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From Reactive Chemicals Control to Comprehensive Chemicals Policy: An Evolution and Opportunity 从活性化学品管制到综合化学品政策:演变与机遇
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX115
J. Tickner
The present chapter provides an overview for the improvements in chemical information, assessment, and management and emphasizes the need of comprehensive chemicals policy that leads to more sustainable chemicals, materials, and products. For many years, there has been widespread public concern about human exposure to toxic substances and the lack of information on how chemicals are used and how these exposures might affect health. It has been realized that the amount of exposure is not the only factor that produces risks but also the timing of the dose, particularly during critical windows of developmental vulnerability. During the past two decades, governments, companies, and nongovernmental organizations (NGOs) have identified significant limitations in existing structures for chemicals assessment and management. Many large users and producers of chemicals are now interested in developing sustainability policies that call for safer chemicals and products. The field of green chemistry and prevention through design (PtD) are contributing significantly in developing more sustainable chemicals management policies. There is a need for new chemical assessment and evaluation approaches that advance the development and adoption of safer alternatives and that do not shift risks to workers. Keywords: bisphenol A; dioxins; furans; green chemistry; persistent organic pollutants; Toxic Substances Control Act
本章概述了化学品信息、评估和管理方面的改进,并强调需要制定全面的化学品政策,以实现更可持续的化学品、材料和产品。多年来,公众普遍关注人类接触有毒物质的问题,以及缺乏关于化学品如何使用以及这些接触可能如何影响健康的信息。人们已经认识到,暴露量并不是产生危险的唯一因素,而且剂量的时机也是产生危险的唯一因素,特别是在发育脆弱的关键时期。在过去的二十年中,政府、公司和非政府组织(ngo)已经发现了现有化学品评估和管理结构的重大局限性。许多化学品的大用户和生产商现在有兴趣制定可持续性政策,要求使用更安全的化学品和产品。绿色化学和通过设计预防(PtD)领域在制定更可持续的化学品管理政策方面做出了重大贡献。有必要采用新的化学品评估和评价方法,以促进开发和采用更安全的替代品,同时不将风险转移给工人。关键词:双酚A;二恶英;呋喃;绿色化学;持久性有机污染物;有毒物质控制法
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引用次数: 1
Cyanides and Nitriles 氰化物和腈
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX061.PUB2
E. Kopras
Cyanides are among the most acutely toxic of all industrial chemicals and are produced in large quantities and used in many different applications. However, they cause few serious accidents or deaths. This is partly because the word cyanide is synonymous with a highly poisonous substance and a certain amount of care in handling is thereby ensured. The cyanides and nitriles are a disparate group of substances characterized by the presence of a cyanide (CN) group in their molecular structure. The cyanide group consists of a carbon bonded to a nitrogen. In those cases where the cyanide group is readily available, toxicity is likely to have similarity to hydrogen cyanide (HCN). The chemical and physical characteristics of the compound will affect the potential availability of the cyanide group and therefore, the hazards associated with different chemical species. For purposes of the toxicologist, cyanides and nitriles can be classified into groups based on their common properties. Group 1, inorganic cyanides, includes hydrogen cyanide, cyanogen, and simple salts such