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Potassium nitrate

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(Redirected from Nitrate of potash)
"Saltpeter" redirects here. For other uses, see Saltpeter (disambiguation).
Potassium nitrate[1]
Potassium nitrate
Names
IUPAC name
Potassium nitrate
Other names
  • Saltpeter
  • Saltpetre
  • Nitrate of potash
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.028.926 Edit this at Wikidata
EC Number
  • 231-818-8
E number E252 (preservatives)
KEGG
RTECS number
  • TT3700000
UNII
UN number 1486
  • InChI=1S/K.NO3/c;2-1(3)4/q+1;-1 checkY
    Key: FGIUAXJPYTZDNR-UHFFFAOYSA-N checkY
  • InChI=1/K.NO3/c;2-1(3)4/q+1;-1
    Key: FGIUAXJPYTZDNR-UHFFFAOYAM
  • [K+].[O-][N+]([O-])=O
Properties
KNO3
Molar mass 101.1032 g/mol
Appearance white solid
Odor odorless
Density 2.109 g/cm3 (16 °C)
Melting point 334 °C (633 °F; 607 K)
Boiling point 400 °C (752 °F; 673 K) (decomposes)
  • 133 g/(1000 g) (0 °C)
  • 316 g/(1000 g) (20 °C)
  • 383 g/(1000 g) (25 °C)
  • 2439 g/(1000 g) (100 °C)
[2]
Solubility slightly soluble in ethanol
soluble in glycerol, ammonia
Basicity (pKb) 15.3[3]
−33.7·10−6 cm3/mol
1.335, 1.5056, 1.5604
Structure
Orthorhombic, Aragonite
Thermochemistry
95.06 J/mol K
−494.00 kJ/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Oxidant, harmful if swallowed, inhaled, or absorbed on skin. Causes irritation to skin and eye area.
GHS labelling:
GHS03: Oxidizing GHS07: Exclamation mark
H272, H315, H319, H335
P102, P210, P220, P221, P280
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
1
0
0
OX
Flash point non-flammable (oxidizer)
Lethal dose or concentration (LD, LC):
1901 mg/kg (oral, rabbit)
3750 mg/kg (oral, rat)[4]
Safety data sheet (SDS) ICSC 0184
Related compounds
Other anions
 Potassium nitrite
Other cations
Related compounds
Supplementary data page
Potassium nitrate (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Potassium nitrate is a chemical compound with a sharp, salty, bitter taste and the chemical formula KNO3. It is a potassium salt of nitric acid. This salt consists of potassium cations K+ and nitrate anions NO−3, and is therefore an alkali metal nitrate. It occurs in nature as a mineral, niter (or nitre outside the US).[5] It is a source of nitrogen, and nitrogen was named after niter. Potassium nitrate is one of several nitrogen-containing compounds collectively referred to as saltpetre (or saltpeter in the US).[5]

Major uses of potassium nitrate are in fertilizers, tree stump removal, rocket propellants and fireworks. It is one of the major constituents of gunpowder (black powder).[6] In processed meats, potassium nitrate reacts with hemoglobin and myoglobin generating a red color.[7]

Etymology

[edit]

Nitre, or potassium nitrate, because of its early and global use and production, has many names.

As for nitrate, Egyptian and Hebrew words for it had the consonants n-t-r, indicating likely cognation in the Greek nitron, which was Latinised to nitrum or nitrium. Thence Old French had niter and Middle English nitre. By the 15th century, Europeans referred to it as saltpetre,[8] specifically Indian saltpetre (Chilean saltpetre is sodium nitrate[9]) and later as nitrate of potash, as the chemistry of the compound was more fully understood.

The Arabs called it "Chinese snow" (Arabic: ثلج الصين, romanized: thalj al-ṣīn) as well as bārūd (بارود), a term of uncertain origin that later came to mean gunpowder. It was called "Chinese salt" by the Iranians/Persians[10][11][12] or "salt from Chinese salt marshes" (Persian: نمک شوره چينی namak shūra chīnī).[13]: 335 [14] The Tiangong Kaiwu, published in the 17th century by members of the Qing dynasty, detailed the production of gunpowder and other useful products from nature.

