Phosphorus, Selenium, Tellurium, and Sulfur

E. Bingham
{"title":"Phosphorus, Selenium, Tellurium, and Sulfur","authors":"E. Bingham","doi":"10.1002/0471435139.TOX044","DOIUrl":null,"url":null,"abstract":"Phosphorus and sulfur are elements 15 and 16 in the periodic chart and selenium and tellurium are in the same group as sulfur. Sulfur was not covered in the persons edition, but they have been added in this edition because of the importance of sulfur compounds. \n \n \n \nElemental phosphorous is produced as a by-product or intermediate in the production of phosphate fertilizer. Environmental contamination with phosphorus results from its manufacture into phosphorus compounds and during the transport and use of these compounds. In the manufacturing process, phosphate rock containing the mineral apatite (tricalcium phosphate) is heated, and elementary phosphorus is liberated as a vapor. Phosphorus is used to manufacture explosives, incendiaries, smoke bombs, chemicals, rodenticides, phosphor bronze, and fertilizer. The use of phosphate fertilizers results in increased nutrients in fresh water and is a major environmental pollution problem. \n \n \n \nPhosphorus exists in several allotropic forms: white (or yellow), red, and black (or violet). The last is of no industrial importance. Elemental yellow phosphorus extracted from bone was used to make “strike-anywhere” matches. In 1845, the occupational disease “phossy jaw,” a jaw bone necrosis, was recognized in workers who manufactured such matches. A prohibitive tax imposed in 1912 on matches made from yellow phosphorus led to the use of less toxic materials, red phosphorus and phosphorus sesquisulfide. The United States appears to have lagged behind European countries in that signatories of the Berne Convention of 1906 agreed not to manufacture or import matches made with yellow phosphorus. Occasional injuries continued to result from using yellow phosphorus to manufacture fireworks until 1926, when an agreement was reached to discontinue using yellow phosphorus for this purpose. \n \n \n \nThe world production of elemental phosphorus exceeds 1,000,000 metric tons. It is manufactured either in electric or blast furnaces. Both depend on silica as a flux for the calcium present in the phosphate rock. Nearly all of the phosphorus produced is converted into phosphoric acid or other phosphorus compounds. \n \n \n \nRed phosphorus does not ignite spontaneously but may be ignited by friction, static electricity, heating, or oxidizing agents. Handling it in an aqueous solution helps prevent fires. \n \n \n \nPhosphorus (white-yellow) can be absorbed through the skin, respiratory tract, and gastrointestinal (GI) tract. Experimental investigations in rats show the highest retention 5 days after oral administration in the liver, skeletal muscle, GI tract, blood, and kidney. Phosphorus is converted to phosphates in the body. Urinary excretion, the chief mode of elimination, is largely as organic and inorganic phosphates. \n \n \n \nSelenium (Se), a nonmetallic element of the sulfur group, is widely distributed in nature. It is obtained along with tellurium as a by-product of metal or refining, chiefly from copper. About sixteen tons are mined a year globally. \n \n \n \nBecause selenium is present in fossil fuels, up to 90% of the selenium content in ambient air is emitted during combustion of them. Air pollution concentrations averaged from 13 ng/mg3 in urban areas to 0.38 in remote areas. The mass medium diameter was 0.92 mm. The worldwide emissions of 10,000 tons/year from natural sources exceeds the atmospheric emissions from anthropogenic sources (5100 tons). However, 41,000 tons is emitted into the aquatic ecosystems. The largest contributor is electric power generating plants that produce 18,000 tons; manufacturing processes account for 12,000 tons. \n \n \n \nSelenium is an essential trace metal. Because of data suggesting