Pub Date : 2012-08-17DOI: 10.1002/0471435139.TOX107.PUB2
A. Scott
“… and God divided the light from the darkness, and God called the light day, and the darkness He called night. And the evening and the morning were the first day” (Genesis 1:4–5, King James Version). Thus, as has been recognized for millennia, Homo sapiens, as well as all other living creatures on earth, are destined to live in a regular cycle of light and darkness, that is, the 24-h solar day. For diurnal species, such as human beings, the sunlight portion of the day is the time of activity and the dark, nighttime portion the time for sleeping. Periodicity is an integral part of life. Although we are under the influence of environmental rhythms, such as the daylight–night cycle, we are also under the physiological influence of our own internal biological clock. Normally the synchronization of our biological rhythms with each other and with environmental rhythms (external time cues) maximizes our waking and sleeping performance and promotes overall well-being. Night work is opposed to the innate drive to sleep at night and work during the daytime. This unnatural mismatch of environmental and internal temporal influences is of concern for shiftworkers due to the often disruptive effect of schedule-related time shifts on the normal synchronization of individual biological rhythms with each other as well as with the external time cues. This chapter reviews basic chronobiological principles as they relate to shiftworker safety and health. Studies dealing with the effects of time shifts on sleep and alertness are discussed as well as performance rhythms. Research exploring the consequences of shiftwork on physical and mental health is reviewed. Countermeasures for minimizing adverse health and safety effects of sleep deprivation and biological rhythm disruption are presented, including work scheduling considerations and medical surveillance. Industrial hygiene considerations related to control of worker exposure to potential toxins during extended and rotating shifts are presented. Finally, international and U.S. regulatory policy regarding shiftwork scheduling and special provisions for shiftworkers are reviewed. Keywords: Circadian rhythms; Biological rhythms; Biological clock; Time shifts; Zeitgebers; Melatonin; Photoreceptors; Shiftwork; Performance; Safety; Sleep; Sleep deprivation; Rotating schedule job; Accidents; Errors; Public disasters; Transportation incidents; Medical disorders; Depression; Medical screening; Surveillance; Gastrointestinal disorders; Cardiovascular morbidity; Mental health; Reproduction; Scedule changes; Regulation; Countermeasures; Caffeine; Diet; Exercise
{"title":"Biological Rhythms, Shiftwork, and Occupational Health","authors":"A. Scott","doi":"10.1002/0471435139.TOX107.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX107.PUB2","url":null,"abstract":"“… and God divided the light from the darkness, and God called the light day, and the darkness He called night. And the evening and the morning were the first day” (Genesis 1:4–5, King James Version). Thus, as has been recognized for millennia, Homo sapiens, as well as all other living creatures on earth, are destined to live in a regular cycle of light and darkness, that is, the 24-h solar day. For diurnal species, such as human beings, the sunlight portion of the day is the time of activity and the dark, nighttime portion the time for sleeping. Periodicity is an integral part of life. \u0000 \u0000 \u0000 \u0000Although we are under the influence of environmental rhythms, such as the daylight–night cycle, we are also under the physiological influence of our own internal biological clock. Normally the synchronization of our biological rhythms with each other and with environmental rhythms (external time cues) maximizes our waking and sleeping performance and promotes overall well-being. Night work is opposed to the innate drive to sleep at night and work during the daytime. This unnatural mismatch of environmental and internal temporal influences is of concern for shiftworkers due to the often disruptive effect of schedule-related time shifts on the normal synchronization of individual biological rhythms with each other as well as with the external time cues. \u0000 \u0000 \u0000 \u0000This chapter reviews basic chronobiological principles as they relate to shiftworker safety and health. Studies dealing with the effects of time shifts on sleep and alertness are discussed as well as performance rhythms. Research exploring the consequences of shiftwork on physical and mental health is reviewed. Countermeasures for minimizing adverse health and safety effects of sleep deprivation and biological rhythm disruption are presented, including work scheduling considerations and medical surveillance. Industrial hygiene considerations related to control of worker exposure to potential toxins during extended and rotating shifts are presented. Finally, international and U.S. regulatory policy regarding shiftwork scheduling and special provisions for shiftworkers are reviewed. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Circadian rhythms; \u0000Biological rhythms; \u0000Biological clock; \u0000Time shifts; \u0000Zeitgebers; \u0000Melatonin; \u0000Photoreceptors; \u0000Shiftwork; \u0000Performance; \u0000Safety; \u0000Sleep; \u0000Sleep deprivation; \u0000Rotating schedule job; \u0000Accidents; \u0000Errors; \u0000Public disasters; \u0000Transportation incidents; \u0000Medical disorders; \u0000Depression; \u0000Medical screening; \u0000Surveillance; \u0000Gastrointestinal disorders; \u0000Cardiovascular morbidity; \u0000Mental health; \u0000Reproduction; \u0000Scedule changes; \u0000Regulation; \u0000Countermeasures; \u0000Caffeine; \u0000Diet; \u0000Exercise","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"15 1","pages":"333-398"},"PeriodicalIF":0.0,"publicationDate":"2012-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83299675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-08-17DOI: 10.1002/0471435139.TOX054.PUB2
