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Tuesday, September 30, 2014

Arsenic



Elemental Arsenic



Arsenic is a chemical element found in many minerals, usually in conjunction with sulfur and metals, and also as a pure elemental crystal. [1]



Realgar, an arsenic sulfide mineral As4S4 [41]
 



Elemental arsenic and arsenic compounds are classified as "toxic" and "dangerous for the environment" in the European Union under directive 67/548/EEC. The International Agency for Research on Cancer (IARC) recognizes arsenic and arsenic compounds as group 1 carcinogens.
[1]


By competing with phosphate, arsenate acts to inhibit mitochondrial respiration and ATP synthesis. Hydrogen peroxide production is also increased, which, it is speculated, has potential to form reactive oxygen species and oxidative stress. These metabolic interferences lead to death from multi-system organ failure. The organ failure is presumed to be from necrotic cell death, not apoptosis, since energy reserves have been too depleted for apoptosis to occur. [30]


A few species of bacteria are able to use arsenic compounds as respiratory metabolites. Under oxidative environmental conditions these bacteria are able to oxidize arsenite to arsenate for use as fuel for their metabolism. [19]



Dimercaprol
Chronic arsenic poisoning is treated with British anti-lewisite (Dimercaprol) for a duration of approximately ten days. [32] 
Dimercaprol is on the World Health Organization's List of Essential Medicines, a list of the most important medications needed in a basic health system. [35][36]


Blood, urine, hair, and nails may be tested for arsenic; however, these tests cannot foresee possible health outcomes from the exposure. [22]

Excretion occurs in the urine and long-term exposure to arsenic has been linked to bladder and kidney cancer in addition to cancer of the liver, prostate, skin, lungs, and nasal cavity. [33]


Arsenic contamination of groundwater is a problem that affects millions of people across the world. Epidemiological studies have suggested a correlation between chronic consumption of drinking water contaminated with arsenic and the incidence of all leading causes of mortality. [23]


For several centuries, the people of San Pedro de Atacama in Chile have been drinking water that is contaminated with arsenic, and it is believed that they may have developed some immunity to the ill effects of consuming it. [24][25]


Prior to the discovery of antibiotics, arsphenamine was indicated for syphilis. [36][37]


Until the advent of the Marsh test, a sensitive chemical test to detect its presence, arsenic was frequently used as a tool for murder. 

Owing to its use by the ruling class to murder one another and its potency and discreetness, arsenic has been called the Poison of Kings and the King of Poisons. [3]



Paris Green is an inorganic compound more precisely known as copper(II) acetoarsenite. It is a highly toxic emerald-green crystalline powder [42][43] that has been used as a rodenticide and insecticide, and also as a pigment, despite its toxicity. It is also used as a blue colorant for fireworks. [44][45]











Arsenite of lime and arsenate of lead were used widely as insecticides until the discovery of DDT in 1942. [4][5][6] 

(Photo) Mixing "Paris Green" and road dust, preparing to dust streams and breeding places of mosquitoes during WWII. [8]

The toxicity of arsenic to insects, bacteria and fungi led to its use as a wood preservative. [7]





During the Vietnam War the United States used Agent Blue, an arsenic herbicide, to deprive invading North Vietnamese soldiers of foliage cover and rice. [15][16]



More recently,

Arsenic is used as a feed additive in poultry and swine production, in particular in the United States (US) to increase weight gain, improve feed efficiency, and to prevent disease.
[8][9] An example is Roxarsone, which had been used as a broiler starter by about 70% of US broiler growers. [10]
“FDA announced that Alpharma, a subsidiary of Pfizer Inc., will voluntarily suspend sale of the animal drug 3-Nitro® (Roxarsone) in response to a new FDA study of 100 broiler chickens that detected inorganic arsenic, a known carcinogen, at higher levels in the livers of chickens treated with the drug 3-Nitro® (Roxarsone) than in untreated chickens. FDA officials stress that the levels of inorganic arsenic detected were very low and that continuing to eat chicken as 3-Nitro® is suspended from the market does not pose a health risk.” [38]


The above statement from the FDA was made in 2011. A successor to Alpharma, a company called Zoetis, continues to sell *Nitarsone primarily for use in turkeys. [11]