that it may inhibit chemical carcinogenesis, it has been widely promoted as a dietary supplement. Selenium may replace sulfur and forms selenoproteins in plants and animal systems. \n \n \n \nMost of the world's selenium today is provided by recovery from anode muds of electrolytic copper refineries. Selenium is recovered by roasting these muds with soda or sulfuric acid or by melting them with a soda and niter. \n \n \n \nOne of the important uses of selenium is in photoelectric cells. \n \n \n \nToxic gases and vapors may be released in a fire involving selenium. Selenium can react violently with chromic oxide (CrO3), lithium silicon (Li6Si2), nitric acid, nitrogen trichloride, oxygen, potassium bromate, silver bromate, and fluorine. \n \n \n \nSelenium is an essential element. It interacts with a wide variety of vitamins, xenobiotics, and sulfur-containing amino acids. Selenium reduces the toxicity of many metals such as mercury, cadmium, lead, silver, copper, and arsenic. \n \n \n \nSelenium and most of its compounds are readily absorbed by oral intake or by breathing. Dermal exposure generally does not result in elevated selenium blood concentration. After absorption, high concentrations are found in the liver and kidney. In humans, dimethylselenide is formed and may account for the garlic odor of the breath. \n \n \n \nIn farm animals (cattle, sheep, hogs, and horses), toxicity from intake of feed containing excessive selenium has resulted. \n \n \n \nElemental tellurium (Te) has some metallic properties, although it is classed as a nonmetal or metalloid. The name is derived from the Latin word for earth. Tellurium is occasionally found naturally, more often as telluride of gold, calaverite. The elemental form has a bright luster, is brittle, readily powders, and burns slowly in air. Tellurium exists in two allotropic forms, as a powder and in the hexagonal crystalline form (isomorphous) with gray selenium. The concentration in the earth's crust is about 0.002 ppm. It is recovered from anode muds during the refining of blister copper. It is also found in various sulfide ores along with selenium and is produced as a by-product of metal refineries. The United States, Canada, Peru, and Japan are the largest producers. \n \n \n \nTellurium's industrial applications include its use as a metallurgical additive to improve the characteristics of alloys of copper, steel, lead, and bronze. \n \n \n \nElemental tellurium is poorly absorbed, but its more soluble compounds may undergo some oral absorption. Soluble tellurium can be absorbed through the skin, although ingestion or inhalation of fumes presents the greatest industrial hazard. A metallic taste in the mouth may result from excessive absorption. The characteristic sign of tellurium absorption is the garlic-like odor attributed to dimethyltelluride in the breath and sweat. This may persist for many days after exposure. Urinary, fecal, and biliary excretion also occur. Urinary excretion is probably more important than respiratory excretion in eliminating absorbed tellurium. Tellurium is complexed to plasma proteins, and little is found in the red blood cells. In the nervous system, tellurium accumulates in the gray matter, not the white matter, when injected intracerebrally. The metal is found in phagocytic and ependymal cells and in lysosomes as fine needles. The whole-body retention model assumes a long half-life based on tellurium dioxide. \n \n \n \nSulfur (S) occurs naturally as a yellow, water-insoluble solid. The name is from the Latin “sulphur.” Early Greek physicians mention sulfur and the fumes from burning sulfur in religious ceremonies. Sulfur constitutes about 0.053% of the earth's crust and occurs in two allotropic crystalline forms, rhombic and monoclinic. Below 96°C, only the rhombic form is stable. Large sedimentary deposits of almost pure sulfur are mined in Texas and Louisiana. Sulfur can