J. Ovesen
Although aliphatic nitro compounds, aliphatic nitrates, and aliphatic nitrites have several features in common (nitrogen–oxygen grouping, explosiveness, methemoglobin formation), there are significant differences in their toxic effects. Some of their attributes are summarized. The esters of nitric and nitrous acids, whose nitrogen is linked to carbon through oxygen, are very similar in their pharmacological effects. Both produce methemoglobinemia and vascular dilatation with hypotension and headache. These effects are transient. None of the series has appreciable irritant properties. Pathological changes occur in animals only after high levels of exposure and are generally nonspecific and reversible. The nitric acid esters of the monofunctional and lower polyfunctional alcohols are absorbed through the skin. Information is not available on the skin absorption of alkyl nitrites. Members of both groups are well absorbed from the mucous membranes and lungs. Heinz body formation has been observed with the nitrates but not with the nitrites. Nitro compounds, like nitrates and nitrites, cause methemoglobinemia in animals. Heinz body formation parallels this activity within the series. Although some members are metabolized to nitrate and nitrite, there is no significant effect on blood pressure or respiration. As with the lower nitrates and nitrites, anesthetic symptoms are observed in animals during acute exposures, but these occur late. The prominent effect is irritation of the skin, mucous membranes, and respiratory tract. This is most marked with chlorinated nitroparaffins and nitroolefins. In addition to respiratory tract injury, cellular damage may be observed in the liver and kidneys. Skin absorption is negligible except for the nitroolefins. The nitramines have entirely different activity. RDX is a convulsant for humans and animals. Skin absorption, irritation, vasodilatation, methemoglobin formation, and permanent pathological damage are either insignificant or absent after repeated doses. Transient illness has been associated with the industrial use or manufacture of these materials, but fatalities and chronic intoxication have been uncommon. Some members of each group present extremely high fire and explosion hazards. Keywords: Aliphatic nitrates; aliphatic nitrites; aliphatic nitro compounds; alkyl nitrites; nitroolefins
{"title":"Aliphatic Nitro, Nitrate, and Nitrite Compounds","authors":"J. Ovesen","doi":"10.1002/0471435139.TOX054.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX054.PUB2","url":null,"abstract":"Although aliphatic nitro compounds, aliphatic nitrates, and aliphatic nitrites have several features in common (nitrogen–oxygen grouping, explosiveness, methemoglobin formation), there are significant differences in their toxic effects. Some of their attributes are summarized. The esters of nitric and nitrous acids, whose nitrogen is linked to carbon through oxygen, are very similar in their pharmacological effects. Both produce methemoglobinemia and vascular dilatation with hypotension and headache. These effects are transient. None of the series has appreciable irritant properties. Pathological changes occur in animals only after high levels of exposure and are generally nonspecific and reversible. The nitric acid esters of the monofunctional and lower polyfunctional alcohols are absorbed through the skin. Information is not available on the skin absorption of alkyl nitrites. Members of both groups are well absorbed from the mucous membranes and lungs. Heinz body formation has been observed with the nitrates but not with the nitrites. \u0000 \u0000 \u0000 \u0000Nitro compounds, like nitrates and nitrites, cause methemoglobinemia in animals. Heinz body formation parallels this activity within the series. Although some members are metabolized to nitrate and nitrite, there is no significant effect on blood pressure or respiration. As with the lower nitrates and nitrites, anesthetic symptoms are observed in animals during acute exposures, but these occur late. The prominent effect is irritation of the skin, mucous membranes, and respiratory tract. This is most marked with chlorinated nitroparaffins and nitroolefins. In addition to respiratory tract injury, cellular damage may be observed in the liver and kidneys. Skin absorption is negligible except for the nitroolefins. \u0000 \u0000 \u0000 \u0000The nitramines have entirely different activity. RDX is a convulsant for humans and animals. Skin absorption, irritation, vasodilatation, methemoglobin formation, and permanent pathological damage are either insignificant or absent after repeated doses. \u0000 \u0000 \u0000 \u0000Transient illness has been associated with the industrial use or manufacture of these materials, but fatalities and chronic intoxication have been uncommon. Some members of each group present extremely high fire and explosion hazards. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Aliphatic nitrates; \u0000aliphatic nitrites; \u0000aliphatic nitro compounds; \u0000alkyl nitrites; \u0000nitroolefins","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"26 1","pages":"1-50"},"PeriodicalIF":0.0,"publicationDate":"2012-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75528448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-08-17DOI: 10.1002/0471435139.TOX086.PUB2
S. Cragg
