it. The tumult of the people I will not encourage: but God alone can appease it." By Thursday, the emperor gave in, bitterly responding: "Soon, if Ambrose gives the orders, you will be sending me to him in chains." In 386, Justina and Valentinian II received the Arian bishop Auxentius the younger, and Ambrose was again ordered to hand over a church in Milan for Arian usage. Ambrose and his congregation barricaded themselves inside the church, and again the imperial order was rescinded. There was an attempted kidnapping, and another attempt to arrest him and force him to leave the city. Several accusations were made, but unlike John Chrysostum, no formal charges were brought. The emperor certainly had the power to do so, and probably didn't solely because of Ambrose' popularity with the people and what they might do. When Magnus Maximus usurped power in Gaul, and was considering a descent upon Italy, Valentinian sent Ambrose to dissuade him, and the embassy was successful. A second later embassy was unsuccessful. The enemy entered Italy and Milan was taken. Justina and her son fled, but Ambrose remained, and had the plate of the church melted for the relief of the poor. After defeating the usurper Maximus at Aquileia in 388 Theodosius handed the western realm back to the young Valentinian II, the seventeen-year-old son of the forceful and hardy Pannonian general Valentinian I and his wife, the Arian Justina. Furthermore, the Eastern emperor remained in Italy for a considerable period to supervise affairs, returning to Constantinople in 391 and leaving behind the Frankish general Arbogast to keep an eye on the young emperor. By May of the following year Arbogast's ward was dead amidst rumours of both treachery and suicide... Theodosius
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