be extracted from crude oil in the refining process, as well as from stack gases resulting from coal combustion. Sulfur occurs in fossil fuels and in metal (Fe, Pb) ores. Exposure may occur in numerous operations related to the mining and recovery of sulfur. The recovery of sulfur as a by-product accounts for a larger portion of the world's production than the mined mineral. Sulfur is one of the most important raw materials, particularly in the fertilizer industry. \n \n \n \nOrganic sulfur compounds occur in garlic, mustard, onions, and cabbage and are responsible for the odor of skunks. Sulfur occurs in living tissue and is part of some amino acids. Unlike many other inorganic elements, sulfur itself is relatively nontoxic. Sulfur and some of its salts have been used medicinally. The consumption of sulfur is a measure of national industrial development and economic activity. Sulfur is most often used as a chemical reagent, rather than as part of a finished product. \n \n \n \nVarious sulfur preparations have been used therapeutically. Exposure to sulfur particulates produces tracheobronchitis, characterized by cough, sore throat, chest pain, and lightheadedness. \n \n \nKeywords: \n \nPhosphorus; \nSelenium; \nTellurium; \nSulfur; \nSelenium compounds; \nSelenium compounds; \nTellurium compounds; \nSulfur compounds; \nPhossy jaw; \nPhosphorus poisoning; \nPhosphoric acid; \nSulfides; \nChlorides; \nFluorides; \nSulfuric acid; \nSulfides; \nSelenides","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2001-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"8","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Patty's Toxicology","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/0471435139.TOX044","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 8

Abstract

Phosphorus and sulfur are elements 15 and 16 in the periodic chart and selenium and tellurium are in the same group as sulfur. Sulfur was not covered in the persons edition, but they have been added in this edition because of the importance of sulfur compounds. Elemental phosphorous is produced as a by-product or intermediate in the production of phosphate fertilizer. Environmental contamination with phosphorus results from its manufacture into phosphorus compounds and during the transport and use of these compounds. In the manufacturing process, phosphate rock containing the mineral apatite (tricalcium phosphate) is heated, and elementary phosphorus is liberated as a vapor. Phosphorus is used to manufacture explosives, incendiaries, smoke bombs, chemicals, rodenticides, phosphor bronze, and fertilizer. The use of phosphate fertilizers results in increased nutrients in fresh water and is a major environmental pollution problem. Phosphorus exists in several allotropic forms: white (or yellow), red, and black (or violet). The last is of no industrial importance. Elemental yellow phosphorus extracted from bone was used to make “strike-anywhere” matches. In 1845, the occupational disease “phossy jaw,” a jaw bone necrosis, was recognized in workers who manufactured such matches. A prohibitive tax imposed in 1912 on matches made from yellow phosphorus led to the use of less toxic materials, red phosphorus and phosphorus sesquisulfide. The United States appears to have lagged behind European countries in that signatories of the Berne Convention of 1906 agreed not to manufacture or import matches made with yellow phosphorus. Occasional injuries continued to result from using yellow phosphorus to manufacture fireworks until 1926, when an agreement was reached to discontinue using yellow phosphorus for this purpose. The world production of elemental phosphorus exceeds 1,000,000 metric tons. It is manufactured either in electric or blast furnaces. Both depend on silica as a flux for the calcium present in the phosphate rock. Nearly all of the phosphorus produced is converted into phosphoric acid or