There are seven U.S. manufacturers of ethers and other derivatives of ethylene glycol (EG), diethylene glycol (DEG), and higher glycols. Five of them are members of the American Chemistry Council (ACC) Glycol Ethers' Panel. The glycol ethers most commonly encountered industrially are colorless liquids that have mild ethereal odors. Alkyl glycol ethers are manufactured in a closed, continuous process by reacting ethylene oxide with an anhydrous alcohol in the presence of a suitable catalyst. Depending on the molar ratios of the reactants and other process parameters, the product mixtures obtained contain varying amounts of the monoethylene, diethylene, triethylene, and higher glycol ethers. Typically, the products in these mixtures are separated and purified by fractional distillation. The miscibility of most of these ethers with water and with a large number of organic solvents makes them especially useful as solvents in oil–water compositions. Their relatively slow rate of evaporation also makes them useful as solvents and coalescing agents in paints. Other uses include inks, cleaners, chemical intermediates, process solvents, brake fluids, and deicers. The ethers of the higher glycols are used as hydraulic fluids. An estimate of the U.S. production and use of representative ethylene glycol ethers is presented. Production of ethylene glycol ethers (total) in Western Europe amounted to 245 thousand metric tons in 1995. Occupational exposure to glycol ethers occurs dermally and by inhalation. Ingestion is not a concern in industrial exposure, although some cases of intentional ingestion of consumer products containing ethylene glycol ethers have been reported. A number of analytical methods have been published that are suitable for detecting glycol ethers in environmental air samples. Glycol ethers generally have low acute, single-dose toxicity, and LD50 values generally range from 1.0 to 4.0 g/kg of body weight. In animals and humans, high-dose administrations (>350 mg/kg) result in central nervous system (CNS) depression, although the results from many studies show no specific damage to neural tissues. Other toxicological effects attributable to glycol ethers are associated with metabolism to the corresponding alkoxyacetic acids. In the case of EGME, EGEE, and certain other glycol ether derivatives, significant reproductive, developmental, hematologic, and immunologic effects have been associated with the formation of either methoxyacetic acid (MAA) or ethoxyacetic acids (EAA). For other glycol ether derivatives substituted with propyl, butyl, or higher homologues, both developmental effects secondary to maternal toxicity (without teratogenic effects) and hematologic effects are observed. Ethylene glycol ethers and acetates may enter the environment from manufacturing effluents and emissions and as a result of their use in commercial products. Keywords: ethylene glycol ethers; ethylene glycol et
{"title":"Ethers of Ethylene Glycol and Derivatives","authors":"S. Cragg","doi":"10.1002/0471435139.TOX086.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX086.PUB2","url":null,"abstract":"There are seven U.S. manufacturers of ethers and other derivatives of ethylene glycol (EG), diethylene glycol (DEG), and higher glycols. Five of them are members of the American Chemistry Council (ACC) Glycol Ethers' Panel. \u0000 \u0000 \u0000 \u0000The glycol ethers most commonly encountered industrially are colorless liquids that have mild ethereal odors. Alkyl glycol ethers are manufactured in a closed, continuous process by reacting ethylene oxide with an anhydrous alcohol in the presence of a suitable catalyst. Depending on the molar ratios of the reactants and other process parameters, the product mixtures obtained contain varying amounts of the monoethylene, diethylene, triethylene, and higher glycol ethers. Typically, the products in these mixtures are separated and purified by fractional distillation. \u0000 \u0000 \u0000 \u0000The miscibility of most of these ethers with water and with a large number of organic solvents makes them especially useful as solvents in oil–water compositions. Their relatively slow rate of evaporation also makes them useful as solvents and coalescing agents in paints. Other uses include inks, cleaners, chemical intermediates, process solvents, brake fluids, and deicers. The ethers of the higher glycols are used as hydraulic fluids. An estimate of the U.S. production and use of representative ethylene glycol ethers is presented. Production of ethylene glycol ethers (total) in Western Europe amounted to 245 thousand metric tons in 1995. \u0000 \u0000 \u0000 \u0000Occupational exposure to glycol ethers occurs dermally and by inhalation. Ingestion is not a concern in industrial exposure, although some cases of intentional ingestion of consumer products containing ethylene glycol ethers have been reported. \u0000 \u0000 \u0000 \u0000A number of analytical methods have been published that are suitable for detecting glycol ethers in environmental air samples. \u0000 \u0000 \u0000 \u0000Glycol ethers generally have low acute, single-dose toxicity, and LD50 values generally range from 1.0 to 4.0 g/kg of body weight. In animals and humans, high-dose administrations (>350 mg/kg) result in central nervous system (CNS) depression, although the results from many studies show no specific damage to neural tissues. Other toxicological effects attributable to glycol ethers are associated with metabolism to the corresponding alkoxyacetic acids. In the case of EGME, EGEE, and certain other glycol ether derivatives, significant reproductive, developmental, hematologic, and immunologic effects have been associated with the formation of either methoxyacetic acid (MAA) or ethoxyacetic acids (EAA). For other glycol ether derivatives substituted with propyl, butyl, or higher homologues, both developmental effects secondary to maternal toxicity (without teratogenic effects) and hematologic effects are observed. \u0000 \u0000 \u0000 \u0000Ethylene glycol ethers and acetates may enter the environment from manufacturing effluents and emissions and as a result of their use in commercial products. \u0000 \u0000 \u0000Keywords: \u0000 \u0000ethylene glycol ethers; \u0000ethylene glycol et","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"42 1","pages":"641-788"},"PeriodicalIF":0.0,"publicationDate":"2012-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80050551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-08-17DOI: 10.1002/0471435139.TOX078.PUB2