as sodium, potassium, calcium, and ammonium cyanide of hydrogen cyanide that dissociate readily to release CN−1 ions. Group 2 includes halogenated compounds such as cyanogen chloride or bromide. Group 3 comprises simple and complex salts such as cobalt cyanide trihydrate, cupric and cuprous cyanide, silver cyanide, and ferricyanide and ferrocyanide salts of hydrogen cyanide that do not dissociate readily to release CN−1 ions. Group 4, organic cyanides, includes cyanide glycosides produced by plants such as amygdalin and linamarin. Group 5, nitriles, have a general structure R-CNO, and include compounds such as acetonitrile (methyl cyanide), acrylonitrile, and isobutyronitrile. Keywords: Bhopal; cyanides; India; methylisocyanate release; nitriles
氰化物是所有工业化学品中毒性最大的一种,被大量生产并用于许多不同的用途。然而,它们很少造成严重事故或死亡。这在一定程度上是因为“氰化物”这个词是剧毒物质的同义词,因此在处理时一定程度上要小心。氰化物和腈是一组完全不同的物质,其特征是在其分子结构中存在氰化物(CN)基团。氰化物基团由一个碳和一个氮相连组成。在容易获得氰化物基团的情况下,毒性可能与氰化氢(HCN)相似。化合物的化学和物理特性将影响氰化物基团的潜在可用性,从而影响与不同化学种类相关的危害。为了毒理学家的目的,氰化物和腈可以根据它们的共同特性分类。第一类,无机氰化物,包括氰化氢、氰和简单的盐,如钠、钾、钙和氰化氢的氰化铵,它们容易解离释放CN - 1离子。第二类包括卤化化合物,如氯化氰或溴化物。第3组包括简单和复杂的盐,如三水合氰化钴、铜和亚氰化铜、氰化银、不容易解离释放CN - 1离子的氰化氢的铁氰化和亚铁氰化盐。第4类,有机氰化物,包括由植物产生的氰化物苷,如苦杏仁苷和亚麻苦素。第5族腈的一般结构为R-CNO,包括乙腈(甲基氰化物)、丙烯腈和异丁腈等化合物。关键词:博;氰化物;印度;methylisocyanate释放;腈
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引用次数: 0
Organic Chlorofluoro Hydrocarbons 有机氯氟烃
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX068.PUB2
G. Rusch
The chlorofluorocarbons (CFCs) were introduced in the 1930s as “safe” replacements for refrigerants such as sulfur dioxide, ammonia, carbon tetrachloride, and chloroform. In World War II, they were used to produce insecticide aerosols to protect the troops in tropical areas against malaria and other insectborne diseases. During the next 40–50 years, the number and type of applications expanded to include foam blowing, precision cleaning, and propellants for medicinal, cosmetic, and general-purpose aerosols, air conditioning, and refrigeration. These uses eventually resulted in emission of the CFCs into the atmosphere. Because of their low chemical reactivity, they typically have long atmospheric residence times, and as a consequence, they are distributed globally. In 1974 Molina and Rowland hypothesized that, once the CFCs reach the stratosphere, they will undergo breakdown to release chlorine atoms. The chlorine atoms could then react with the stratospheric ozone breaking it down into oxygen. Since the stratospheric ozone absorbed much of the sun's ultraviolet β radiation (UVB), decreased ozone levels would lead to increases in ground-level UVB. This could affect crop growth and lead to increases in cataracts and nonmelanoma skin cancers. Following reports of a marked drop in column ozone over Antarctica (the “ozone hole”) during the Antarctic winter, in 1987 most of the nations of the world drafted and signed an agreement calling for the phaseout of CFCs. This agreement is known as the Montreal Protocol. Development was initiated on two types of “in-kind” replacements. The first were the hydrochlorofluorocarbons (HCFCs) and the second were the hydrofluorocarbons (HFCs). Both contain hydrogen and are susceptible to attack by hydroxyl radicals present in the atmosphere. Therefore, they have a shorter atmospheric lifetime