*Nitarsone is an organoarsenic compound that is used in poultry production as a feed additive to increase weight gain, improve feed efficiency, and prevent blackhead disease. It is marketed as Histostat® by Zoetis, a publicly traded subsidiary of Pfizer. [39][40]



The US Food and Drug Administration in 2000 approved arsenic trioxide to treat patients with acute promyelocytic leukemia that is resistant to ATRA (a chemotherapy drug). [12]



New research is looking into using arsenic-74 (a positron emitter) to locate tumors. The advantages of using this isotope instead of the previously used iodine-124 is that the signal in the PET scan is clearer as the body tends to transport iodine to the thyroid gland producing a lot of noise. [13]



Up to 2% of arsenic is used in lead alloys for lead shots and bullets. [17]


Until recently arsenic was used in optical glass. Modern glass manufacturers, under pressure from environmentalists, have removed it, along with lead. [18]


The main use of metallic arsenic is for alloying with lead. Lead components in car batteries are strengthened by the presence of a very small percentage of arsenic. [2][14] 

Gallium arsenide is an important semiconductor material, used in integrated circuits. [2]


Occupational exposure and arsenic poisoning may occur in persons working in industries involving the use of inorganic arsenic and its compounds, such as wood preservation, glass production, nonferrous metal alloys, and electronic semiconductor manufacturing. Inorganic arsenic is also found in coke oven emissions associated with the smelter industry. [31]


Arsenic is found in food, water, soil, and air. [20] It is absorbed by all plants, but is more concentrated in leafy vegetables, rice, apple and grape juice, and seafood. [21]


Regarding apple juice:

In 2011, the national Dr. Oz television show broadcast a program highlighting tests performed by an independent lab hired by the producers. Though the methodology was disputed (it did not distinguish between organic and inorganic arsenic) the tests showed levels of arsenic up to 36 ppb. [27] 
Subsequent FDA testing of the worst brand from the Dr. Oz show found much lower levels, and its ongoing testing found 95% of apple juice samples were below the level of concern. Later testing by Consumer Reports showed inorganic arsenic at levels slightly above 10 ppb, with the organization urging parents to reduce consumption. [28] 
In July 2013, after taking into account consumption by children, chronic exposure, and carcinogenic effect, the FDA established an "action level" of 10 ppb for apple juice, the same as the drinking water standard. [26]



Regarding rice:

Consumer Reports recommends that the EPA and FDA eliminate arsenic-containing fertilizer, drugs, and pesticides in food production; that the FDA establish a legal limit for food; that industry change production practices to lower arsenic levels, especially in food for children; and that consumers test home water supplies, eat a varied diet, and cook rice with excess water which is drained off (reducing inorganic arsenic by about one third along with only a slight reduction in vitamin content). [29]