C. Bevan
This chapter reviews linear and branched C7 to C18 monohydric aliphatic alcohols as well as aromatic, alicyclic, aliphatic unsaturated, and aliphatic halogenated alcohols. The CAS registry number and molecular structures have been provided for all of the alcohols, except for the oxo alcohols. These alcohols are mixtures of isomeric alcohols with the same molecular formula, with the composition and CAS registry number dependent on the olefin feedstock. The physical and chemical properties for these alcohols are listed. The National Fire Protection Association (NFPA) has prepared a rating system to assess the physical and chemical hazards of chemicals with respect to flammability, health, and reactivity. In general, these alcohols are not reactive chemicals, except for the unsaturated alcohols. The most important commercial member of the heptanols is isoheptyl alcohol, which is a mixture of branched C7 alcohols. This alcohol is used for the manufacture of esters such as phthalate plasticizers. 1-Heptanol has little commercial value. Other C7 alcohols are 2,3-dimethyl-1-pentanol and the secondary alcohols, 2-heptanol, 3-heptanol, 4-heptanol, and 2,4-dimethyl-3-pentanol. 2-Heptanol and 3-heptanol can exist as enantiomers. The available toxicity data indicate that heptanols have a low order of acute toxicity and no occupational exposure standards exist for them. The most important commercial C8 alcohols are 2-ethylhexanol and a mixture of branched C8 alcohols referred to as isooctyl alcohol. Other octanols of lesser commercial interest are 2-octanol, 1-octanol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, and 2-ethyl-4-methyl-1-pentanol. These alcohols are liquids at ambient temperature and are used primarily in producing esters, such as plasticizers. No occupational exposure standards exist for octanols except for isooctyl alcohol. The most important commercial members of this subgroup of alcohols are the C9 oxo alcohols, which are a mixture of predominantly C9 branched alcohols, diisobutyl carbinol, and 2,6-dimethyl-4-heptanol. Two C9 alcohols of lesser commercial importance are 1-nonanol and 3,5,5-trimethyl-1-hexanol. All of these alcohols are liquids at ambient temperatures. Acute studies in animals indicate a low order of toxicity. These alcohols are irritating to the skin, eyes, and respiratory tract. They are also aspirations hazard. No serious adverse effects from industrial exposure were reported in humans. Prolonged or excessive exposure to the alcohols can produce local irritation and narcosis. No occupational exposure standards have been established for any of the nonanols. The decanols consist of more than 20 structural isomers, including a number of enantiomers. The most important commercial members are the C10 oxo alcohols, which exist as a mixture of C10 branched alcohols. Many of these alcohols are liquids. Unlike the lower alcohols, the decanols are less volatile and flammable.
{"title":"Monohydric Alcohols—C7 to C18, Aromatic, and Other Alcohols","authors":"C. Bevan","doi":"10.1002/0471435139.TOX078.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX078.PUB2","url":null,"abstract":"This chapter reviews linear and branched C7 to C18 monohydric aliphatic alcohols as well as aromatic, alicyclic, aliphatic unsaturated, and aliphatic halogenated alcohols. The CAS registry number and molecular structures have been provided for all of the alcohols, except for the oxo alcohols. These alcohols are mixtures of isomeric alcohols with the same molecular formula, with the composition and CAS registry number dependent on the olefin feedstock. \u0000 \u0000 \u0000 \u0000The physical and chemical properties for these alcohols are listed. The National Fire Protection Association (NFPA) has prepared a rating system to assess the physical and chemical hazards of chemicals with respect to flammability, health, and reactivity. In general, these alcohols are not reactive chemicals, except for the unsaturated alcohols. \u0000 \u0000 \u0000 \u0000The most important commercial member of the heptanols is isoheptyl alcohol, which is a mixture of branched C7 alcohols. This alcohol is used for the manufacture of esters such as phthalate plasticizers. 1-Heptanol has little commercial value. Other C7 alcohols are 2,3-dimethyl-1-pentanol and the secondary alcohols, 2-heptanol, 3-heptanol, 4-heptanol, and 2,4-dimethyl-3-pentanol. 2-Heptanol and 3-heptanol can exist as enantiomers. \u0000 \u0000 \u0000 \u0000The available toxicity data indicate that heptanols have a low order of acute toxicity and no occupational exposure standards exist for them. \u0000 \u0000 \u0000 \u0000The most important commercial C8 alcohols are 2-ethylhexanol and a mixture of branched C8 alcohols referred to as isooctyl alcohol. Other octanols of lesser commercial interest are 2-octanol, 1-octanol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, and 2-ethyl-4-methyl-1-pentanol. These alcohols are liquids at ambient temperature and are used primarily in producing esters, such as plasticizers. No occupational exposure standards exist for octanols except for isooctyl alcohol. \u0000 \u0000 \u0000 \u0000The most important commercial members of this subgroup of alcohols are the C9 oxo alcohols, which are a mixture of predominantly C9 branched alcohols, diisobutyl carbinol, and 2,6-dimethyl-4-heptanol. Two C9 alcohols of lesser commercial importance are 1-nonanol and 3,5,5-trimethyl-1-hexanol. All of these alcohols are liquids at ambient temperatures. \u0000 \u0000 \u0000 \u0000Acute studies in animals indicate a low order of toxicity. These alcohols are irritating to the skin, eyes, and respiratory tract. They are also aspirations hazard. No serious adverse effects from industrial exposure were reported in humans. Prolonged or excessive exposure to the alcohols can produce local irritation and narcosis. No occupational exposure standards have been established for any of the nonanols. \u0000 \u0000 \u0000 \u0000The decanols consist of more than 20 structural isomers, including a number of enantiomers. The most important commercial members are the C10 oxo alcohols, which exist as a mixture of C10 branched alcohols. Many of these alcohols are liquids. Unlike the lower alcohols, the decanols are less volatile and flammable. ","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"5 1","pages":"1-54"},"PeriodicalIF":0.0,"publicationDate":"2012-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82052405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-01-27DOI: 10.1002/0471435139.TOX035.PUB2