and either are not transported to the stratosphere or are transported there only in small amounts. The HCFCs contain chlorine and are still capable of causing ozone depletion, although, since their atmospheric lifetimes are short, their ozone-depleting potential (ODP) is lower than those associated with the CFCs. The HFCs do not contain chlorine (or bromine, also associated with ozone depletion). They, therefore, do not cause ozone depletion. A ranking scale has been developed using CFC11 as the reference compound, with an assigned value of 1. These values are also presented. A second concern, regarding both CFCs and their replacements, is that they are greenhouse warming gases. They, along with other substances such as carbon dioxide, trap the sun's infrared radiation and convert it to heat. However, they are also good insulating materials, and frequently their use as foam blowing agents in refrigeration equipment can lead to considerable energy savings, reducing carbon dioxide emissions. The greenhouse warming potentials (GWPs) for many of the CFCs, HCFCs, and HFCs are given. Many methods have been d
20世纪30年代,氯氟烃作为二氧化硫、氨、四氯化碳和氯仿等制冷剂的“安全”替代品问世。在第二次世界大战中,它们被用来生产杀虫剂气雾剂,以保护热带地区的部队免受疟疾和其他虫媒疾病的侵害。在接下来的40-50年里,应用的数量和类型扩大到包括泡沫吹制、精密清洁、医药、化妆品和通用气雾剂的推进剂、空调和制冷。这些用途最终导致氟氯化碳排放到大气中。由于它们的化学反应性低,它们通常在大气中停留时间长,因此它们分布在全球。1974年,莫利纳和罗兰假设,一旦氟氯化碳到达平流层,它们将发生分解,释放氯原子。氯原子随后会与平流层的臭氧发生反应,将其分解成氧气。由于平流层臭氧吸收了大部分太阳的紫外线β辐射(UVB),臭氧水平的降低将导致地面UVB的增加。这可能会影响作物生长,导致白内障和非黑色素瘤皮肤癌的增加。在南极冬季出现南极上空臭氧柱明显下降(即“臭氧空洞”)的报告后,1987年,世界上大多数国家起草并签署了一项协议,呼吁逐步淘汰氟氯化碳。这项协议被称为《蒙特利尔议定书》。开发了两种“实物”替代品。第一种是氢氯氟烃(HCFCs),第二种是氢氟烃(hfc)。两者都含有氢,容易受到大气中羟基自由基的攻击。因此,它们在大气中的寿命较短,要么不被输送到平流层,要么只少量输送到平流层。氟氯烃含有氯,仍然能够造成臭氧消耗,但由于其在大气中的寿命较短,其臭氧消耗潜能值(ODP)低于与氟氯烃相关的潜能值。氢氟碳化物不含氯(或溴,也与臭氧消耗有关)。因此,它们不会造成臭氧消耗。以CFC11为参比化合物,编制了排序量表,赋值为1。还给出了这些值。关于氟氯化碳及其替代品的第二个担忧是,它们是温室气体。它们与二氧化碳等其他物质一起捕获太阳的红外辐射并将其转化为热量。然而,它们也是良好的绝缘材料,并且经常将它们用作制冷设备中的泡沫发泡剂,可以节省大量能源,减少二氧化碳排放。给出了许多CFCs、HCFCs和hfc的温室增温潜能值(GWPs)。已经开发了许多方法对这些物质进行大气监测。由于它们的广泛使用以及对其环境影响和健康影响的关注,已经对这些材料进行了一些评论。从评论以及本章后面提供的数据可以看出,这些化学品中的许多都不是剧毒的。事实上,在空气暴露水平高达几个百分点甚至超过5%或10%的情况下,有些没有显示出明显的毒性迹象。过度接触后最典型的反应是与这些化学物质的麻醉特性有关的中枢神经系统抑制。此外,有些还会引起肝毒性,偶尔还会对生殖产生影响。每个化合物都单独讨论。它们大致分为三大类:氯氟烃、氢氯氟烃和氢氟烃。关键词:CFC 11-13;氯氟化碳112 - 115;HFC 21、22、123、124、132、133a、141b、142b, HFC 32、125、1344a、152a、245fa;臭氧消耗潜力;Chlorofluorcarbons;温室效应;全球变暖;大气一生
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引用次数: 2
Health Effects from Hand‐Transmitted Vibration 手传播振动对健康的影响
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX105.PUB2
H. Mason
Pneumatic tools and rotating tools, such as grinders have been recorded as being used in many countries. Poorly maintained tools are well-established causes of significantly increased transmission of vibrational energy into the hands of workers causing episodic finger blanching, symptoms of numbness and tingling and neurosensory deficit in the hands, and loss of grip strength. Collectively these health problems are termed HAVS and can become significantly disabling in severer cases. The term HAVS began to have widespread coinage as describing the range of vascular, neurosensory, and musculoskeletal problems associated with excessive exposure to HTV. There have been a number of reports that address the possible pathophysiological basis of the elements of HAVS. However, the exact