Historical production

[edit]
See also: Nitre § Availability

From mineral sources

[edit]

In Mauryan India saltpeter manufacturers formed the Nuniya & Labana caste.[15] Saltpeter finds mention in Kautilya's Arthashastra (compiled 300BC – 300AD), which mentions using its poisonous smoke as a weapon of war,[16] although its use for propulsion did not appear until medieval times.

A purification process for potassium nitrate was outlined in 1270 by the chemist and engineer Hasan al-Rammah of Syria in his book al-Furusiyya wa al-Manasib al-Harbiyya (The Book of Military Horsemanship and Ingenious War Devices). In this book, al-Rammah describes first the purification of barud (crude saltpeter mineral) by boiling it with minimal water and using only the hot solution, then the use of potassium carbonate (in the form of wood ashes) to remove calcium and magnesium by precipitation of their carbonates from this solution, leaving a solution of purified potassium nitrate, which could then be dried.[17] This was used for the manufacture of gunpowder and explosive devices. The terminology used by al-Rammah indicated the gunpowder he wrote about originated in China.[18]

At least as far back as 1845, nitratite deposits were exploited in Chile and California.

From caves

[edit]

Major natural sources of potassium nitrate were the deposits crystallizing from cave walls and the accumulations of bat guano in caves.[19] Extraction is accomplished by immersing the guano in water for a day, filtering, and harvesting the crystals in the filtered water. Traditionally, guano was the source used in Laos for the manufacture of gunpowder for Bang Fai rockets.[20]

Calcium nitrate, or lime saltpetre, was discovered on the walls of stables, from the urine of barnyard animals.[9]

Nitraries

[edit]
See also: Saltpetre works

Potassium nitrate was produced in a nitrary or "saltpetre works".[21] The process involved burial of excrements (human or animal) in a field beside the nitraries, watering them and waiting until leaching allowed saltpeter to migrate to the surface by efflorescence. Operators then gathered the resulting powder and transported it to be concentrated by ebullition in the boiler plant.[22][23]

Besides "Montepellusanus", during the thirteenth century (and beyond) the only supply of saltpeter across Christian Europe (according to "De Alchimia" in 3 manuscripts of Michael Scot, 1180–1236) was "found in Spain in Aragon in a certain mountain near the sea".[13]: 89, 311 [24]

In 1561, Elizabeth I, Queen of England and Ireland, who was at war with Philip II of Spain, became unable to import saltpeter (of which the Kingdom of England had no home production), and had to pay "300 pounds gold" to the German captain Gerrard Honrik for the manual "Instructions for making saltpeter to growe" (the secret of the "Feuerwerkbuch" -the nitraries-).[25]

Nitre bed

[edit]

A nitre bed is a similar process used to produce nitrate from excrement. Unlike the leaching-based process of the nitrary, however, one mixes the excrements with soil and waits for soil microbes to convert amino-nitrogen into nitrates by nitrification. The nitrates are extracted from soil with water and then purified into saltpeter by adding wood ash. The process was discovered in the early 15th century and was very widely used until the Chilean mineral deposits were found.[26]

The Confederate side of the American Civil War had a significant shortage of saltpeter. As a result, the Nitre and Mining Bureau was set up to encourage local production, including by nitre beds and by providing excrement to government nitraries. On November 13, 1862, the government advertised in the Charleston Daily Courier for 20 or 30 "able bodied Negro men" to work in the new nitre beds at Ashley Ferry, S.C. The nitre beds were large rectangles of rotted manure and straw, moistened weekly with urine, "dung water", and liquid from privies, cesspools and drains, and turned over regularly. The National Archives published payroll records that account for more than 29,000 people compelled to such labor in the state of Virginia. The South was so desperate for saltpeter for gunpowder that one Alabama official reportedly placed a newspaper ad asking that the contents of chamber pots be saved for collection. In South Carolina, in April 1864, the Confederate government forced 31 enslaved people to work at the Ashley Ferry Nitre Works, outside Charleston.[27]

Perhaps the most exhaustive discussion of the niter-bed production is the 1862 LeConte text.[28] He was writing with the express purpose of increasing production in the Confederate States to support their needs during the American Civil War. Since he was calling for the assistance of rural farming communities, the descriptions and instructions are both simple and explicit. He details the "French Method", along with several variations, as well as a "Swiss method". N.B. Many references have been made to a method using only straw and urine, but there is no such method in this work.