Barbara Malczewska‐Toth
Titanium, zirconium, and hafnium belong to the group IVB of the periodic table. A characteristic feature of these transition elements is the ease with which they form stable complex ions. Features that contribute to this ability are favorably high charge-to-radius ratios and the availability of unfilled d orbitals. The ability of forming metallic bonds is demonstrated by the existence of a wide variety of alloys among different transition metals. Other features of these metals are high densities, high melting points, and low vapor pressures. Within this group, these properties tend to increase with increasing atomic weight. This chapter discusses the chemical and physical properties followed by the toxicity of each chemical and compound in three sections: the first section provides details on titanium, the second section on zirconium, and the third section on hafnium. Tables present the atomic number, atomic weight, and natural isotopes of titanium, zirconium, and hafnium. Keywords: Alloys; by-products; exposure assessment; hafnium; hafnium compounds; lung function; physical and chemical properties; production; occurrence; standards, guidelines, and regulations; superalloys; titanium; titanium compounds; toxic effects; use; zirconium; zirconium compounds
{"title":"Titanium, Zirconium, and Hafnium","authors":"Barbara Malczewska‐Toth","doi":"10.1002/0471435139.TOX035.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX035.PUB2","url":null,"abstract":"Titanium, zirconium, and hafnium belong to the group IVB of the periodic table. A characteristic feature of these transition elements is the ease with which they form stable complex ions. Features that contribute to this ability are favorably high charge-to-radius ratios and the availability of unfilled d orbitals. The ability of forming metallic bonds is demonstrated by the existence of a wide variety of alloys among different transition metals. Other features of these metals are high densities, high melting points, and low vapor pressures. Within this group, these properties tend to increase with increasing atomic weight. \u0000 \u0000 \u0000 \u0000This chapter discusses the chemical and physical properties followed by the toxicity of each chemical and compound in three sections: the first section provides details on titanium, the second section on zirconium, and the third section on hafnium. Tables present the atomic number, atomic weight, and natural isotopes of titanium, zirconium, and hafnium. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Alloys; \u0000by-products; \u0000exposure assessment; \u0000hafnium; \u0000hafnium compounds; \u0000lung function; \u0000physical and chemical properties; \u0000production; \u0000occurrence; \u0000standards, guidelines, and regulations; \u0000superalloys; \u0000titanium; \u0000titanium compounds; \u0000toxic effects; \u0000use; \u0000zirconium; \u0000zirconium compounds","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"12 1","pages":"427-474"},"PeriodicalIF":0.0,"publicationDate":"2012-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76786716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-01-27DOI: 10.1002/0471435139.TOX028.PUB2
M. Genter
Magnesium, calcium, strontium, barium, and radium are among the alkaline-earth metals, found in group IIA of the periodic table. Sir Humphrey Davy first described the electrochemical isolation of barium, magnesium, calcium, and strontium in 1808, and the isolation of a radium salt from waste uranium ore was described by the Curies in 1898. These metals are being presented separately from other metals in this edition. Beryllium, the lightest of the alkaline-earth metals, is also being handled separately from the alkaline earths covered in this chapter, as beryllium has a number of special immunological and pulmonary toxicology concerns that impact workplace practices and industrial hygiene concerns. Topics covered include chemical and physical properties, production and use, exposure assessments, toxic effects, standards regulations, and guidelines for each matter. Keywords: barium; biomarkers; calcium; exposure assessment; magnesium; mechanisms; production; radium; regulations; standards; strontium; use; toxic effects
{"title":"Magnesium, Calcium, Strontium, Barium, and Radium","authors":"M. Genter","doi":"10.1002/0471435139.TOX028.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX028.PUB2","url":null,"abstract":"Magnesium, calcium, strontium, barium, and radium are among the alkaline-earth metals, found in group IIA of the periodic table. Sir Humphrey Davy first described the electrochemical isolation of barium, magnesium, calcium, and strontium in 1808, and the isolation of a radium salt from waste uranium ore was described by the Curies in 1898. These metals are being presented separately from other metals in this edition. Beryllium, the lightest of the alkaline-earth metals, is also being handled separately from the alkaline earths covered in this chapter, as beryllium has a number of special immunological and pulmonary toxicology concerns that impact workplace practices and industrial hygiene concerns. Topics covered include chemical and physical properties, production and use, exposure assessments, toxic effects, standards regulations, and guidelines for each matter. \u0000 \u0000 \u0000Keywords: \u0000 \u0000barium; \u0000biomarkers; \u0000calcium; \u0000exposure assessment; \u0000magnesium; \u0000mechanisms; \u0000production; \u0000radium; \u0000regulations; \u0000standards; \u0000strontium; \u0000use; \u0000toxic effects","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"11 1","pages":"145-166"},"PeriodicalIF":0.0,"publicationDate":"2012-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78779845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-01-27DOI: 10.1002/0471435139.TOX033.PUB2
