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Esters of Carbonic and Orthocarbonic Acid, Organic Phosphorous, Monocarboxylic Halogenated Acids, Haloalcohols, and Organic Silicon 采购产品碳酸和正碳酸酯,有机磷,单羧基卤化酸,卤醇和有机硅
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX081.PUB2
W. A. Toscano, K. Coleman
This chapter covers (1) esters of carbonic and orthocarbonic acid, (2) esters of organic phosphorous compounds, (3) esters of monocarboxylic halogenated acids, alkanols, or haloalcohols, and (4) organic silicon esters. Other classes of esters are summarized in Chapters 57 and 58. Refer to the Introduction in Chapter 57 for a more detailed overview of general properties of esters. Unfortunately, as shown in the two prior chapters, mainly fragmented toxicological evaluations are available for esters. Most of these esters are characterized by low toxicity. Indeed, as expressed in Chapter 57, lethal dose (e.g., LD50) values are frequently difficult or impractical to measure. Localized dermal irritation is one common effect characteristic of exposures to most organic solvents. Few esters are readily absorbed, but there are exceptions, such as tri-o-cresyl phosphate (TOCP). Several of the halogenated derivatives, such as ethylchloro- and ethylbromo-, are potent lacrimators. Ethyl fluoroacetate and fluoroacetic acid exhibit about the same mode of action, which may indicate that the acetate is rapidly hydrolyzed and metabolized in the mammalian system. The unsaturated carbonates are also associated with high lacrimatory activity. TOCP is an example of an ester that can cause neuropathy in a variety of animal species. The initial weakness and paralysis are normally reversible in early stages, but repeated or massive assaults result in demyelination of the nerve fibers. The mechanism of action is not yet certain, but it appears to involve phosphorylation of proteins. Only selected phosphates exhibit neuropathic effects, including diisopropyl fluorophosphorate and N,N′-diisopropyl phosphorodiamidic fluoride. As was expressed in Chapter 57, industrial hygiene evaluation of esters involves collecting and analyzing air samples to determine their airborne concentrations. Published industrial hygiene air sampling and analytical methods, however, are unavailable for most esters. In relation, there are few occupational exposure and biological limits. A list of ester compounds covered in this chapter that have industrial hygiene sampling and analytical methods are presented here along with their respective occupational exposure limits, established by the American Conference of Governmental Industrial Hygienists (ACGIH), the Occupational Safety and Health Administration (OSHA), and the National Institute for Occupational Safety and Health (NIOSH). As stated in Chapter 57, since sampling and analytical methods and occupational exposure limits are subject to periodic revision, the reader is encouraged to refer to current publications of ACGIH, OSHA, and NIOSH. Keywords: alkyl phosphates; alkyl phosphines; aryl phosphates; aryl phosphines; bromoesters; carbonates; chloroesters; cyclic carbonates; esters of organic phosphorus compounds; fluroesters; haloalcohols; halogenated phosphate esters; organic silicon esters; ortho acid e
本章涵盖(1)碳酸酯和正碳酸酯,(2)有机磷化合物酯,(3)单羧基卤化酸,烷醇或卤醇酯,以及(4)有机硅酯。其他类酯在第57章和第58章中进行了总结。关于酯类化合物一般性质的更详细的概述,请参阅第57章的介绍。不幸的是,正如前两章所示,酯类的毒理学评估主要是碎片化的。这些酯类大多具有低毒性。事实上,如第57章所述,致死剂量(如LD50)值往往难以测量或不实际。局部皮肤刺激是暴露于大多数有机溶剂的常见影响特征。很少有酯容易被吸收,但也有例外,如三邻甲酰磷酸(TOCP)。一些卤化衍生物,如乙基氯-和乙基溴-,是有效的催泪剂。氟乙酸乙酯和氟乙酸表现出大致相同的作用模式,这可能表明乙酸在哺乳动物系统中被迅速水解和代谢。不饱和碳酸盐也与高催泪活性有关。TOCP是一种在多种动物中可引起神经病变的酯的一个例子。最初的虚弱和瘫痪通常在早期阶段是可逆的,但反复或大规模的攻击会导致神经纤维脱髓鞘。其作用机制尚不确定,但似乎与蛋白质磷酸化有关。只有选定的磷酸盐表现出神经病变作用,包括氟磷酸二异丙基和N,N ' -二异丙基磷二二氟化。如第57章所述,酯类的工业卫生评价包括收集和分析空气样本以确定其在空气中的浓度。然而,出版的工业卫生空气采样和分析方法对大多数酯是不可用的。相对而言,很少有职业接触和生物限制。本章所涵盖的具有工业卫生采样和分析方法的酯类化合物清单,以及它们各自的职业暴露限值,由美国政府工业卫生学家会议(ACGIH)、职业安全与健康管理局(OSHA)和国家职业安全与健康研究所(NIOSH)建立。如第57章所述,由于采样和分析方法以及职业暴露限值受到定期修订,因此鼓励读者参考ACGIH, OSHA和NIOSH的最新出版物。关键词:烷基磷酸盐;烷基膦类化合物;芳基磷酸盐;芳基膦类化合物;bromoesters;碳酸盐;chloroesters;循环碳酸盐;有机磷化合物的酯类;fluroesters;haloalcohols;卤代磷酸酯;有机硅酯;邻位酸酯;silanal酯;硅烷
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引用次数: 1
Aldehydes and Acetals 醛和缩醛
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX073.PUB2
M. Borchers