relationship between the dose and either the vascular or neurosensory elements of HAVS has remained unclear as to how much the nature of the exposure data, often relying on retrospective exposure assessment, or the extent of individual susceptibility adds to the uncertainty or noise in any reported relationships. There has been considerable international effort to reduce exposures, especially through better ergonomically designed tools with lower vibration emissions. Keywords: carpal tunnel syndrome; hand-arm vibration syndrome; Purdue pegboard test; Raynaud's phenomenon; vibration white finger; whole body vibration
据记载,许多国家都在使用气动工具和旋转工具,如磨床。维修不善的工具是造成振动能量明显增加传递到工人手中的原因,造成间歇性手指变白、手部麻木和刺痛以及神经感觉缺陷的症状,以及握力丧失。这些健康问题统称为HAVS,在严重的情况下会严重致残。HAVS一词开始被广泛使用,用于描述与过度暴露于HTV相关的血管、神经感觉和肌肉骨骼问题。已经有一些报告,解决可能的病理生理基础的要素HAVS。然而,剂量与HAVS的血管或神经感觉因素之间的确切关系仍然不清楚,暴露数据的性质有多少,通常依赖于回顾性暴露评估,或者个体易感性的程度增加了任何报告关系的不确定性或噪音。国际上已经做出了相当大的努力来减少暴露,特别是通过更好的符合人体工程学设计的工具,降低振动排放。关键词:腕管综合征;手臂振动综合征;普渡钉板试验;雷诺氏现象;震动白手指;全身振动
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引用次数: 0
Metalworking Fluids (MWF) 金属加工液(MWF)
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX117
F. Mirer
The present chapter summarizes metalworking fluid (MWF). MWF is the term also used for fluids used in various processes and operation for the manufacture of engines, transmissions, and chassis parts. There are two general categories and four major types of MWF. The characteristics and composition of fluids, as well as technological details of application have been reviewed. The experimental evidence suggests that several agents known to be present in MWF have been classified as carcinogenic. Studies also identified the associations of both straight oil and water-reduced MWF with several respiratory diseases. NIOSH and the OSHA Metalworking Fluids Standards Advisory Committee have reviewed the health hazards and protective measures. Keywords: aerosols; endotoxin; cancer; hypersensitivity pneumonitis; asthma; skin disorders
本章概述了金属加工液。MWF这个术语也用于制造发动机、变速器和底盘部件的各种过程和操作中使用的流体。MWF有两大类和四种主要类型。综述了流体的特性、组成以及应用的技术细节。实验证据表明,已知存在于MWF中的几种物质已被列为致癌物。研究还确定了直接油和水还原的MWF与几种呼吸系统疾病的关联。NIOSH和OSHA金属加工液标准咨询委员会审查了对健康的危害和保护措施。关键词:气溶胶;内毒素;癌症;过敏性肺炎;哮喘;皮肤疾病
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引用次数: 0
N-Nitroso Compounds†
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX055.PUB2
R. Clapp, M. Jacobs, W. Lijinsky
N-Nitroso compounds, which include nitrosamines and nitrosamides, have been known for more than 100 years, but nothing was known of their toxicologic properties until 1937, when Freund described a laboratory poisoning by nitrosodimethylamine (NDMA). Then Barnes and Magee in 1954 (also following an accidental exposure of humans to NDMA being used as a solvent) described a thorough toxicological examination of the compound in several species, in which liver and/or lung injury caused death. This culminated in a chronic toxicity test in rats, which resulted in a high incidence of animals with liver tumors within a year. The finding that a member of a large class of water-soluble compounds was carcinogenic aroused considerable interest and an investigation began into the relationship between the chemical structure of N-nitroso compounds and their carcinogenic properties, initially by Druckrey et