Cih Csp James H. Stewart Ph.D., Cih David Macintosh ScD, Joseph Allen ScD, Cih John McCarthy ScD
Germanium, tin, and copper have each played a major role in the development of civilization although at distinctly different periods of history . A German chemist Clemens A. Winkler first isolated Germanium in 1886 from the mineral argyrodite, a mixed sulfide of silver and germanium, and named it after his home country Germany. Today germanium is used in the computer industry (as resistors on computer chips), in fiber optics, solar applications, metallurgy, and chemotherapy. In contrast, the archaeological record shows that tin and copper were components of man-made objects found in Iraq that date back to 9000 BC. The Bronze Age began approximately 3500 bc with the discovery that easily smelted soft copper could be made harder and stronger by alloying with tin. Tin and copper remain important for the manufacture of numerous commercially valuable products including electrical conductors, piping, and antimicrobial agents. Germanium is a semiconducting metal from Group IVA of the periodic table and it forms a series of hydrides, which correspond chemically to the methane series of hydrocarbons and to silanes (silicon series of hydrides). Selected physical and chemical properties of germanium and some of its more common compounds are provided. There are numerous organogermanium compounds. Interest in the organogermanium compounds has centered on their antimicrobial activity and the fact that their mammalian toxicity is considerably lower than the corresponding derivatives of tin or lead. In recent years various germanium compounds, for example, carboxyethyl germanium sesquioxide (Ge-132) and lactate–citrate–germanate, have been sold as nutritional supplements, thereby creating a new exposure pathway for germanium and increasing exposure above levels predicted from industrial uses. Tin is a solid, rather an unreactive metal in Group IVA of the periodic table and has the largest number of stable isotopes of any element. Tin also has a large number of unstable isotopes with half-lives ranging from 2.2 min to 105 years. The physical and chemical properties of tin and some of its compounds are provided. Data are shown for elemental tin, organotin compounds, and some inorganic tin compounds. Copper is located in Group IB of the periodic table and was one of the first metals used by humans. The electrical conductivity and malleability of copper are important commercial properties of the metal. The physical and chemical properties of copper and its related compounds are provided. The adverse health effects associated with copper production may be due to the large amounts of sulfur oxides generated during smelting or because of the impurities, such as arsenic and antimony. Exposure to copper can occur from environmental sources such as food, water from copper pipes, and soil ingestion near copper smelting operations. Keywords: agriculture; copper; environmental impact; exposure assessment; fish; germanium; guidelines;
锗、锡和铜虽然处于不同的历史时期，但在人类文明的发展中都发挥了重要作用。1886年，德国化学家克莱门斯·温克勒(Clemens A. Winkler)首先从银和锗的混合硫化物银辉石(argyroite)中分离出锗，并以他的祖国德国命名。今天，锗被用于计算机工业(作为计算机芯片上的电阻器)、光纤、太阳能应用、冶金和化学治疗。相比之下，考古记录显示，锡和铜是公元前9000年在伊拉克发现的人造物品的成分。青铜时代大约始于公元前3500年，人们发现容易冶炼的软铜可以通过与锡合金化而变得更硬更强。锡和铜对于制造许多有商业价值的产品仍然很重要，包括导体、管道和抗菌剂。锗是元素周期表中IVA族的一种半导体金属，它形成了一系列的氢化物，在化学上对应于甲烷系列的碳氢化合物和硅烷(硅系列的氢化物)。提供了锗及其一些较常见化合物的选定物理和化学性质。有许多有机锗化合物。人们对有机锗化合物的兴趣主要集中在它们的抗菌活性和它们对哺乳动物的毒性远低于锡或铅的相应衍生物这一事实。近年来，各种锗化合物，例如羧乙基倍半氧化锗(Ge-132)和乳酸-柠檬酸-锗酸盐作为营养补充剂出售，从而创造了锗的新接触途径，并使接触量增加到超出工业用途所预测的水平。锡是一种固体，在元素周期表的IVA族中是一种不活泼的金属，在所有元素中拥有最多的稳定同位素。锡也有大量半衰期从2.2分钟到105年不等的不稳定同位素。介绍了锡及其某些化合物的物理和化学性质。显示了元素锡、有机锡化合物和一些无机锡化合物的数据。铜位于元素周期表的IB族，是人类最早使用的金属之一。铜的导电性和延展性是铜的重要商业性能。介绍了铜及其相关化合物的理化性质。与铜生产有关的不利健康影响可能是由于冶炼过程中产生大量硫氧化物，或由于砷和锑等杂质。铜的接触可能来自环境来源，如食物、铜管道中的水以及铜冶炼作业附近的土壤摄入。关键词:农业;铜;环境影响;暴露评估;鱼;锗;指导方针;无机锡化合物;物理和化学性质;有机锡化合物;生产;监管;肾功能衰竭;标准;锡;镀锡;毒性作用;使用
{"title":"Germanium, Tin, and Copper","authors":"Cih Csp James H. Stewart Ph.D., Cih David Macintosh ScD, Joseph Allen ScD, Cih John McCarthy ScD","doi":"10.1002/0471435139.TOX033.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX033.PUB2","url":null,"abstract":"Germanium, tin, and copper have each played a major role in the development of civilization although at distinctly different periods of history . A German chemist Clemens A. Winkler first isolated Germanium in 1886 from the mineral argyrodite, a mixed sulfide of silver and germanium, and named it after his home country Germany. Today germanium is used in the computer industry (as resistors on computer chips), in fiber optics, solar applications, metallurgy, and chemotherapy. \u0000 \u0000 \u0000 \u0000In contrast, the archaeological record shows that tin and copper were components of man-made objects found in Iraq that date back to 9000 BC. The Bronze Age began approximately 3500 bc with the discovery that easily smelted soft copper could be made harder and stronger by alloying with tin. Tin and copper remain important for the manufacture of numerous commercially valuable products including electrical conductors, piping, and antimicrobial agents. \u0000 \u0000 \u0000 \u0000Germanium is a semiconducting metal from Group IVA of the periodic table and it forms a series of hydrides, which correspond chemically to the methane series of hydrocarbons and to silanes (silicon series