More than 300 aldehydes occur in foods, water, and air. Due to the electrophilicity of the carbonyl carbon, particularly when proximal to a carbon–carbon double bond, aldehydes react with thiols and amines to form protein–protein, DNA–protein, and DNA–DNA cross-links. Despite their potential for causing cell damage, toxicological and exposure data for a large number of aldehydes are lacking. Inhalation and ingestion studies have demonstrated that a number of aldehydes are irritants and can induce tumors in animal models. Formaldehyde, which is a suspected carcinogen, is the most widely studied of these compounds. The physicochemical properties of saturated aldehydes are summarized. Toxicological and health effects are given. Keywords: acetals; aliphatic dialdehydes; aromatic aldehydes; Clean Air Act; EPA; flavoring agents; formaldehyde; halogenated aldehydes; heterocyclic aldehydes; saturated aliphatic aldehydes; unsaturated aliphatic aldehydes; urea–formaldehyde resins
有300多种醛存在于食物、水和空气中。由于羰基碳的亲电性,特别是当邻近碳-碳双键时,醛与硫醇和胺反应形成蛋白质-蛋白质、dna -蛋白质和DNA-DNA交联。尽管它们有可能造成细胞损伤,但缺乏大量醛类物质的毒理学和暴露数据。吸入和摄入的研究表明,在动物模型中,许多醛是刺激物,可以诱发肿瘤。甲醛被怀疑是一种致癌物,是这些化合物中研究最广泛的。综述了饱和醛的理化性质。给出了毒理学和健康影响。关键词:缩醛;脂肪族醛;芳香醛;清洁空气法;环保局;调味剂;甲醛;卤代醛;杂环醛;饱和脂肪醛;不饱和脂肪醛;脲醛树脂
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引用次数: 11
Petroleum, Coal Tar, and Related Products 采购产品石油,煤焦油和相关产品
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX022.PUB2
R. Niemeier
The chemical composition of coal tar, coal tar pitch, and related materials is complex and variable. The estimated number of compounds present in these complex mixtures is in thousands. Because of variation in source materials and manufacturing processes, including different temperatures and times of carbonization, no two coal tars or pitches are chemically identical, and their toxicity may differ with their origin. In general, however, approximately 80% of the total carbon present in coal tars exists in aromatic form. Benzo[a]pyrene (B[a]P) is probably the most potent, widespread occupational carcinogen in coal tar, coal tar pitch and its volatiles, coke oven emissions, and creosote, all of which have corresponding work exposure standards; however, there is no occupational workplace standard for B[a]P in the United States. B[a]P may account for more than 75% of the carcinogenic activity of coal tar pitch fume condensate. Individuals who work in tarring facilities, roofing operations, power plants, and asphalt and coke manufacturing facilities may be exposed to benzo[a]pyrene and related PAHs. These mixtures may differ qualitatively and quantitatively. Coal tar is completely or nearly completely soluble in benzene and nitrobenzene and it is partially soluble in acetone, carbon disulfide, chloroform, diethyl ether, ethanol, methanol, petroleum ether, hexane, and sodium hydroxide solution, and slightly soluble in water. It has a characteristic naphthalene-like odor. Coal tar is heavier than water and on ignition it burns with a reddish, luminous, and very sooty flame. Coal tar fumes are highly flammable and are easily ignited by heat, sparks, or flames. Vapors are heavier than air. They may travel to a source of ignition and flash back and may form explosive mixtures with air. Vapors will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion is a potential hazard indoors, outdoors, or in sewers. Some may polymerize explosively when heated or involved in a fire. Runoff to a sewer may create a fire or explosion hazard. Containers may explode when heated. Coal tar may be transported hot. The greatest complexity occurs when toxicity is based on the effects of a class of compounds or of a material of a certain physical description. Some polynuclear aromatic hydrocarbons (PNAs) and polycyclic aromatic hydrocarbons (PAHs) are carcinogens of varying potency, and they usually exist in mixtures with other PNAs/PAHs and with compounds (activators, promoters, and inhibitors) that modify their activity. Analysis of each individual compound is very difficult and when done does not yield a clear answer. Given the complexity of the mixture of biologically active agents and their interactions, a calculated equivalent dose would have little accuracy. In these instances, it is common to measure some quantity related to the active agents and to base the occupational exposure limit on that index. An oc