al. (mainly in rats), followed by other chemists and pathologists. The objective was to obtain clues to the mechanism(s) of carcinogenesis by these compounds, but other issues arose. One of the most interesting was the widespread nature of nitrosamine carcinogenesis that affected all species examined, although not always were tumors of the same type induced in all species. Indeed, as the number of N-nitroso compounds tested increased (more than 300 have been examined), it became apparent that virtually every type of human tumor was reproduced in some animal with some N-nitroso compound. The N-nitroso compounds varied widely in toxic and carcinogenic potency, but not in parallel, although the most acutely toxic compounds tended to be the most potent carcinogens. Many quite potent carcinogens, however, showed relatively low toxicity, and vice versa. For many years, the carcinogenic N-nitroso compounds were considered an interesting curiosity, but in the 1960s it was found that some batches of fish meal which had been treated with sodium nitrite for preservation caused toxic liver injury in sheep. The cause of the injury was traced to nitrosodimethylamine (NDMA) which had formed in the fish meal. This was a surprise because nitrosamines, it was thought, formed by interaction of secondary amines with nitrite in acid solution, not at neutral pH. It has since become obvious that tertiary amines, as well as secondary amines, interact with nitrite under certain conditions (above pH 4) to form nitrosamines. This was information previously known but, like Freund's report, was buried in the literature. Further investigations revealed that many commonly used drugs and medicines which are tertiary amines are also easily nitrosated to form N-nitroso compounds, thereby presenting a risk of human exposure to these carcinogens. In the case of the nitrite-treated fish meal, it is not clearly known whether the NDMA arises by nitrosation of dimethylamine, trimethylamine, trimethylamine-N-oxide, or some other precursor. In addition to nitrites, nitrosation can
n -亚硝基化合物,包括亚硝胺和亚硝胺,已经被发现了100多年,但直到1937年,人们才知道它们的毒理学特性,当时弗洛伊德描述了一次亚硝基二甲胺(NDMA)的实验室中毒。然后,巴恩斯和马吉在1954年(也是在人类意外暴露于NDMA作为溶剂之后)描述了对几种物种中该化合物的彻底毒理学检查,其中肝脏和/或肺部损伤导致死亡。这在大鼠的慢性毒性试验中达到高潮,结果一年内动物肝脏肿瘤的发病率很高。一大类水溶性化合物中的一种具有致癌性,这一发现引起了人们极大的兴趣,并开始对n -亚硝基化合物的化学结构与其致癌性之间的关系进行调查,最初是由Druckrey等人(主要在大鼠中)进行的,随后是其他化学家和病理学家。目的是获得这些化合物致癌机制的线索,但其他问题出现了。其中最有趣的是亚硝胺致癌作用的广泛性,它影响到所有被检查的物种,尽管并非所有物种都诱发相同类型的肿瘤。事实上,随着测试的n -亚硝基化合物数量的增加(已经测试了300多种),很明显,几乎每种类型的人类肿瘤都可以在某些动物体内复制某些n -亚硝基化合物。n -亚硝基化合物在毒性和致癌性方面差异很大,但不是平行的,尽管毒性最强的化合物往往是最有效的致癌物。然而,许多相当强的致癌物显示出相对较低的毒性,反之亦然。多年来,致癌的n -亚硝基化合物被认为是一种有趣的好奇心,但在20世纪60年代,人们发现,一些批次的鱼粉经亚硝酸钠处理后保存,会对绵羊造成毒性肝损伤。受伤的原因是在鱼粉中形成的亚硝基二甲胺(NDMA)。这是一个惊喜,因为亚硝胺被认为是由仲胺与亚硝酸盐在酸性溶液中相互作用形成的,而不是在中性pH下形成的。从那以后,很明显,叔胺和仲胺在一定条件下(pH高于4)与亚硝酸盐相互作用,形成亚硝胺。这是以前已知的信息,但像弗洛伊德的报告一样,被埋没在文献中。进一步的调查显示,许多常用的叔胺类药物也很容易亚硝化形成n -亚硝基化合物,从而给人类带来接触这些致癌物的风险。就亚硝酸盐处理的鱼粉而言,尚不清楚NDMA是由二甲胺、三甲胺、三甲胺- n -氧化物或其他前体亚硝化引起的。除亚硝酸盐外,燃烧燃料中的“亚氮气体”(氮氧化物)、烷基亚硝酸盐或亚硝胺(通常是无生物活性的),如亚硝胺酸,也可通过称为亚硝化的过程影响亚硝化。这些古老的研究指出,人体接触到n -亚硝基化合物可能是因为食用了含有n -亚硝基化合物的亚硝酸盐腌制食品(肉或鱼)。啤酒中有NDMA,可能现在仍然存在,它是由麦芽中的生物碱(hordenine和gramine)和其他叔胺与用于加热麦芽的气体中的氮氧化物相互作用产生的;据报道,某些啤酒中的NDMA含量高达百万分之50。在腌肉中寻找烷基亚硝基源物质是由于一些流行病学观察结果,这些观察结果将儿童脑癌与怀孕母亲大量食用腌肉联系起来,而且烷基亚硝基源物质在怀孕大鼠或小鼠中的经胎盘作用可能是诱发神经系统肿瘤的最佳动物模型。