of hydrides). Selected physical and chemical properties of germanium and some of its more common compounds are provided. There are numerous organogermanium compounds. Interest in the organogermanium compounds has centered on their antimicrobial activity and the fact that their mammalian toxicity is considerably lower than the corresponding derivatives of tin or lead. In recent years various germanium compounds, for example, carboxyethyl germanium sesquioxide (Ge-132) and lactate–citrate–germanate, have been sold as nutritional supplements, thereby creating a new exposure pathway for germanium and increasing exposure above levels predicted from industrial uses. \u0000 \u0000 \u0000 \u0000Tin is a solid, rather an unreactive metal in Group IVA of the periodic table and has the largest number of stable isotopes of any element. Tin also has a large number of unstable isotopes with half-lives ranging from 2.2 min to 105 years. The physical and chemical properties of tin and some of its compounds are provided. Data are shown for elemental tin, organotin compounds, and some inorganic tin compounds. \u0000 \u0000 \u0000 \u0000Copper is located in Group IB of the periodic table and was one of the first metals used by humans. The electrical conductivity and malleability of copper are important commercial properties of the metal. The physical and chemical properties of copper and its related compounds are provided. The adverse health effects associated with copper production may be due to the large amounts of sulfur oxides generated during smelting or because of the impurities, such as arsenic and antimony. Exposure to copper can occur from environmental sources such as food, water from copper pipes, and soil ingestion near copper smelting operations. \u0000 \u0000 \u0000Keywords: \u0000 \u0000agriculture; \u0000copper; \u0000environmental impact; \u0000exposure assessment; \u0000fish; \u0000germanium; \u0000guidelines;","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"254 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2012-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91445844","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-01-27DOI: 10.1002/0471435139.TOX047.PUB2
G. Leikauf, D. Prows
{"title":"Inorganic Compounds of Carbon, Nitrogen, and Oxygen","authors":"G. Leikauf, D. Prows","doi":"10.1002/0471435139.TOX047.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX047.PUB2","url":null,"abstract":"","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"22 1","pages":"949-1032"},"PeriodicalIF":0.0,"publicationDate":"2012-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88219416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-01-27DOI: 10.1002/0471435139.TOX041.PUB2
S. Czerczak, J. Gromiec
Nickel (1–3) is a transition element in group VIII of the periodic system belonging with palladium and platinum to the 10 (nickel) triad. It is a silver-white metal with characteristic gloss and is ductile and malleable. It occurs in two allotropic forms. The specific density of nickel is 8.90 g/cm3, melting point 1455°C, and boiling point 2730°C. Nickel is not soluble in water, but it does dissolve in dilute oxidizing acids. It is resistant to lyes. Nickel is obtained by processing sulfide and laterite ore concentrates using pyrometallurgic and hydrometallurgic processes. The resultant nickel matte obtained by roasting and smelting is subjected to further cleaning by electro-, vapo-, and hydrometallurgic refining methods. Some portion of the matte is roasted to obtain commercial nickel oxide agglomerate. Pure, 99.9% nickel can be obtained by electrolytic refining process. Nickel has been used predominantly as a component of alloys. Information on the acute and chronic poisonings by nickel metal in people is limited and, in the majority of cases, refers to effects of the combined exposure to dusts or fumes comprising mixtures of metallic nickel, and its oxides and salts. Contact hypersensitivity to nickel and its salts, however, is quite well documented. Ruthenium, a transition element, belongs to group VIII (iron) of the periodic classification and to the light platinum metals triad. It is a hard and brittle metal that resembles platinum. Ruthenium compounds are usually dark brown (ranging from yellow to black). Ruthenium forms alloys with platinum, palladium, cobalt, nickel, and tungsten. Elemental ruthenium occurs in native alloys of iridium and osmium (irridosmine, siskerite) and in sulfide and other ores (pentlandite, laurite, etc.) in very small quantities that are commercially recovered. Ruthenium is used in electronics and electrical engineering, and also in the chemical industry. Ruthenium metal is used as a catalyst in the oxidizing reactions and in the synthesis of long-chain hydrocarbons. Because of its catalytic activity, it is also used in the catalytic converters for motor car engines. Ruthenium is used to increase the hardness of platinum alloys designed to make electric contacts, to make resistance wires, circuit breakers, and other components. It is also employed as a substitute for platinum in jewelry and to make the tips of fountain pen nibs. Certain derived ruthenium(III) complexes are used in cancer therapy to prevent metaplasia or to inhibit tumor cell growth. Ruthenium 106 is also used for that purpose. Ruthenium(III) complexes may be also applied to treat diseases resulting from exposure to nitric oxide. Ammoniated ruthenium oxychloride (Ruthenium Red) has been used as staining agent in microscopy. Rhodium is a transition element belonging to the cobalt group and to the light platinum triad at the same time. There is only one stable isotope: 103Rh. Rhodium, in the elemental state, is a q