French method

[edit]

Turgot and Lavoisier created the Régie des Poudres et Salpêtres a few years before the French Revolution. Niter-beds were prepared by mixing manure with either mortar or wood ashes, common earth and organic materials such as straw to give porosity to a compost pile typically 4 feet (1.2 m) high, 6 feet (1.8 m) wide, and 15 feet (4.6 m) long.[28] The heap was usually under a cover from the rain, kept moist with urine, turned often to accelerate the decomposition, then finally leached with water after approximately one year, to remove the soluble calcium nitrate which was then converted to potassium nitrate by filtering through potash.

Swiss method

[edit]

Joseph LeConte describes a process using only urine and not dung, referring to it as the Swiss method. Urine is collected directly, in a sandpit under a stable. The sand itself is dug out and leached for nitrates which are then converted to potassium nitrate using potash, as above.[29]

From nitric acid

[edit]

From 1903 until the World War I era, potassium nitrate for black powder and fertilizer was produced on an industrial scale from nitric acid produced using the Birkeland–Eyde process, which used an electric arc to oxidize nitrogen from the air. During World War I the newly industrialized Haber process (1913) was combined with the Ostwald process after 1915, allowing Germany to produce nitric acid for the war after being cut off from its supplies of mineral sodium nitrates from Chile (see nitratite).

Modern production

[edit]

Potassium nitrate can be made by combining ammonium nitrate and potassium hydroxide.

NH4NO3 + KOH → NH3 + KNO3 + H2O

An alternative way of producing potassium nitrate without a by-product of ammonia is to combine ammonium nitrate, found in instant ice packs,[30] and potassium chloride, easily obtained as a sodium-free salt substitute.

NH4NO3 + KCl → NH4Cl + KNO3

Potassium nitrate can also be produced by neutralizing nitric acid with potassium hydroxide. This reaction is highly exothermic.

KOH + HNO3 → KNO3 + H2O

On industrial scale it is prepared by the double displacement reaction between sodium nitrate and potassium chloride.

NaNO3 + KCl → NaCl + KNO3

Properties

[edit]

Potassium nitrate has an orthorhombic crystal structure at room temperature,[31] which transforms to a trigonal system at 128 °C (262 °F). On cooling from 200 °C (392 °F), another trigonal phase forms between 124 °C (255 °F) and 100 °C (212 °F).[32][33]

Sodium nitrate is isomorphous with calcite, the most stable form of calcium carbonate, whereas room-temperature potassium nitrate is isomorphous with aragonite, a slightly less stable polymorph of calcium carbonate. The difference is attributed to the similarity in size between nitrate (NO−3) and carbonate (CO2−3) ions and the fact that the potassium ion (K+) is larger than sodium (Na+) and calcium (Ca2+) ions.[34]

In the room-temperature structure of potassium nitrate, each potassium ion is surrounded by 6 nitrate ions. In turn, each nitrate ion is surrounded by 6 potassium ions.[31]

Room temperature crystal structure and coordination geometry of potassium nitrate[31]
Unit cell Potassium coordination Nitrate coordination

Potassium nitrate is moderately soluble in water, but its solubility increases with temperature. The aqueous solution is almost neutral, exhibiting pH 6.2 at 14 °C (57 °F) for a 10% solution of commercial powder. It is not very hygroscopic, absorbing about 0.03% water in 80% relative humidity over 50 days. It is insoluble in alcohol and is not poisonous; it can react explosively with reducing agents, but it is not explosive on its own.[2]

Thermal decomposition

[edit]

Between 550–790 °C (1,022–1,454 °F), potassium nitrate reaches a temperature-dependent equilibrium with potassium nitrite:[35]

2 KNO3 ⇌ 2 KNO2 + O2

Uses

[edit]

Potassium nitrate has a wide variety of uses, largely as a source of nitrate.

Nitric acid production

[edit]

Historically, nitric acid was produced by combining sulfuric acid with nitrates such as saltpeter. In modern times this is reversed: nitrates are produced from nitric acid produced via the Ostwald process.