煤焦油、煤焦油沥青及相关材料的化学成分复杂多变。在这些复杂混合物中存在的化合物估计有数千种。由于原料和制造工艺的差异,包括不同的温度和碳化时间,没有两种煤焦油或沥青的化学成分是相同的,它们的毒性可能因其来源而异。然而,一般来说,煤焦油中大约80%的碳以芳香形式存在。苯并[a]芘(B[a]P)可能是煤焦油、煤焦油沥青及其挥发物、焦炉排放物和杂酚油中最有效、最广泛的职业致癌物,所有这些都有相应的工作接触标准;然而,美国并没有针对B[a]P的职业工作场所标准。B[a]P可能占煤焦油沥青烟冷凝物致癌性的75%以上。在沥青设施、屋顶作业、发电厂以及沥青和焦炭生产设施工作的个人可能会接触到苯并[a]芘和相关的多环芳烃。这些混合物在质量和数量上可能不同。煤焦油完全或几乎完全溶于苯和硝基苯,部分溶于丙酮、二硫化碳、氯仿、乙醚、乙醇、甲醇、石油醚、己烷和氢氧化钠溶液,微溶于水。它有一种典型的类似萘的气味。煤焦油比水重,点燃后燃烧时发出红色的、明亮的、烟熏的火焰。煤焦油烟雾是高度易燃的,很容易被热、火花或火焰点燃。蒸气比空气重。它们可能到达点火源并回弹,并可能与空气形成爆炸性混合物。蒸汽会沿地面扩散,并聚集在低矮或密闭的地方(下水道、地下室、水箱)。蒸汽爆炸在室内、室外或下水道都是一种潜在的危险。有些在加热或起火时会发生爆炸性聚合。流入下水道可能产生火灾或爆炸危险。容器受热时可能爆炸。煤焦油可以热运输。当毒性是基于一类化合物或具有某种物理性质的材料的作用时,就会出现最复杂的情况。一些多核芳烃(PNAs)和多环芳烃(PAHs)是不同效力的致癌物,它们通常与其他PNAs/PAHs以及与改变其活性的化合物(激活剂、启动剂和抑制剂)混合存在。分析每一个单独的化合物是非常困难的,即使完成了也不能得到一个明确的答案。考虑到生物活性制剂混合物及其相互作用的复杂性,计算出的等效剂量几乎不准确。在这些情况下,通常测量一些与活性剂有关的量,并根据该指数确定职业暴露限值。PNAs的职业暴露限值是基于苯或己烷可溶性空气传播物质的总重量。该限值可能适用于煤焦油沥青挥发物(CTPV),但它可能不适用于其他含PNA/PAH的材料。原油、沥青油烟和裂解的石油原料可能含有PNA/PAH。煤焦油沥青挥发物中混合的煤尘颗粒不溶于苯,而与PNAs/PAHs混合的石油衍生物质几乎都溶于苯。一些最高水平的煤沥青挥发物已经发生在铝还原行业,特别是在索德伯格工艺锅室。在混合大气中区分几类化合物(如煤焦油沥青挥发物)的问题增加了采样方法选择的复杂性,有时有必要做出某些简化假设,并在结果旁边清楚地说明。在测量一种元素的毒性更强的可溶形式时,通常假设可以做出“安全”的假设,即存在的整个元素都是可溶的。在一项生物修复效果的研究中,通过气相色谱分析生物处理过的地下水的有机提取物,确定了本地土壤微生物从水溶液中去除这些污染物的能力。通过" Microtox "试验和鱼类毒性和致畸性试验,每隔一段时间确定与这种材料的生物降解有关的潜在环境和人类健康危害的变化。关键词:烷烃;沥青;煤焦油;煤焦油沥青;原油;柴油;汽油;指导方针;燃料油;喷气燃料;液化气体;医药产品;天然气;职业;油;石油馏分油;生产;流程;法规;焦油蒸馏;稀释剂;毒性作用;使用;美国暴露限值;蜡
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引用次数: 2
Synthetic Polymers: Polyesters, Polyethers, Polysulfones, and Other Polymers 采购产品合成聚合物:聚酯,聚醚,聚砜和其他聚合物
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX092.PUB2
Amy Benson
Commercial use of polyester resins dates from the early twentieth century, when alkyd resins were first used in surface coatings. The polyesters are found today as fibers, films, laminating resins, molding resins, and engineering plastics. Many of the high molecular weight polyethers are used as engineering plastics, as are the polysulfides and the polysulfones. Important properties of these compounds and production data for the general categories are provided. Processing techniques vary widely and are discussed in the sections in this chapter. Although toxicity data for some of these polymers are limited, information is discussed in the sections in this chapter. In many cases, the finished polymers are associated with low toxicity. However, some chemicals within the finished products have been known to migrate from the polymers (although usually in small amounts). Further, some of the polymers described in this chapter are used in biomedical equipment, including grafts and other implants, dialysis membranes, or as vehicles for intravenous injections, and there may be toxicity associated with these uses. For specific medical applications, any risks should be weighed against benefits derived from the products. Consultation with medical professionals is necessary before deciding on whether to use particular devices. Certainly some of the highest potentials for concern associated with these polymers are for workers at manufacturing or processing sites. Workers may be exposed to volatile chemicals (e.g., monomers, flame retardants, additives) generated during processing of flammable solvents, elevated temperatures, or fires. Workers may also be exposed to dust or particulates generated in the manufacturing and processing of polyester fibers. Finally, explosion hazards might be possible where static charges are generated (e.g., during physical processing of polyester films over rollers) where flammable materials are used. Industrial hygiene concerns with these polymers depend on the type of resin. Examples of such concerns include the following: significant quantities of styrene may be released during the fabrication of unsaturated polyester resins; particulates that have biologically significant consequences when inhaled in large amounts may be generated in the manufacturing and processing of polyester fibers; processing of polyoxymethylene in a poorly ventilated space may release biologically significant amounts of formaldehyde into the adjacent atmosphere; or sulfur-containing engineering resins may yield hydrogen sulfide or sulfur dioxide if heated to decomposition temperatures. The chemical inputs typically used to synthesize each of the polymers as well as relevant additives are discussed in the sections in this chapter. Toxicity data for most of these inputs can be found in other chapters of this edition of Patty's Industrial Hygiene and Toxicology. No specific standards are known that pertain to ordinary industrial