other phosphorus compounds. Red phosphorus does not ignite spontaneously but may be ignited by friction, static electricity, heating, or oxidizing agents. Handling it in an aqueous solution helps prevent fires. Phosphorus (white-yellow) can be absorbed through the skin, respiratory tract, and gastrointestinal (GI) tract. Experimental investigations in rats show the highest retention 5 days after oral administration in the liver, skeletal muscle, GI tract, blood, and kidney. Phosphorus is converted to phosphates in the body. Urinary excretion, the chief mode of elimination, is largely as organic and inorganic phosphates. Selenium (Se), a nonmetallic element of the sulfur group, is widely distributed in nature. It is obtained along with tellurium as a by-product of metal or refining, chiefly from copper. About sixteen tons are mined a year globally. Because selenium is present in fossil fuels, up to 90% of the selenium content in ambient air is emitted during combustion of them. Air pollution concentrations averaged from 13 ng/mg3 in urban areas to 0.38 in remote areas. The mass medium diameter was 0.92 mm. The worldwide emissions of 10,000 tons/year from natural sources exceeds the atmospheric emissions from anthropogenic sources (5100 tons). However, 41,000 tons is emitted into the aquatic ecosystems. The largest contributor is electric power generating plants that produce 18,000 tons; manufacturing processes account for 12,000 tons. Selenium is an essential trace metal. Because of data suggesting that it may inhibit chemical carcinogenesis, it has been widely promoted as a dietary supplement. Selenium may replace sulfur and forms selenoproteins in plants and animal systems. Most of the world's selenium today is provided by recovery from anode muds of electrolytic copper refineries. Selenium is recovered by roasting these muds with soda or sulfuric acid or by melting them with a soda and niter. One of the important uses of selenium is in photoelectric cells. Toxic gases and vapors may be released in a fire involving selenium. Selenium can react violently with chromic oxide (CrO3), lithium silicon (Li6Si2), nitric acid, nitrogen trichloride, oxygen, potassium bromate, silver bromate, and fluorine. Selenium is an essential element. It interacts with a wide variety of vitamins, xenobiotics, and sulfur-containing amino acids. Selenium reduces the toxicity of many metals such as mercury, cadmium, lead, silver, copper, and arsenic. Selenium and most of its compounds are readily absorbed by oral intake or by breathing. Dermal exposure generally does not result in elevated selenium blood concentration. After absorption, high concentrations are found in the liver and kidney. In humans, dimethylselenide is formed and may account for the garlic odor of the breath. In farm animals (cattle, sheep, hogs, and horses), toxicity from intake of feed containing excessive selenium has resulted. Elemental tellurium (Te) has some metallic properties, although it is classed as a nonmetal or metalloid. The name is derived from the Latin word for earth. Tellurium is occasionally found naturally, more often as telluride of gold, calaverite. The elemental form has a bright luster, is brittle, readily powders, and burns slowly in air. Tellurium exists in two allotropic forms, as a powder and in the hexagonal crystalline form (isomorphous) with gray selenium. The concentration in the earth's crust is about 0.002 ppm. It is recovered from anode muds during the refining of blister copper. It is also found in various sulfide ores along with selenium and is produced as a by-product of metal refineries. The United States, Canada, Peru, and Japan are the largest producers. Tellurium's industrial applications include its use as a metallurgical additive to improve the characteristics of alloys of copper, steel, lead, and bronze. Elemental tellurium is poorly absorbed, but its more soluble compounds may