Oxidizer

[edit]
A demonstration of the oxidation of a piece of charcoal in molten potassium nitrate

The most famous use of potassium nitrate is probably as the oxidizer in blackpowder. From the most ancient times until the late 1880s, blackpowder provided the explosive power for all the world's firearms. After that time, small arms and large artillery increasingly began to depend on cordite, a smokeless powder. Blackpowder remains in use today in black powder rocket motors, but also in combination with other fuels like sugars in "rocket candy" (a popular amateur rocket propellant). It is also used in fireworks such as smoke bombs.[36] It is also added to cigarettes to maintain an even burn of the tobacco[37] and is used to ensure complete combustion of paper cartridges for cap and ball revolvers.[38] It can also be heated to several hundred degrees to be used for niter bluing, which is less durable than other forms of protective oxidation, but allows for specific and often beautiful coloration of steel parts, such as screws, pins, and other small parts of firearms.

Meat processing

[edit]

Potassium nitrate has been a common ingredient of salted meat since antiquity[39] or the Middle Ages.[40] The widespread adoption of nitrate use is more recent and is linked to the development of large-scale meat processing.[6] The use of potassium nitrate has been mostly discontinued because it gives slow and inconsistent results compared with sodium nitrite preparations such as "Prague powder" or pink "curing salt". Even so, potassium nitrate is still used in some food applications, such as salami, dry-cured ham, charcuterie, and (in some countries) in the brine used to make corned beef (sometimes together with sodium nitrite).[41] In the Shetland Islands (UK) it is used in the curing of mutton to make reestit mutton, a local delicacy.[42] When used as a food additive in the European Union,[43] the compound is referred to as E252; it is also approved for use as a food additive in the United States[44] and Australia and New Zealand[45] (where it is listed under its INS number 252).[2]

Possible cancer risk

[edit]

Since October 2015, WHO classifies processed meat as Group 1 carcinogen (based on epidemiological studies, convincingly carcinogenic to humans).[46]

In April 2023 the French Court of Appeals of Limoges confirmed that food-watch NGO Yuka was legally legitimate in describing Potassium Nitrate E249 to E252 as a "cancer risk", and thus rejected an appeal by the French charcuterie industry against the organisation.[47]

Fertilizer

[edit]

Potassium nitrate is used in fertilizers as a source of nitrogen and potassium – two of the macronutrients for plants. When used by itself, it has an NPK rating of 13-0-44.[48][49]

Pharmacology

[edit]

Other uses

[edit]
[edit]

Potassium nitrate was once thought to induce impotence, and is still rumored to be in institutional food (such as military fare). There is no scientific evidence for such properties.[64][65] In Bank Shot, El (Joanna Cassidy) propositions Walter Ballantine (George C. Scott), who tells her that he has been fed saltpeter in prison.[citation needed] In One Flew Over the Cuckoo's Nest, Randle is asked by the nurses to take his medications, but not knowing what they are, he mentions he does not want anyone to "slip me saltpeter". He then proceeds to imitate the motions of masturbation.

In 1776, John Adams asks his wife Abigail to make saltpeter for the Continental Army. She, eventually, is able to do so in exchange for pins for sewing.[66]

In the Star Trek episode "Arena", Captain Kirk injures a gorn using a rudimentary cannon that he constructs using potassium nitrate as a key ingredient of gunpowder.[citation needed]

In 21 Jump Street, Jenko, played by Channing Tatum, gives a rhyming presentation about potassium nitrate for his chemistry class.[citation needed]

In Eating Raoul, Paul hires a dominatrix to impersonate a nurse and trick Raoul into consuming saltpeter in a ploy to reduce his sexual appetite for his wife.[citation needed]

In The Simpsons episode "El Viaje Misterioso de Nuestro Jomer (The Mysterious Voyage of Our Homer)", Mr. Burns is seen pouring saltpeter into his chili entry, titled Old Elihu's Yale-Style Saltpeter Chili.[citation needed]

In the Sharpe novel series by Bernard Cornwell, numerous mentions are made of an advantageous supply of saltpeter from India being a crucial component of British military supremacy in the Napoleonic Wars. In Sharpe's Havoc, the French Captain Argenton laments that France needs to scrape its supply from cesspits.[citation needed]