聚酯树脂的商业应用始于20世纪初,当时醇酸树脂首次用于表面涂层。聚酯今天被发现作为纤维,薄膜,层压树脂,成型树脂和工程塑料。许多高分子量聚醚用作工程塑料,如聚硫化物和聚砜。提供了这些化合物的重要性质和一般类别的生产数据。处理技术差别很大,在本章各节中讨论。虽然这些聚合物的毒性数据有限,但本章各节将讨论这些信息。在许多情况下,成品聚合物具有低毒性。然而,成品中的一些化学物质已知会从聚合物中迁移(尽管通常是少量的)。此外,本章中描述的一些聚合物用于生物医学设备,包括移植物和其他植入物、透析膜或静脉注射载体,并且可能存在与这些用途相关的毒性。对于特定的医疗应用,应将任何风险与产品带来的益处进行权衡。在决定是否使用特定装置之前,有必要咨询医疗专业人员。当然,与这些聚合物相关的一些最可能引起关注的是制造或加工场所的工人。工人可能会接触到易燃溶剂、高温或火灾过程中产生的挥发性化学品(如单体、阻燃剂、添加剂)。工人也可能接触到聚酯纤维制造和加工过程中产生的灰尘或微粒。最后,在产生静电荷的地方(例如,在使用易燃材料的聚酯薄膜在滚筒上的物理加工过程中),可能会产生爆炸危险。这些聚合物的工业卫生问题取决于树脂的类型。这些问题的例子包括:在制造不饱和聚酯树脂的过程中可能释放出大量的苯乙烯;在聚酯纤维的制造和加工过程中,大量吸入可能产生具有显著生物学后果的微粒;在通风不良的空间中加工聚甲醛可能会释放大量的甲醛到邻近的大气中;如果加热到分解温度,含硫工程树脂可能产生硫化氢或二氧化硫。化学输入通常用于合成每一个聚合物以及相关的添加剂将在本章的各节中讨论。大多数这些输入的毒性数据可以在帕蒂的《工业卫生与毒理学》的其他章节中找到。目前还没有关于聚合物成品的普通工业用途的具体标准。然而,用于合成或加工这些聚合物的化学品可能存在职业接触限制。此外,还有可能适用的粉尘和颗粒的职业接触限值。还有几个可能需要的一般保护措施的例子,例如,建议向工作场所持续供应新鲜空气,并通过排气系统去除加工烟雾。此外,应使用适当的个人防护,定期从排气罩、管道系统和其他表面清除有毒或有火灾危险的加工烟气冷凝物。通风要求必须在当地确定,以限制在其使用点接触材料。在清洁或处理冷凝物和塑料加工烟雾时,应注意使用适当的个人防护。本章描述的聚合物通常很少或没有燃烧毒性的数据。塑料燃烧产物的毒理学方面可能非常复杂,部分原因是很难在受控条件下模拟真实环境。此外,根据各种因素,燃烧产物混合物中存在的化学物质的定性和定量性质也会有所不同。可能导致这些聚合物燃烧产物毒性的一些因素包括一氧化碳和二氧化碳的增加、氧气的减少和刺激性气体的存在。火灾的主要影响通常是缺氧引起的窒息、一氧化碳中毒、组织的热损伤以及燃烧气体对呼吸道的刺激。一些聚合物用于包装(或直接用于食品),直接或间接食品接触应用的许可列在联邦法规第21章中,并在本章各节中列出。 其他聚合物已被批准用于可植入体内或用于透析机的特定医疗设备。关键词:食品添加剂;醇酸树脂;烯丙基聚合物;燃烧产品;火灾烟雾;线性对苯二甲酸酯聚合物;个人防护;聚碳酸酯;聚醚;聚苯硫醚;聚砜;处理气体;硫聚合物;合成纤维;热降解;不饱和聚酯树脂
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引用次数: 1
Human Health Effects of Nonionizing Electromagnetic Fields 非电离电磁场对人体健康的影响
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX100.PUB2
D. Carpenter
The present chapter deals with that portion of the electromagnetic spectrum that has lower energy and longer wavelengths than the infrared, including the extra low frequency (ELF) magnetic fields from electricity and radiofrequency (RF) fields used in communication. The energies at these frequencies are not sufficient to directly break chemical bonds, and the question to be examined is whether they have sufficient energy to cause human disease by other mechanisms, particularly at intensities that do not cause measurable heating. Present research indicates a consistent pattern of elevated risk of cancer, especially leukemia, and some neurodegenerative diseases at ELF magnetic field levels commonly found in residences and occupations. The relationship between childhood magnetic field exposure and brain cancer is also reviewed. Human studies and meta-analyses of research of mobile phone use show a consistent and elevated risk of brain cancer and acoustic neuroma upon intense and long-term use. International and national standards of human exposure to ELF and RF frequencies are presented and found to be inadequate for the protection of human health. The evidence of human harm from excessive exposure to both ELF and RF is stronger and more consistent for cancer and neurodegenerative diseases than is commonly recognized. While there is less strong reproducibility and consistency for some other proposed health outcomes, this indicates only the need for more research with better exposure assessment. Keywords: Leukemia; brain cancer; acoustic neuroma; Alzheimer's disease; amyotrophic lateral sclerosis; electromagnetic fields (EMFs); mutations; radiofrequency; Universal Mobile Telecommunications System
本章讨论的是能量较低、波长较长的电磁波谱部分,包括通信中使用的电场和射频场产生的极低频(ELF)磁场。这些频率的能量不足以直接破坏化学键,需要研究的问题是它们是否有足够的能量通过其他机制引起人类疾病,特别是在不引起可测量的加热的强度下。目前的研究表明,在住宅和职业中常见的极低频磁场水平下,癌症,特别是白血病和一些神经退行性疾病的风险升高的模式是一致的。本文还对儿童磁场暴露与脑癌的关系进行了综述。人体研究和手机使用研究的荟萃分析表明,长期高强度使用手机会持续增加患脑癌和听神经瘤的风险。提出了人类接触极低频和射频频率的国际和国家标准,并发现这些标准不足以保护人类健康。对于癌症和神经退行性疾病而言,过度暴露于极低频和射频对人类造成伤害的证据比通常认识到的更有力、更一致。虽然其他一些拟议的健康结果的可重复性和一致性较差,但这只表明需要进行更多的研究和更好的接触评估。关键词:白血病;脑癌;听神经瘤;阿尔茨海默病;肌萎缩性侧索硬化症;电磁场(EMFs);突变;射频;通用移动通信系统
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引用次数: 4
Dibenzo-p-Dioxins: 2,3,7,8-Tetrachlorodibenzo-p-Dioxin 8-Tetrachlorodibenzo-p-Dioxin Dibenzo-p-Dioxins: 2、3、7日
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX065.PUB2
S. Hee
Chlorinated dibenzo-para-dioxins or dibenzo-p-dioxins (CDDs) are a class of compounds with 75 possible congeners. When the CDDs contain more than one chlorine they are termed polychlorinated dibenzo-p-dioxins (PCDDs). Most of the information is for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), the most toxic congener. The bulk of the material in this chapter relates to this compound. The toxic PCDD congeners are substituted with chlorines in the 2,3,7, and 8 positions. The least toxic congeners are the monochlorinated PCDDs and octachlorodibenzo-p-dioxin [CAS RN 3268-87-9], the fully chlorinated PCDD. PCDDs often are accompanied by the dibenzofuran analogs, the polychlorinated dibenzofurans (PCDFs), and the diphenyl ether analogs, the polychlorinated diphenyl ethers (PCDPEs). The cumulative toxicity of the toxic congeners of polychlorinated biphenyls (PCBs), PCDDs, PCDFs, and PCDPEs in a sample is expressed through the 2,3,7,8-TCDD toxicity equivalent (TEQ) and toxicity equivalency factor (TEF) concepts because real-life exposures are to mixtures of PCDDs, PCDFs, PCDEs, and PCBs rather than to 2,3,7,8-TCDD alone. Keywords: 2,3,7,8-Tetrachlorodibenzo-p-dioxin; accidents; Agent Orange; body burden; Cachexia; chloracne; chlorinated dibenzo-p-dioxins; dioxin; endocrine effects; IARC carcinogenic evaluation; tissues; US/foreign standards