自1974年首次报道烟草烟雾中的亚硝胺(NDMA)以来,主要由Hoffmann和Hecht小组对这一主题进行了大量研究。除了挥发性亚硝胺、亚硝基吡咯烷、NDMA、NMEA和NDEA外,还发现了一些所谓的“烟草特异性”亚硝胺:亚硝基烟碱和4-(甲基亚硝胺)-1-(3-吡啶基)-1-丁酮(简称NNK),这是一种强致癌物,可导致大鼠和仓鼠的肝脏和肺部肿瘤,是烟草和烟草烟雾中最丰富的致癌物之一。NNK也是咀嚼烟草或鼻烟中的重要成分(高达8ppm),是这些产品中为数不多的致癌物之一(亚硝基索尼古丁是另一种,但弱得多),它肯定会增加使用者的致癌风险,他们经常患上口腔癌。 人类接触n -亚硝基化合物的其他来源包括生产或使用亚硝胺(通常是NDMA)的工厂(如生产或使用火箭燃料1,1-二甲肼的工厂)内和附近的空气,以及生产农药的工厂(农药通常以二甲胺盐的形式储存或销售,氮氧化物可转化为挥发性NDMA)。亚硝胺的一个重要来源是橡胶和轮胎工业。在制革场所也发现了亚硝胺(主要是NDMA)。亚硝胺的最大工业暴露可能来自金属加工液(包括切削油),其中亚硝基二乙醇胺(NDELA)的浓度高达3%,尽管通常较低。NDELA是由作为乳化剂的三乙醇胺(含有二乙醇胺)与作为缓蚀剂的亚硝酸钠结合而成。金属加工液中可能存在的烷醇胺、醛和亚硝酸盐的组合也可产生含氧的环亚硝胺,如亚硝基恶唑烷,这是一种强致癌物。通常使用亚硝酸盐作为易拉罐的腐蚀抑制剂,导致罐装运输的许多胺受到污染,并导致洗发水和其他个人卫生制剂中存在亚硝胺,如甲基亚硝基十二烷基胺和甲基亚硝基十四乙胺。据报道,土壤、水和污水中都含有亚硝胺,但信息不完整。关键词:代谢;激活;亚硝胺的食物来源;N-Nitroso化合物;诱变;风险评估;致癌性 人类接触n -亚硝基化合物的其他来源包括生产或使用亚硝胺(通常是NDMA)的工厂(如生产或使用火箭燃料1,1-二甲肼的工厂)内和附近的空气,以及生产农药的工厂(农药通常以二甲胺盐的形式储存或销售,氮氧化物可转化为挥发性NDMA)。亚硝胺的一个重要来源是橡胶和轮胎工业。在制革场所也发现了亚硝胺(主要是NDMA)。亚硝胺的最大工业暴露可能来自金属加工液(包括切削油),其中亚硝基二乙醇胺(NDELA)的浓度高达3%,尽管通常较低。NDELA是由作为乳化剂的三乙醇胺(含有二乙醇胺)与作为缓蚀剂的亚硝酸钠结合而成。金属加工液中可能存在的烷醇胺、醛和亚硝酸盐的组合也可产生含氧的环亚硝胺,如亚硝基恶唑烷,这是一种强致癌物。通常使用亚硝酸盐作为易拉罐的腐蚀抑制剂,导致罐装运输的许多胺受到污染,并导致洗发水和其他个人卫生制剂中存在亚硝胺,如甲基亚硝基十二烷基胺和甲基亚硝基十四乙胺。据报道,土壤、水和污水中都含有亚硝胺,但信息不完整。关键词:代谢;激活;亚硝胺的食物来源;N-Nitroso化合物;诱变;风险评估;致癌性
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引用次数: 0
Miscellaneous Chlorinated Hydrocarbon Pesticides 杂类氯代烃杀虫剂
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX069.PUB2
J. Bus, A. Leber
This chapter presents information on two structurally and toxicologically different classes of chlorinated pesticides: the organochlorine insecticides and the herbicide 2,4-dichlorophenoxyacetic acid (2,4D). The first group described, the chlorinated hydrocarbon insecticides, belong to a structural class containing only carbon, hydrogen and chlorine. This pesticide group has dramatically decreased in use and fallen into regulatory disfavor because, in general, its structural properties promote both persistence in the environment and bioaccumulation within the food chain. In contrast the herbicide 2,4D contains carbon, hydrogen, chlorine, and oxygen, and is a widely used herbicide with environmental and toxicological properties distinctly different from the organochlorine insecticides. The organochlorine insecticides represent the first group of synthetic compounds to have a significant impact on the control of infectious diseases transmitted via insect vectors. These insecticides were used extensively in the United States and other Western countries, and are still used in Third World regions as both agricultural insecticides and agents to combat such vectorborne diseases as malaria, typhus, plague, Chagas' disease, yellow fever, dengue, encephalitis, filariasis, and African trypanosomiasis (sleeping sickness). Of these insecticides, DDT (dichlorodiphenyltrichloroethane) is credited as the primary compound that, for the first time in history, brought epidemics of malaria, typhus, and plague to a complete stop. DDT was introduced in 1943, with related insecticides following shortly thereafter. This chemical is still used extensively in tropical regions to combat malarial mosquitoes, and substitution of this pesticide with others such as malathion would be most expensive. One attribute that contributes to the effectiveness of this chemical class is its persistence in the