{"title":"Nickel, Ruthenium, Rhodium, Palladium, Osmium, and Platinum","authors":"S. Czerczak, J. Gromiec","doi":"10.1002/0471435139.TOX041.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX041.PUB2","url":null,"abstract":"Nickel (1–3) is a transition element in group VIII of the periodic system belonging with palladium and platinum to the 10 (nickel) triad. It is a silver-white metal with characteristic gloss and is ductile and malleable. It occurs in two allotropic forms. The specific density of nickel is 8.90 g/cm3, melting point 1455°C, and boiling point 2730°C. Nickel is not soluble in water, but it does dissolve in dilute oxidizing acids. It is resistant to lyes. Nickel is obtained by processing sulfide and laterite ore concentrates using pyrometallurgic and hydrometallurgic processes. The resultant nickel matte obtained by roasting and smelting is subjected to further cleaning by electro-, vapo-, and hydrometallurgic refining methods. Some portion of the matte is roasted to obtain commercial nickel oxide agglomerate. Pure, 99.9% nickel can be obtained by electrolytic refining process. Nickel has been used predominantly as a component of alloys. \u0000 \u0000 \u0000 \u0000Information on the acute and chronic poisonings by nickel metal in people is limited and, in the majority of cases, refers to effects of the combined exposure to dusts or fumes comprising mixtures of metallic nickel, and its oxides and salts. Contact hypersensitivity to nickel and its salts, however, is quite well documented. Ruthenium, a transition element, belongs to group VIII (iron) of the periodic classification and to the light platinum metals triad. It is a hard and brittle metal that resembles platinum. Ruthenium compounds are usually dark brown (ranging from yellow to black). Ruthenium forms alloys with platinum, palladium, cobalt, nickel, and tungsten. \u0000 \u0000 \u0000 \u0000Elemental ruthenium occurs in native alloys of iridium and osmium (irridosmine, siskerite) and in sulfide and other ores (pentlandite, laurite, etc.) in very small quantities that are commercially recovered. \u0000 \u0000 \u0000 \u0000Ruthenium is used in electronics and electrical engineering, and also in the chemical industry. Ruthenium metal is used as a catalyst in the oxidizing reactions and in the synthesis of long-chain hydrocarbons. Because of its catalytic activity, it is also used in the catalytic converters for motor car engines. Ruthenium is used to increase the hardness of platinum alloys designed to make electric contacts, to make resistance wires, circuit breakers, and other components. It is also employed as a substitute for platinum in jewelry and to make the tips of fountain pen nibs. \u0000 \u0000 \u0000 \u0000Certain derived ruthenium(III) complexes are used in cancer therapy to prevent metaplasia or to inhibit tumor cell growth. Ruthenium 106 is also used for that purpose. Ruthenium(III) complexes may be also applied to treat diseases resulting from exposure to nitric oxide. Ammoniated ruthenium oxychloride (Ruthenium Red) has been used as staining agent in microscopy. \u0000 \u0000 \u0000 \u0000Rhodium is a transition element belonging to the cobalt group and to the light platinum triad at the same time. There is only one stable isotope: 103Rh. Rhodium, in the elemental state, is a q","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"1 1","pages":"653-768"},"PeriodicalIF":0.0,"publicationDate":"2012-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88277259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-01-27DOI: 10.1002/0471435139.TOX039.PUB2
T. Santonen, A. Aitio
Manganese is chemically reactive metal with physical characteristics varying from hard and brittle to soft and flexible. Main use of manganese is in steel production. The major non-metallurgical use of manganese is as manganese dioxide for producing dry-cell batteries. Organic manganese compounds include methylcyclopentadienyl manganese tricarbonyl used as an additive to gasoline, ethylene-bis-dithiocarbamate pesticides maneb and mancozeb, and an image enhancer manganese dipyridoxyl diphosphate. Main health hazard of manganese is neurotoxicity. Recent epidemiological studies show that subtle neurobehavioral effects, including fine deficits in motor performance and in attention, can be seen at exposure levels of ≥0.02–0.03 mg Mn/m3 as respirable dust. Rhenium is characterized by a very high melting temperature and density. Very few data exist on the toxicity of rhenium. Keywords: manganism; neurotoxicity; welding; ferroalloy production; manganese dioxide; methylcyclopentadienyl manganese tricarbonyl ; perrhenates
{"title":"Manganese and Rhenium","authors":"T. Santonen, A. Aitio","doi":"10.1002/0471435139.TOX039.PUB2","DOIUrl":"https://doi.org/10.1002/0471435139.TOX039.PUB2","url":null,"abstract":"Manganese is chemically reactive metal with physical characteristics varying from hard and brittle to soft and flexible. Main use of manganese is in steel production. The major non-metallurgical use of manganese is as manganese dioxide for producing dry-cell batteries. Organic manganese compounds include methylcyclopentadienyl manganese tricarbonyl used as an additive to gasoline, ethylene-bis-dithiocarbamate pesticides maneb and mancozeb, and an image enhancer manganese dipyridoxyl diphosphate. Main health hazard of manganese is neurotoxicity. Recent epidemiological studies show that subtle neurobehavioral effects, including fine deficits in motor performance and in attention, can be seen at exposure levels of ≥0.02–0.03 mg Mn/m3 as respirable dust. Rhenium is characterized by a very high melting temperature and density. Very few data exist on the toxicity of rhenium. \u0000 \u0000 \u0000Keywords: \u0000 \u0000manganism; \u0000neurotoxicity; \u0000welding; \u0000ferroalloy production; \u0000manganese dioxide; \u0000methylcyclopentadienyl manganese tricarbonyl ; \u0000perrhenates","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":"91 3 1","pages":"607-636"},"PeriodicalIF":0.0,"publicationDate":"2012-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87736439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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