氯化二苯并对二恶英或二苯并对二恶英(cdd)是一类具有75种可能同系物的化合物。当cdd含有一个以上氯时,它们被称为多氯二苯并对二恶英(pcdd)。大多数信息是关于2,3,7,8-四氯二苯并-对二恶英(2,3,7,8- tcdd)的,它是毒性最大的同源物。本章的大部分内容都与这种化合物有关。有毒的PCDD同系物在2、3、7和8位被氯取代。毒性最小的同系物是单氯PCDD和八氯二苯并对二恶英[CAS RN 3268-87-9],即全氯化PCDD。多氯联苯醚通常伴随着二苯并呋喃类似物,即多氯联苯呋喃(PCDFs)和二苯醚类似物,即多氯联苯醚(pcdpe)。样品中多氯联苯(PCBs)、pcdd、PCDFs和pcdpe的毒性同系物的累积毒性通过2,3,7,8- tcdd毒性当量(TEQ)和毒性当量因子(TEF)概念来表达,因为现实生活中暴露于pcdd、pcdf、PCDEs和PCBs的混合物中,而不是单独暴露于2,3,7,8- tcdd中。关键词:2、3、7,8-Tetrachlorodibenzo-p-dioxin;事故;橘剂;身体的负担;恶病质;氯痤疮;氯化dibenzo-p-dioxins;二恶英;内分泌的影响;IARC致癌性评价;组织;美国/外国标准
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引用次数: 0
Noncancer Risk Assessment: Principles and Practice in Environmental and Occupational Settings 非癌症风险评估:环境和职业环境中的原则和实践
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX005.PUB2
L. Haber, Joan E. Strawson, A. Maier, Irene M. Baskerville-Abraham, A. Parker, M. Dourson
The approach to assessing the risks of noncancer toxicity has differed historically from that used to assess the potential risks of carcinogenicity. Assessment of risks of carcinogenicity has historically assumed that a small number of molecular events can evoke mutagenic changes in a single cell, ultimately leading to self-replicating damage and carcinogenicity. Generally, this is considered a nonthreshold effect because presumably all levels of exposure may pose a small, but finite, probability of generating a response. In contrast, it is most often assumed that noncarcinogenic changes have a threshold, a dose level below which a response is unlikely, because homeostatic, compensating, and adaptive mechanisms in the cell protect against toxic effects. Modern understanding of mode of action (MOA), loosely defined as how a chemical causes the observed effect, has led to refinements in this dichotomy. Rather than considering cancer versus noncancer effects, the focus is on whether or not the chemical causes its effects by a mutagenic MOA, specifically DNA interaction. Nonthreshold approaches are generally used for effects resulting from interaction with DNA, while effects resulting from a nonmutagenic MOA (including both cancer and noncancer endpoints) are generally evaluated using threshold approaches. A recent NRC publication [1], however, recommended linear extrapolation under certain conditions for noncancer endpoints that do not involved interaction with DNA. The issues raised by that publication are addressed later in this chapter. Recognizing both the historical approach and the importance of evaluation of MOA, this chapter will continue to use the term “noncancer risk,” but the methods described here should be understood to apply to both noncancer endpoints and cancer endpoints for which MOA information indicates that a threshold applies. This chapter describes the general framework for noncancer risk assessment and some salient principles for evaluating the quality of data and formulating judgments about the nature and magnitude of the hazard. Highlights of noncancer risk assessment methods used by a variety of agencies and organizations, and examples of how occupational risk assessment is moving toward a more systematic use of risk assessment principles are presented. This chapter also has several specific aims. The first is to provide scientifically supportable quantitative risk assessment procedures to meet the risk assessment goals listed in the following paragraph. A second aim is to provide a scientific rationale that may be used to determine whether new quantitative risk assessment procedures not specifically examined in this chapter are scientifically supportable. The final aim of this chapter is to provide a basis for developing new or improved quantitative risk assessment procedures. The quantitative risk assessment procedures described in this chapter have been developed to meet a variety of risk ass