environment, providing not only an immediate impact on insect populations but also a prolonged insecticidal presence extending well beyond the time of application. This persistence is now generally considered an undesirable feature owing to findings suggesting delayed adverse impacts on nontarget populations of insects as well as birds. In addition, increased cancer risks for humans are alleged to result from exposures to these chemicals such as those resulting from pesticide applications and ingestion of contaminated fish and other food species. Although the actual balance of risks versus benefits associated with the use of these insecticides is debated, regulatory action has virtually eliminated their use in the United States and other western countries. Summarizes the regulatory status of these products. The persistence of these insecticides in the environment and their prolonged activity against pests following application can be attributed to a combination of their insolubility in water and high solubility in fats, absorption and adsorption onto particulate
本章介绍了两种结构和毒性不同的氯化农药:有机氯杀虫剂和除草剂2,4-二氯苯氧乙酸(2,4d)。描述的第一组,氯化烃杀虫剂,属于只含有碳、氢和氯的结构类。这类农药的使用急剧减少,并受到监管部门的反对,因为总的来说,它的结构特性促进了环境中的持久性和食物链中的生物积累。相比之下,除草剂2,4d含有碳、氢、氯、氧,是一种广泛使用的除草剂,其环境和毒理学性质与有机氯杀虫剂明显不同。有机氯杀虫剂是对控制通过昆虫媒介传播的传染病产生重大影响的第一组合成化合物。这些杀虫剂在美国和其他西方国家广泛使用,在第三世界地区仍被用作农业杀虫剂和防治病媒传播疾病的药剂,如疟疾、斑疹伤寒、鼠疫、南美锥虫病、黄热病、登革热、脑炎、丝虫病和非洲锥虫病(昏睡病)。在这些杀虫剂中,滴滴涕(二氯二苯三氯乙烷)被认为是历史上第一次完全制止疟疾、斑疹伤寒和鼠疫流行的主要化合物。滴滴涕于1943年引入,此后不久又引入了相关的杀虫剂。这种化学品仍在热带地区广泛使用,以对抗疟疾蚊子,用马拉硫磷等其他农药替代这种农药将是最昂贵的。这类化学物质有效的一个特点是它在环境中的持久性,不仅对昆虫种群有直接的影响,而且在施用时间之后还能有长期的杀虫作用。由于研究结果表明对非目标种群的昆虫和鸟类的延迟不利影响,这种持久性现在普遍被认为是不可取的特征。此外,人类癌症风险的增加据称是由于接触这些化学物质造成的,例如农药的使用和摄入受污染的鱼类和其他食物。尽管使用这些杀虫剂的风险与收益之间的实际平衡存在争议,但在美国和其他西方国家,监管行动实际上已经消除了它们的使用。总结了这些产品的监管现状。这些杀虫剂在环境中的持久性及其在施用后对害虫的持久活性可归因于它们在水中的不溶性和在脂肪中的高溶解度,对颗粒物质的吸收和吸附以及对化学,物理和微生物降解的抵抗力。从目标作物和周围的土壤和水,这些化合物已经进入哺乳动物、鸟类、鱼类和其他动物物种的食物链。滴滴涕尤其与鱼类和鸟类因生物积累而引起急性甚至可能是慢性杀虫剂中毒有关。史密斯讨论了这样一个事实,即动物和人类在过度暴露于氯化杀虫剂后的主要急性毒性是神经功能亢进。对于滴滴涕和相关化合物,其影响从轻微震颤逐渐发展到抽搐,而抽搐是林丹、艾氏、狄氏、恩德林、毒杀芬和相关物质等化合物中毒的第一个迹象。后者可产生不协调、虚弱和与震颤无关的共济失调状态,将这些物质引起的中毒与滴滴涕引起的中毒区别开来。一般来说,急性效应尚未显示对暴露人群构成重大危害,目前对这些化合物毒性的关注主要与下文讨论的慢性低水平暴露有关。如上所述,由于这些农药对环境的影响,加上它们在20世纪70年代初被列为“潜在的人类致癌物”,在美国、加拿大和大多数欧洲国家,大多数有机氯农药的使用已被停止或显著减少。所谓的人类危害,癌症,是基于对实验室动物(主要是小鼠)肿瘤诱导的观察,这些化合物产生了良性和恶性的肝细胞肿瘤。争论的一个原因是,很少有化学物质能诱导啮齿动物的肿瘤在人类身上产生活性。在美国、加拿大和西欧文献中,没有报道过对肝脏或其他人体器官的直接和无可争议的损伤。 据我们所知,美国人在家庭和餐馆准备的食物和饮料中摄入有机氯杀虫剂(单独或组合使用)已经超过35年(DDT于1943年引入),随后摄入量大幅减少,没有造成公认的或明确定义的有害影响。啮齿动物肝脏肿瘤作为人类癌症风险指标的重要性在科学界仍存在争议。顺便说一句,虽然有机氯杀虫剂被认为是潜在的人类致癌物。虽然肝癌死亡率有所下降,但人类乳腺癌的发病率却有所上升。乳腺癌发病率的增加在很大程度上归因于乳房x光检查和其他筛查技术的更频繁使用,以及其他风险因素的其他变化,如某些生殖变量的流行。关键词:农药;滴滴涕;DDE;奥尔德林;氯丹;狄氏剂;2,4 - d;七氯;开蓬;除草剂;传染病;环境持久性
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引用次数: 1
Esters of Mono‐, Di‐, and Tricarboxylic Acids 单羧酸、二羧酸和三羧酸酯
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX080.PUB2
R. M. David, Ammie N. Bachman, J. Butala, J. Piper, Catherine Shelp