undergo some oral absorption. Soluble tellurium can be absorbed through the skin, although ingestion or inhalation of fumes presents the greatest industrial hazard. A metallic taste in the mouth may result from excessive absorption. The characteristic sign of tellurium absorption is the garlic-like odor attributed to dimethyltelluride in the breath and sweat. This may persist for many days after exposure. Urinary, fecal, and biliary excretion also occur. Urinary excretion is probably more important than respiratory excretion in eliminating absorbed tellurium. Tellurium is complexed to plasma proteins, and little is found in the red blood cells. In the nervous system, tellurium accumulates in the gray matter, not the white matter, when injected intracerebrally. The metal is found in phagocytic and ependymal cells and in lysosomes as fine needles. The whole-body retention model assumes a long half-life based on tellurium dioxide. Sulfur (S) occurs naturally as a yellow, water-insoluble solid. The name is from the Latin “sulphur.” Early Greek physicians mention sulfur and the fumes from burning sulfur in religious ceremonies. Sulfur constitutes about 0.053% of the earth's crust and occurs in two allotropic crystalline forms, rhombic and monoclinic. Below 96°C, only the rhombic form is stable. Large sedimentary deposits of almost pure sulfur are mined in Texas and Louisiana. Sulfur can be extracted from crude oil in the refining process, as well as from stack gases resulting from coal combustion. Sulfur occurs in fossil fuels and in metal (Fe, Pb) ores. Exposure may occur in numerous operations related to the mining and recovery of sulfur. The recovery of sulfur as a by-product accounts for a larger portion of the world's production than the mined mineral. Sulfur is one of the most important raw materials, particularly in the fertilizer industry. Organic sulfur compounds occur in garlic, mustard, onions, and cabbage and are responsible for the odor of skunks. Sulfur occurs in living tissue and is part of some amino acids. Unlike many other inorganic elements, sulfur itself is relatively nontoxic. Sulfur and some of its salts have been used medicinally. The consumption of sulfur is a measure of national industrial development and economic activity. Sulfur is most often used as a chemical reagent, rather than as part of a finished product. Various sulfur preparations have been used therapeutically. Exposure to sulfur particulates produces tracheobronchitis, characterized by cough, sore throat, chest pain, and lightheadedness. Keywords: Phosphorus; Selenium; Tellurium; Sulfur; Selenium compounds; Selenium compounds; Tellurium compounds; Sulfur compounds; Phossy jaw; Phosphorus poisoning; Phosphoric acid; Sulfides; Chlorides; Fluorides; Sulfuric acid; Sulfides; Selenides
磷,硒,碲和硫
在农场动物(牛、羊、猪和马)中,由于摄入含有过量硒的饲料而导致中毒。元素碲(Te)具有一些金属性质,尽管它被归类为非金属或类金属。这个名字来源于拉丁语中的“地球”。碲偶尔在自然界中被发现,更常见的形式是金的碲化物——钙钙石。单质具有明亮的光泽,易碎,易成粉末,在空气中燃烧缓慢。碲以两种同素异形体存在,一种是粉末,另一种是与灰色硒呈六方晶状(同形)。在地壳中的浓度约为0.002 ppm。它是在泡铜精炼过程中从阳极泥中回收的。它也与硒一起存在于各种硫化物矿石中,是金属精炼厂的副产品。美国、加拿大、秘鲁和日本是最大的生产国。碲的工业应用包括用作冶金添加剂,以改善铜、钢、铅和青铜合金的特性。元素碲吸收不良,但其较易溶的化合物可经口服吸收。可溶性碲可通过皮肤吸收,但摄入或吸入烟雾是最大的工业危害。口中有金属味可能是由于吸收过多造成的。碲吸收的特征标志是呼吸和汗液中二甲基碲化物引起的大蒜味。这种情况可能在接触后持续许多天。尿、粪、胆排泄也会发生。在消除吸收的碲方面,尿排泄可能比呼吸排泄更重要。碲与血浆蛋白结合,在红细胞中发现很少。在神经系统中,当注入脑内时,碲在灰质而不是白质中积累。这种金属存在于吞噬细胞和室管膜细胞以及溶酶体中,呈细针状。全身保留模型假定以二氧化碲为基础的半衰期很长。硫(S)是一种黄色的、不溶于水的固体。这个名字来自拉丁语“硫磺”。早期的希腊医生在宗教仪式上提到硫磺和硫磺燃烧产生的烟雾。硫约占地壳的0.053%,以两种同素异形体晶体形式存在,菱形和单斜晶。在96℃以下,只有菱形是稳定的。德克萨斯州和路易斯安那州开采了大量几乎纯硫的沉积层。硫可以在精炼过程中从原油中提取,也可以从煤燃烧产生的烟囱气体中提取。硫存在于化石燃料和金属(铁、铅)矿石中。在与硫的开采和回收有关的许多作业中都可能发生接触。作为副产品的硫的回收占世界产量的比例比开采的矿物要大。硫是最重要的原料之一,特别是在化肥工业中。有机硫化合物存在于大蒜、芥末、洋葱和卷心菜中,是臭鼬发出气味的原因。硫存在于活组织中,是一些氨基酸的组成部分。与许多其他无机元素不同,硫本身是相对无毒的。硫和它的一些盐类已被用作医药。硫的消耗量是衡量一个国家工业发展和经济活动的一个指标。硫通常用作化学试剂,而不是成品的一部分。各种硫制剂已用于治疗。接触硫微粒会导致气管支气管炎,其特征是咳嗽、喉咙痛、胸痛和头晕。关键词:磷;硒;碲;硫;硒化合物;硒化合物;碲化合物;硫化合物;磷的下巴;磷中毒;磷酸;硫化物;氯化物;氟化物;硫酸;硫化物;硒化物
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