评估非癌症毒性风险的方法历来不同于评估潜在致癌性风险的方法。对致癌性风险的评估历来假设,少数分子事件可以引起单个细胞的诱变变化,最终导致自我复制损伤和致癌性。一般来说,这被认为是一种非阈值效应,因为所有水平的暴露都可能造成很小但有限的产生反应的概率。相反,人们通常认为非致癌性变化有一个阈值,低于这个剂量水平就不可能产生反应,因为细胞中的稳态、补偿和适应性机制保护细胞免受毒性作用的影响。对作用方式(MOA)的现代理解,粗略地定义为一种化学物质如何引起所观察到的效果,使这种二分法得到了改进。而不是考虑癌症与非癌症的影响,重点是化学物质是否通过诱变的MOA引起其影响,特别是DNA相互作用。非阈值方法通常用于与DNA相互作用产生的效应,而非诱变MOA(包括癌症和非癌症终点)产生的效应通常使用阈值方法进行评估。然而,最近NRC的一份出版物[1]建议在某些条件下,对不涉及DNA相互作用的非癌症终点进行线性外推。该出版物提出的问题将在本章后面讨论。认识到历史方法和评估MOA的重要性,本章将继续使用术语“非癌症风险”,但这里描述的方法应被理解为既适用于非癌症终点,也适用于MOA信息表明适用阈值的癌症终点。本章描述了非癌症风险评估的一般框架,以及评估数据质量和制定有关危害性质和程度的判断的一些重要原则。重点介绍了各种机构和组织使用的非癌症风险评估方法,并举例说明了职业风险评估如何朝着更系统地使用风险评估原则的方向发展。本章还有几个具体的目的。第一是提供科学支持的定量风险评估程序,以实现下文所列的风险评估目标。第二个目的是提供一种科学依据,用于确定本章未具体审查的新的定量风险评估程序是否在科学上可支持。本章的最终目的是为开发新的或改进的定量风险评估程序提供基础。本章中描述的定量风险评估程序是为了满足各种风险评估目标而开发的。尽管保护公众健康和职业健康是贯穿这些单独的风险评估目标的共同主题,但这些目标差别很大,有必要采取单独和不同的程序。这些目标的例子如下:根据可能的危害对化学品进行排序;结合接触信息,优先考虑进一步评价的化学品;筛选化学品(例如新化学品或正在开发的化学品),以确定哪些化学品适合进一步发展;确定和/或估计在一生中可能不会有明显有害影响风险的每日暴露水平;确定和/或估计人体暴露于不同水平的特定化学品或混合物时可能产生的反应。此外,不同的定量程序需要不同数量的毒性数据。因此,要解决的问题和可用数据的数量都会影响程序的选择。关键词:基准剂量;分类回归;剂量反应;剂量测定法;风险特征;作用方式;基于生理的药代动力学建模;概率RfD;问题制定;风险特征;不确定性因素;证据的重要性
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引用次数: 12
Synthetic Polymers—Cellulosics, Other Polysaccharides, Polyamides, and Polyimides 合成聚合物-纤维素,其他多糖,聚酰胺和聚酰亚胺
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX091.PUB2
F. Cavender
Natural polymers are biological macromolecules and are as old as life itself. Hemp, flax, cotton, and wood fibers from plants and silk and wool fibers from animals have been utilized since the dawn of civilization to make rope, paper, clothing, and furniture. What child has not been fascinated by a spider's web? The natural polymers include such diverse materials as proteins, polysaccharides, DNA, and polypeptides. The word polymer is derived from the Greek words poly, or many, and meros, or parts. This chapter will focus on cellulose and it derivatives, polyamides such as nylon and polyimides. Cellulose plastics are produced by the chemical modification of cellulose. Raw cellulose is not a thermoplastic: it does not melt. Cellulose is a substance that forms the cell walls of many trees and other plants. Raw cellulose can be made into a fiber or film, but it must be chemically modified to produce a thermoplastic material. Regenerating cellulose to yield the products rayon and cellophane removes the natural impurities. These regenerated products are essentially inert unless potential toxicants such as finishes and plasticizers are added in sufficient quantities to cause injury. Many cellulose derivatives would appear to be similarly inert. “Rayon” is, by definition, established by the Federal Trade Commission, the “generic name for a manufactured fiber composed of regenerated cellulose as well as manufactured fibers composed of regenerated cellulose in which substitutes have replaced not more than 15% of the hydrogens of the hydroxyl groups.” Cellophane is “regenerated cellulose, chemically similar to rayon, made by mixing cellulose xanthate with a dilute sodium hydroxide solution to form a viscose, then extruding this viscose into an acid for regeneration. The term rayon is used when the material is in fibrous form.” Rayon is made from regenerated cellulose by forcing it through small holes into the coagulating acid bath at the end of the process, while cellophane is the film form of regenerated cellulose that has been forced through a thin slit into an acid bath. All methods of preparation essentially depend upon solubilizing thin, short-fibered forms of natural cellulose, reshaping it into long fibers or film by extrusion through a spinneret or slit aperture, then immediately converting the extruded product back into solid cellulose. Rayon was first commercialized in the nineteenth century by the now discarded Chardonnet process that used highly flammable cellulose nitrate. The cuprammonium process replaced the Chardonnet process and is still used to a limited extent to produce extremely fine, silk-like filaments. Today the most widely used process is the xanthate or viscose process. Generally, alkali cellulose is prepared by reacting wood pulp with excess sodium hydroxide (or other alkali), followed by aging to permit separation of the pulp fibers. The alkali cellulose is reacted with carbon disulfide to form