References & Resources

[1] http://en.wikipedia.org/wiki/Arsenic
[2] Sabina C. Grund, Kunibert Hanusch, Hans Uwe Wolf (2005), "Arsenic and Arsenic Compounds", Ullmann's Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, doi:10.1002/14356007.a03_113.pub2
[3] Vahidnia, A.; Van Der Voet, G. B.; De Wolff, F. A. (2007). "Arsenic neurotoxicity – a review". Human & Experimental Toxicology 26 (10): 823–32. doi:10.1177/0960327107084539. PMID 18025055.
[4] Murphy, E.A.; Aucott, M (1998). "An assessment of the amounts of arsenical pesticides used historically in a geographical area". Science of the Total Environment 218 (2–3): 89. doi:10.1016/S0048-9697(98)00180-6.
[5] Marlatt, C. L (1897). Important Insecticides: Directions for Their Preparation and Use. p. 5.
[6] Kassinger, Ruth (20 April 2010). Paradise Under Glass: An Amateur Creates a Conservatory Garden. ISBN 978-0-06-199130-1.
[7] Rahman, FA; Allan, DL; Rosen, CJ; Sadowsky, MJ (2004). "Arsenic availability from chromated copper arsenate (CCA)-treated wood". Journal of environmental quality 33 (1): 173–80. doi:10.2134/jeq2004.0173. PMID 14964372.
[8] Nachman, Keeve E; Graham, Jay P.; Price, Lance B.; Silbergeld, Ellen K. (2005). "Arsenic: A Roadblock to Potential Animal Waste Management Solutions". Environmental Health Perspective 113 (9): 1123–1124. doi:10.1289/ehp.7834.
[9] "Arsenic. Section 5.3, p. 310". Agency for Toxic Substances and Disease Registry.
[10] Jones, F. T. (2007). "A Broad View of Arsenic". Poultry Science 86 (1): 2–14. doi:10.1093/ps/86.1.2. PMID 17179408.
[11] Staff (8 June 2011). "Questions and Answers Regarding 3-Nitro (Roxarsone)". U.S. Food and Drug Administration.
[12] Antman, Karen H. (2001). "The History of Arsenic Trioxide in Cancer Therapy". The oncologist 6 (Suppl 2): 1–2. doi:10.1634/theoncologist.6-suppl_2-1. PMID 11331433.
[13] Jennewein, Marc; Lewis, M. A.; Zhao, D.; Tsyganov, E.; Slavine, N.; He, J.; Watkins, L.; Kodibagkar, V. D.; O'Kelly, S.; Kulkarni, P.; Antich, P.; Hermanne, A.; Rösch, F.; Mason, R.; Thorpe, Ph. (2008). "Vascular Imaging of Solid Tumors in Rats with a Radioactive Arsenic-Labeled Antibody that Binds Exposed Phosphatidylserine". Journal of Clinical Cancer 14 (5): 1377–1385. doi:10.1158/1078-0432.CCR-07-1516. PMC 3436070. PMID 18316558.
[14] Bagshaw, N.E. (1995). "Lead alloys: Past, present and future". Journal of Power Sources 53: 25. Bibcode:1995JPS....53...25B. doi:10.1016/0378-7753(94)01973-Y.
[15]  Westing, Arthur H. (1972). "Herbicides in war: Current status and future doubt". Biological Conservation 4 (5): 322. doi:10.1016/0006-3207(72)90043-2.
[16] Westing, Arthur H. (1971). "Forestry and the War in South Vietnam". Journal of Forestry 69: 777–783.
[17]  Guruswamy, Sivaraman (1999). "XIV. Ammunition". Engineering Properties and Applications of Lead Alloys. CRC Press. pp. 569–570. ISBN 978-0-8247-8247-4.
[18]  "Arsenic Supply Demand and the Environment". Pollution technology review 214: Mercury and arsenic wastes: removal, recovery, treatment, and disposal. William Andrew. 1993. p. 68. ISBN 978-0-8155-1326-1.
[19] Stolz, John F.; Basu, Partha; Santini, Joanne M.; Oremland, Ronald S. (2006). "Arsenic and Selenium in Microbial Metabolism". Annual Review of Microbiology 60: 107–30. doi:10.1146/annurev.micro.60.080805.142053. PMID 16704340.
[20]  "Case Studies in Environmental Medicine (CSEM) Arsenic Toxicity Exposure Pathways". Agency for Toxic Substances & Disease Registry.
[21] "Arsenic in Food: FAQ". 5 December 2011.
[22] Meharg, Andrew (2005). Venomous Earth – How Arsenic Caused The World's Worst Mass Poisoning. Macmillan Science. ISBN 978-1-4039-4499-3.
[23] Meliker, JR; Wahl, RL; Cameron, LL; Nriagu, JO (2007). "Arsenic in drinking water and cerebrovascular disease, diabetes mellitus, and kidney disease in Michigan: A standardized mortality ratio analysis". Environmental Health 6: 4. doi:10.1186/1476-069X-6-4. PMC 1797014. PMID 17274811.
[24] Goering, P.; Aposhian, HV; Mass, MJ; Cebrián, M; Beck, BD; Waalkes, MP (1999). "The enigma of arsenic carcinogenesis: Role of metabolism". Toxicological Sciences 49 (1): 5–14. doi:10.1093/toxsci/49.1.5. PMID 10367337.
[25] Hopenhayn-Rich, C; Biggs, ML; Smith, AH; Kalman, DA; Moore, LE (1996). "Methylation study of a population environmentally exposed to arsenic in drinking water". Environmental Health Perspectives 104 (6): 620–628. doi:10.1289/ehp.96104620. PMC 1469390. PMID 8793350.
[26]  "Supporting Document for Action Level for Arsenic in Apple Juice". Fda.gov.
[27] Kotz, Deborah (14 September 2011). "Does apple juice have unsafe levels of arsenic? – The Boston Globe". Boston.com.
[28] Morran, Chris. "Consumer Reports Study Finds High Levels Of Arsenic & Lead In Some Fruit Juice". consumerist.com.
[29] "Arsenic in Your Food | Consumer Reports Investigation". Consumerreports.org. 1 November 2012.
[30] Hughes, Michael F (2002). "Arsenic toxicity and potential mechanisms of action". Toxicology Letters 133 (1): 1–16. doi:10.1016/S0378-4274(02)00084-X. PMID 12076506.
[31] "OSHA Arsenic". United States Occupational Safety and Health Administration. Archived from the original on 12 October 2007.
[32]  The Psychiatric, Psychogenic ans Somatopsychic Disorders Handbook. New Hyde Park, NY: Medical Examination Publishing Co. 1978. pp. 81–82. ISBN 0-87488-596-5.
[33] The Tox Guide for Arsenic (2007). The US Agency for Toxic Substances and Disease Registry.
[34] http://en.wikipedia.org/wiki/Dimercaprol
[35]  WHO Model List of EssentialMedicines". World Health Organization. October 2013.
[36] http://en.wikipedia.org/wiki/Arsphenamine
[37] Gibaud, Stéphane; Jaouen, Gérard (2010). "Arsenic - based drugs: from Fowler's solution to modern anticancer chemotherapy". Topics in Organometallic Chemistry. Topics in Organometallic Chemistry 32: 1–20. doi:10.1007/978-3-642-13185-1_1. ISBN 978-3-642-13184-4.
[38] http://www.fda.gov/AnimalVeterinary/SafetyHealth/ProductSafetyInformation/ucm258313.htm#What_did_FDA_announce_
[39] http://en.wikipedia.org/wiki/Nitarsone
[40] Zoetis. "Histostat: Type A Medicated Feed Article".
[41] http://en.wikipedia.org/wiki/Realgar
[42] http://en.wikipedia.org/wiki/Paris_Green
[43] "Hazardous Substance Fact Sheet". NJ Dept. of Health and Senior Services. Retrieved 2011-02-07.
[44] "How to Use Copper in Pyro Star Compositions to Create Blue Fireworks Stars". Skylighter.
[45] http://en.wikipedia.org/wiki/Paris_Green