In the Dr. Stone anime and manga series, the struggle for control over a natural saltpeter source from guano features prominently in the plot.[citation needed]

In the farming lore from the Corn Belt of the 1800s, drought-killed corn[67] in manured fields could accumulate saltpeter to the extent that upon opening the stalk for examination it would "fall as a fine powder upon the table".[68]

In the Slovenian short story Martin Krpan from Vrh pri Sveti Trojici, the titular character and Slovene folk hero Martin Krpan illegally smuggles "English salt" for a living. The exact nature of "English salt" is a matter of debate, but it may have been a euphemism for potassium nitrate (saltpeter) due to its role in manufacturing gunpowder.[citation needed]

In Dexter: Original Sin's first episode, Dexter's first victim uses potassium nitrate to kill her victims.

See also

[edit]

References

[edit]
  1. ^ Record of Potassium nitrate in the GESTIS Substance Database of the Institute for Occupational Safety and Health, accessed on 2007-03-09.
  2. ^ a b c B. J. Kosanke; B. Sturman; K. Kosanke; et al. (2004). "2". Pyrotechnic Chemistry. Journal of Pyrotechnics. pp. 5–6. ISBN 978-1-889526-15-7. Archived from the original on 2016-05-05.
  3. ^ Kolthoff, Treatise on Analytical Chemistry, New York, Interscience Encyclopedia, Inc., 1959.
  4. ^ Ema, M.; Kanoh, S. (1983). "[Studies on the pharmacological bases of fetal toxicity of drugs. III. Fetal toxicity of potassium nitrate in 2 generations of rats]". Nihon Yakurigaku Zasshi. Folia Pharmacologica Japonica. 81 (6): 469–480. doi:10.1254/fpj.81.469. ISSN 0015-5691. PMID 6618340.
  5. ^ a b Shorter Oxford English Dictionary (6th ed.). United Kingdom: Oxford University Press. 2007. p. 3804. ISBN 9780199206872.
  6. ^ a b Lauer, Klaus (1991). "The history of nitrite in human nutrition: A contribution from German cookery books". Journal of Clinical Epidemiology. 44 (3): 261–264. doi:10.1016/0895-4356(91)90037-a. ISSN 0895-4356. PMID 1999685.
  7. ^ Haldane, J. (1901). "The Red Colour of Salted Meat". The Journal of Hygiene. 1 (1): 115–122. doi:10.1017/S0022172400000097. ISSN 0022-1724. PMC 2235964. PMID 20474105.
  8. ^ Spencer, Dan (2013). Saltpeter:The Mother of Gunpowder. Oxford, UK: Oxford University Press. p. 256. ISBN 9780199695751.
  9. ^ a b "Saltpetre | Definition, Uses, & Facts | Britannica". 3 May 2024.
  10. ^ Peter Watson (2006). Ideas: A History of Thought and Invention, from Fire to Freud. HarperCollins. p. 304. ISBN 978-0-06-093564-1. Archived from the original on 2015-10-17.
  11. ^ Cathal J. Nolan (2006). The age of wars of religion, 1000–1650: an encyclopedia of global warfare and civilization. Vol. 1 of Greenwood encyclopedias of modern world wars. Greenwood Publishing Group. p. 365. ISBN 978-0-313-33733-8. Archived from the original on 2014-01-01. Retrieved 2011-11-28. In either case, there is linguistic evidence of Chinese origins of the technology: in Damascus, Arabs called the saltpeter used in making gunpowder "Chinese snow," while in Iran it was called "Chinese salt."
  12. ^ Oliver Frederick Gillilan Hogg (1963). English artillery, 1326–1716: being the history of artillery in this country prior to the formation of the Royal Regiment of Artillery. Royal Artillery Institution. p. 42. The Chinese were certainly acquainted with saltpetre, the essential ingredient of gunpowder. They called it Chinese Snow and employed it early in the Christian era in the manufacture of fireworks and rockets.
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  25. ^ SP Dom Elizabeth vol.xvi 29–30 (1589)
  26. ^ Narihiro, Takashi; Tamaki, Hideyuki; Akiba, Aya; et al. (11 August 2014). "Microbial Community Structure of Relict Niter-Beds Previously Used for Saltpeter Production". PLOS ONE. 9 (8): e104752. Bibcode:2014PLoSO...9j4752N. doi:10.1371/journal.pone.0104752. PMC 4128746. PMID 25111392.