天然聚合物是生物大分子,和生命本身一样古老。自从人类文明出现以来,植物的大麻、亚麻、棉花和木纤维以及动物的丝绸和羊毛纤维就被用来制造绳子、纸、衣服和家具。哪个孩子没有被蜘蛛网迷住过?天然聚合物包括蛋白质、多糖、DNA和多肽等多种材料。聚合物这个词来源于希腊语poly(许多)和meros(部分)。本章将重点介绍纤维素及其衍生物,聚酰胺如尼龙和聚酰亚胺。纤维素塑料是通过对纤维素进行化学改性而生产的。未加工的纤维素不是热塑性塑料:它不熔化。纤维素是一种构成许多树木和其他植物细胞壁的物质。生纤维素可以制成纤维或薄膜,但必须经过化学改性才能制成热塑性材料。再生纤维素生产产品人造丝和玻璃纸去除天然杂质。这些再生产品基本上是惰性的,除非添加足够数量的潜在有毒物质,如整理剂和增塑剂,以造成伤害。许多纤维素衍生物似乎也具有类似的惰性。根据联邦贸易委员会的定义,“人造纤维”是“由再生纤维素组成的人造纤维的通用名称,以及由再生纤维素组成的人造纤维,其中替代品取代了不超过15%的羟基氢。”玻璃纸是一种“再生纤维素”,化学性质类似于人造丝,由纤维素黄原药与稀氢氧化钠溶液混合形成粘胶制成,然后将这种粘胶挤出酸中进行再生。当这种材料呈纤维状时,使用“人造丝”一词。人造纤维是由再生纤维素制成的,在生产过程的最后将其通过小孔进入凝固的酸浴,而玻璃纸是再生纤维素通过细缝进入酸浴的薄膜形式。所有的制备方法基本上都依赖于溶解薄的、短纤维形式的天然纤维素,通过喷丝器或狭缝孔挤压将其重塑成长纤维或薄膜,然后立即将挤压后的产物转化为固体纤维素。人造纤维在19世纪首次商业化,当时使用了高度易燃的硝酸纤维素,现在已被废弃。铜铵法取代了霞多丽法,至今仍在一定程度上用于生产极细的丝状纤维。今天最广泛使用的方法是黄原药或粘胶法。一般来说,碱纤维素是通过将木浆与过量的氢氧化钠(或其他碱)反应,然后老化以使纸浆纤维分离而制备的。碱纤维素与二硫化碳反应形成纤维素黄药钠,然后将其溶解在碱中并挤压到酸浴中,将长丝或薄膜转化为人造丝或玻璃纸。这些长丝和薄膜可以拉伸、脱硫、洗涤、干燥或以其他方式整理。人造丝的工业用途包括轮胎、皮带和软管的加固绳,以及“一次性”非织造织物。一度,人造丝被广泛应用于纺织工业。将粘胶挤出一条细缝,放入酸液中,制成玻璃纸。玻璃纸可以通过用甘油、丙二醇或聚乙二醇洗涤来塑化。再生纤维素也可以通过醋酸纤维素皂化制备。玻璃纸薄膜广泛应用于食品工业。这些产品种类繁多,这里给出的参考资料主要限于评论。未经加工的人造丝不会引起皮炎。商用织物可能含有游离甲醛或甲醛树脂。对12件100%人造丝衣物样本的分析显示,游离甲醛含量在百万分之15至3517之间;甲醛存在于织物整理剂中。在一般人群中,危害更可能是由这些纤维素的可燃性或用于延缓可燃性的手段造成的,而不是与它们的使用相关的任何其他因素。未经处理的纤维素材料暴露在阴燃的火焰中很容易产生致死量的一氧化碳。合成聚酰胺和聚酰亚胺都是阶梯生长或缩合聚合物。作为一个群体,它们被认为是高性能聚合物,而链生长或加成聚合物包括聚乙烯、聚氯乙烯和聚苯乙烯等典型的商品聚合物以及高性能含氟聚合物。聚酰胺与尼龙一词相连,尼龙是第一种主要的合成聚酰胺。尼龙在20世纪30年代被开发为纤维,在40年代被开发为塑料。
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引用次数: 3
Synthetic Polymers—Olefin, Diene Elastomers, and Vinyl Halides 合成聚合物-烯烃,二烯弹性体和乙烯基卤化物
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX089.PUB2
B. Walker, Lynette D. Stokes
Elastomers, also called rubber, can withstand considerably greater deformation than other materials and uniquely return essentially to their original shape even after substantial deformation. A familiar example is the behavior of a stretched rubber band after its release. All elastomers are composed of long macromolecular chains that assume a random coil conformation when undeformed. Deformation causes these coils to straighten out. Upon being allowed to relax, an elastomer returns essentially to its original shape because the chains reassume their random conformation. The first elastomer identified, natural rubber, was described by Columbus as a ball that bounced. The first specialty elastomers, polysulfides and polychloroprene, were commercialized in the 1930s, natural rubber was the major industry product until World War II, when styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR) were established as important synthetic rubbers. From these early beginnings, the elastomer industry grew rapidly to a global elastomer demand of 15 million metric tons in 1990. The range and diversity of synthetic rubber becomes evident upon reviewing the Synthetic Rubber Manual that describes both thermosetting elastomers (TSE) and thermoplastic elastomers (TPE). TSE and TPE exhibit important similarities. The most useful properties are the result of their long molecular chains linking to one another to form a three-dimensional network. In TSE this network is linked together with essentially irreversible cross-links. Vulcanization is the process of forming these cross-links, most typically using sulfur as the cross-linking agent. TSE generally arrives at the rubber fabricators in bales. Ten or more ingredients might be added to the bale in heavy mixers before the compounded elastomer is shaped into a product and vulcanized. Schunk has characterized the health hazards of many of these ingredients, including carbon blacks, mineral fillers, plasticizers, protective and cross-linking agents, and accelerators. Broadly considered, these health hazards can be considered in terms of the following: monomers, solvents, and other materials used to prepare elastomers storage and handling of elastomer (bales, pellets, and powder) processing of elastomers, generally at high temperatures finished rubber product Health hazards in processing, and storage and handling elastomers are the dominant focus of this section; limited references will be made to the other two areas where appropriate. Certain portions of the material refer to monomer toxicology and epidemiology because some of the monomers used in manufacturing elastomers remain at low levels in the polymer. A full discussion of the toxicity of monomers is beyond the scope of this chapter. Typical basic properties of certain elastomers are latter. Properties within a given class of elastomers can vary significantly. For
弹性体,也被称为橡胶,可以承受比其他材料更大的变形,并且即使在剧烈变形后也能独特地恢复到原来的形状。一个熟悉的例子是橡皮筋松开后拉伸的行为。所有弹性体都是由长大分子链组成,在未变形时呈随机线圈形。变形使这些线圈变直。一旦被允许放松,弹性体基本上就会恢复到原来的形状,因为链恢复了它们的随机构象。发现的第一种弹性体是天然橡胶,哥伦布把它描述为一种会弹跳的球。第一批特种弹性体,聚硫化物和氯丁橡胶,在20世纪30年代商业化,天然橡胶是主要的工业产品,直到第二次世界大战,当丁苯橡胶(SBR)和丙烯腈丁二烯橡胶(NBR)被确立为重要的合成橡胶。从这些早期开始,弹性体行业迅速发展到1990年全球弹性体需求达到1500万吨。合成橡胶的范围和多样性在回顾合成橡胶手册时变得明显,该手册描述了热固性弹性体(TSE)和热塑性弹性体(TPE)。TSE和TPE表现出重要的相似性。最有用的特性是它们的长分子链相互连接形成三维网络的结果。在TSE中,这个网络以本质上不可逆的交联连接在一起。硫化是形成这些交联的过程,最典型的是使用硫作为交联剂。TSE通常成捆地到达橡胶制造商处。在复合弹性体成形成产品并硫化之前,可以将十种或更多种成分添加到重混合器中的包中。Schunk描述了许多这些成分对健康的危害,包括炭黑、矿物填料、增塑剂、保护剂和交联剂以及促进剂。从广义上考虑,这些健康危害可从以下方面考虑:单体、溶剂和用于制备弹性体的其他材料储存和处理弹性体(包、球团和粉末)加工弹性体,一般在高温下加工的成品橡胶制品中的健康危害,而储存和处理弹性体是本节的主要重点;在适当的情况下,将有限地提及其他两个领域。材料的某些部分涉及单体毒理学和流行病学,因为用于制造弹性体的一些单体在聚合物中保持低水平。对单体毒性的全面讨论超出了本章的范围。某些弹性体的典型基本性质是后者。在给定的弹性体类别内的性质可以有很大的不同。例如,增加丁腈橡胶中的丙烯腈含量可以减少某些油和溶剂引起的丁腈橡胶膨胀。大多数橡胶都是生的或未固化的固体或液体乳胶。制造某些类型的干合成橡胶的基本步骤是聚合、混凝、洗涤和干燥。生产乳胶的基本步骤是聚合、稳定,通常还有浓缩。乳胶被定义为一种稳定的水性分散体,包含直径约0.05至5mm的离散聚合物颗粒。乳液聚合系统包含水、单体、引发剂和阴离子或阳离子表面活性剂。具有立体定向催化剂的溶液聚合涉及在惰性溶剂中反应一种或多种单体;系统条件可以控制,以最大限度地提高所需的异构体在聚合物中的排列。添加抗氧化剂通常是为了货架、加工和使用中的稳定性。硫化通常用硫、含硫化合物或过氧化物来完成,但也可以用在固化温度下或通过辐射产生自由基的其他化合物来完成。各种辅助材料,如固化促进剂、固化缓凝剂或增强剂,通常是复合配方的一部分。理想情况下,当弹性体在模具中形成最终形状时,硫化就开始了。弹性体类型及其粘度对成型性能有显著影响。干固体聚合物通常比乳胶材料含有更少的残余单体(或溶剂)。生产干燥产品所需的加工通常是通过加热将残留的单体或溶剂从树脂中除去。有几份报告涉及橡胶制造行业工人的健康问题。例如,一项研究表明,在涉及回收、化学品和特殊产品的操作中,肺癌的死亡风险与就业之间存在关联。