http://www.npr.org/blogs/thesalt/2013/05/15/184261664/how-trace-amounts-of-arsenic-end-up-in-grovery-store-meat
http://www.naturalnews.com/035960_arsenic_chicken_Pfizer.html


Photo & Image Credits:

"Arsen 1a" by Arsen_1.jpg: Original uploader was Tomihahndorf at de.wikipediaderivative work: Materialscientist (talk) - Arsen_1.jpg. Licensed under Creative Commons Attribution-Share Alike 3.0 via Wikimedia Commons - http://commons.wikimedia.org/wiki/File:Arsen_1a.jpg#mediaviewer/File:Arsen_1a.jpg

"Realgar-229713" by Rob Lavinsky / iRocks.com - http://www.mindat.org/photo-229713.html. Licensed under Creative Commons Attribution-Share Alike 3.0 via Wikimedia Commons - http://commons.wikimedia.org/wiki/File:Realgar-229713.jpg#mediaviewer/File:Realgar-229713.jpg

"Dimercaprol" by Keenan Pepper - Own work. Licensed under Creative Commons Attribution-Share Alike 3.0 via Wikimedia Commons - http://commons.wikimedia.org/wiki/File:Dimercaprol.svg#mediaviewer/File:Dimercaprol.svg

"Paris Green". Via Wikipedia - http://en.wikipedia.org/wiki/File:Paris_Green.JPG#mediaviewer/File:Paris_Green.JPG

"3298054073 103cba6cc2 oMélangeVertParis" by Otis Historical Archives National Museum of Health & Medicine - http://www.flickr.com/photos/medicalmuseum/3298054073/in/photostream. Licensed under Public domain via Wikimedia Commons - http://commons.wikimedia.org/wiki/File:3298054073_103cba6cc2_oM%C3%A9langeVertParis.jpg#mediaviewer/File:3298054073_103cba6cc2_oM%C3%A9langeVertParis.jpg




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