  27. ^ Ruane, Michael. "During the Civil War, the enslaved were given an especially odious job. The pay went to their owners". Washington Post. Retrieved 10 July 2020.
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  29. ^ LeConte, Joseph (1862). Instructions for the Manufacture of Saltpetre. Charles P. Pelham, State Printer.
  30. ^ "How Refrigerators Work". HowStuffWorks. 2006-11-29. Retrieved 2018-11-02.
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  32. ^ Nimmo, J. K.; Lucas, B. W. (1976). "The crystal structures of γ- and β-KNO3 and the α ← γ ← β phase transformations". Acta Crystallographica Section B. 32 (7): 1968–1971. doi:10.1107/S0567740876006894.
  33. ^ Freney, E. J.; Garvie, L. A. J.; Groy, T. L.; Buseck, P. R. (2009). "Growth and single-crystal refinement of phase-III potassium nitrate, KNO3". Acta Crystallographica Section B. 65 (6): 659–663. doi:10.1107/S0108768109041019. PMID 19923693.
  34. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 407. ISBN 978-0-08-037941-8.
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  36. ^ Amthyst Galleries, Inc Archived 2008-11-04 at the Wayback Machine. Galleries.com. Retrieved on 2012-03-07.
  37. ^ Inorganic Additives for the Improvement of Tobacco Archived 2007-11-01 at the Wayback Machine, TobaccoDocuments.org
  38. ^ Kirst, W.J. (1983). Self Consuming Paper Cartridges for the Percussion Revolver. Minneapolis, Minnesota: Northwest Development Co.
  39. ^ Binkerd, E. F; Kolari, O. E (1975-01-01). "The history and use of nitrate and nitrite in the curing of meat". Food and Cosmetics Toxicology. 13 (6): 655–661. doi:10.1016/0015-6264(75)90157-1. ISSN 0015-6264. PMID 1107192.
  40. ^ "Meat Science", University of Wisconsin. uwex.edu.
  41. ^ Corned Beef Archived 2008-03-19 at the Wayback Machine, Food Network
  42. ^ Brown, Catherine (2011-11-14). A Year In A Scots Kitchen. Neil Wilson Publishing Ltd. ISBN 9781906476847.
  43. ^ UK Food Standards Agency: "Current EU approved additives and their E Numbers". Archived from the original on 2010-10-07. Retrieved 2011-10-27.
  44. ^ US Food and Drug Administration: "Listing of Food Additives Status Part II". Food and Drug Administration. Archived from the original on 2011-11-08. Retrieved 2011-10-27.
  45. ^ Australia New Zealand Food Standards Code "Standard 1.2.4 – Labelling of ingredients". 8 September 2011. Retrieved 2011-10-27.
  46. ^ "Cancer: Carcinogenicity of the consumption of red meat and processed meat". www.who.int. Retrieved 2023-12-29.
  47. ^ Rabino, Thomas (13 April 2023). "Nitrites et jambons "cancérogènes" : nouvelle victoire en appel de Yuka contre un industriel de la charcuterie" [Nitrites and "carcinogenic" hams: Yuka's new appeal victory against a charcuterie manufacturer]. Marianne (in French). Et ce, en dépit de la multiplicité des avis scientifiques, comme celui du Centre international de recherche sur le cancer, classant ces mêmes additifs, connus sous le nom de E249, E250, E251, E252, parmi les « cancérogènes probables », auxquels la Ligue contre le cancer attribue près de 4 000 cancers colorectaux par an. [And this, despite the multiplicity of scientific opinions, such as that of the International Agency for Research on Cancer, classifying these same additives, known as E249, E250, E251, E252, among the "probable carcinogens", to which the League Against Cancer attributes nearly 4,000 colorectal cancers per year.]
  48. ^ Michigan State University Extension Bulletin E-896: N-P-K Fertilizers Archived 2015-12-24 at the Wayback Machine
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Bibliography

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