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引用次数: 1
Monohydric Alcohols—C1 to C6 一元醇- c1到C6
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX077.PUB2
C. Bevan
This chapter reviews both linear and branched monohydric aliphatic C1 to C6 alcohols. The C7 to C20 monohydric alcohols are covered in Chapter 78. The low molecular weight alcohols, including methanol, ethanol, 1-propanol, and isopropanol are used extensively in industry (16). These alcohols exist as volatile liquids at ambient temperatures, and exposure can occur in both industrial and nonindustrial environments. This review discusses primarily dermal and inhalation routes of exposure, which are the major routes of occupational exposure to alcohols. Many of the high-production alcohols such as methanol, ethanol, propanols, and butanols cause adverse effects when ingested; ingestion, however, is not a major route of occupational exposure. There are some alcohols that have produced adverse effects in humans, including death, in an occupational environment. Nevertheless, alcohols have been used extensively in the workplace generally with few or minor problems. Occasionally, methanol, ethanol, and the propanols produce a skin sensitizing response in humans. In some, but not all, cases the sensitization response was considered to be due to contaminants and not to the alcohol itself. A common property of some of the alcohols is to produce local irritation to the skin, eyes, and respiratory tract, and the effect or potency varies for the type of alcohol. Many alcohols produce minimal or no adverse effects in humans, possibly because of low exposure combined with the low toxicity potential of the alcohol. Few alcohols produce neuropathic effects in humans. Abuse of products containing methanol and ethanol has produced some indications of neurotoxicity in humans, but nothing has been reported in an occupational environment. 2-Hexanol produces neurotoxicity by the oral and intraperitoneal routes in animals, but there is no evidence of such an effect having occurred in the workplace. There is no clear evidence that occupational exposures to alcohols represent a carcinogenic risk to humans. Based on epidemiological data, there is an association between the manufacture of ethanol and isopropanol by the strong acid process (a process no longer used in the United States) and an excess of upper respiratory tract cancer in humans. The effect has been attributed to by-products such as dialkyl sulfates and sulfuric acid, not the alcohols themselves. Some of these alcohols such as ethanol and isopropanol can enhance the toxic effects of various chemicals, particularly hepatotoxins. It is thought that the effects may be due largely to an inductive effect of the alcohol on microsomal enzymes, particularly the cytochrome P450 system, which may allow a greater metabolic conversion of the hepatotoxin to its toxic metabolite. Keywords: Methanol; Inhalation studies; Ethanol; 1-Propanol; Isopropanol; Butanols; Amyl alcohols; Hexanols
本章回顾了线性和支链一元脂肪族C1到C6醇。C7至C20一元醇在第78章中有介绍。低分子量醇,包括甲醇、乙醇、1-丙醇和异丙醇,在工业上被广泛使用(16)。这些醇在环境温度下以挥发性液体的形式存在,在工业和非工业环境中都可能发生接触。本综述主要讨论了皮肤接触途径和吸入接触途径,这是职业接触酒精的主要途径。许多高产醇,如甲醇、乙醇、丙醇和丁醇,在摄入时会产生不良反应;然而,摄入并不是职业性接触的主要途径。在职业环境中,有些酒精会对人类产生不利影响,包括死亡。然而,酒精在工作场所被广泛使用,通常很少或很少有问题。甲醇、乙醇和丙醇偶尔会在人体中产生皮肤致敏反应。在某些情况下,但不是所有的情况下,敏化反应被认为是由于污染物而不是酒精本身。一些酒精的共同特性是对皮肤、眼睛和呼吸道产生局部刺激,效果或效力因酒精的类型而异。许多酒精对人体的不良影响很小或没有,这可能是因为接触量低,而且酒精的潜在毒性低。很少有酒精对人产生神经病变作用。滥用含有甲醇和乙醇的产品已经对人类产生了一些神经毒性的迹象,但在职业环境中没有任何报道。2-己醇通过口服和腹腔途径对动物产生神经毒性,但没有证据表明在工作场所发生了这种影响。没有明确的证据表明职业接触酒精对人类有致癌风险。根据流行病学资料,用强酸法(在美国已不再使用这种方法)生产乙醇和异丙醇与人类上呼吸道癌症发病率过高之间存在关联。这种影响被归因于副产品,如硫酸二烷基酯和硫酸,而不是醇本身。其中一些醇类,如乙醇和异丙醇,可以增强各种化学物质,特别是肝毒素的毒性作用。据认为,这种影响可能主要是由于酒精对微粒体酶的诱导作用,特别是细胞色素P450系统,这可能允许肝毒素更大的代谢转化为其有毒代谢物。关键词:甲醇;吸入研究;乙醇;1-Propanol;异丙醇;丁醇;戊醇;己醇
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引用次数: 4
期刊
Patty's Toxicology
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