This chapter presents information on esters of mono-, di-, and tricarboxylic acids with monoalcohols from 1 to over 10 carbons in either a straight chain or branched configuration. In general, the properties (chemical and functional) change with the carbon length of the alcohol. Properties shift from higher water solubility and lower boiling point to lower water solubility and higher boiling point for esters of a particular acid group. There is insufficient information to conclude that the carbon length of the acid group influences the properties significantly. Also included are esters of the trialcohol, glycerol, with monocarboxylic acids. These substances are included for the sake of completeness. All esters are subject to hydrolysis, especially enzymatic hydrolysis. Most esters in biotic systems hydrolyze primarily to the carboxylic acid and alcohol. There are some exceptions such as esters of phthalic acid that form relatively stable monoesters in biotic systems, which can be further oxidized. The uses of various esters are reviewed below and they vary with the acid. The simple aliphatic esters of benzoic acid are liquids that are used as solvents, flavors, or perfumes. Benzyl benzoate is used as a miticide or as a plasticizer. In general, these compounds have a low order of toxicity. The primary effects expected from the ingestion of moderate amounts of benzoates are gastrointestinal (GI) irritation, gastric pain, nausea, and vomiting. Available data indicate a low order of skin absorbability, and the undiluted materials may be either slight or moderate skin irritants. In rabbits, the degree of skin irritation caused by alkyl benzoates increases with an increase in molecular weight. The salicylates are used as flavorants, perfumes, or analgesics. The most commonly used member of this class of compounds is methyl salicylate. Ingestion of relatively small quantities of methyl salicylate may cause severe, rapid-onset salicylate poisoning. The lower alkyl esters of p- or 4-hydroxybenzoic acid (C1–C4), also named the methyl-, ethyl-, propyl-, and butyl parabens, are high-boiling liquids that decompose on heating. They are widely used in the food, cosmetic, and pharmaceutical industries as preservatives, bacteristats, and fungistats. Parabens also have been used therapeutically in the treatment of moniliasis, a Candida albicans infection. By the oral route, parabens are rapidly absorbed, metabolized, and excreted. The lower paraben homologues have low potential for acute or chronic systemic toxicity and are therefore approved as human food additives. Cinnamates (phenyl acrylates and phenylpropenoic acid esters) are mainly used as fragrances in the perfume industry. Cinnamates appear to have low to moderate toxicity in mammals. In humans, dermal exposure to allyl cinnamate may cause skin irritation. Some p-aminobenzoic acid (PABA) esters occur naturally, because the free compound, PABA, that is utili
本章介绍了单、二、三羧酸酯与单醇从1到超过10个碳在直链或分支配置的信息。一般来说,性质(化学和功能)随着醇的碳长度的变化而变化。特定酸基的酯的性质从高水溶性和低沸点转变为低水溶性和高沸点。目前还没有足够的信息来得出酸基的碳长度对性能有显著影响的结论。还包括三醇酯,甘油,与单羧酸。为了完整起见,把这些物质包括在内。所有的酯都可以水解,尤其是酶水解。生物系统中的大多数酯主要水解为羧酸和醇。也有一些例外,如邻苯二甲酸酯在生物系统中形成相对稳定的单酯,可以进一步氧化。下面回顾了各种酯的用途,它们因酸而异。苯甲酸的简单脂肪族酯是用作溶剂、香精或香水的液体。苯甲酸苄酯可用作杀虫剂或增塑剂。一般来说,这些化合物的毒性较低。摄入适量苯甲酸盐的主要影响是胃肠道(GI)刺激、胃痛、恶心和呕吐。现有数据表明,皮肤可吸收性较低,未稀释的材料可能对皮肤有轻微或中度刺激。在家兔中,烷基苯甲酸酯引起的皮肤刺激程度随着分子量的增加而增加。水杨酸盐可用作香料、香水或止痛剂。这类化合物中最常用的成员是水杨酸甲酯。摄入相对少量的水杨酸甲酯可引起严重的、快速发作的水杨酸中毒。对羟基苯甲酸或4-羟基苯甲酸(C1-C4)的低烷基酯,也被称为对羟基苯甲酸甲酯、乙基苯甲酸酯、丙基苯甲酸酯和丁基苯甲酸酯,是加热时分解的高沸点液体。它们广泛用于食品、化妆品和制药行业,作为防腐剂、抑菌剂和真菌剂。对羟基苯甲酸酯也用于治疗念珠菌感染念珠菌病。通过口服途径,对羟基苯甲酸酯被迅速吸收、代谢和排泄。较低的对羟基苯甲酸酯同系物具有较低的急性或慢性全身毒性,因此被批准作为人类食品添加剂。肉桂酸酯(苯基丙烯酸酯和苯基丙烯酸酯)在香水工业中主要用作香料。肉桂酸酯对哺乳动物似乎有低到中等的毒性。在人类,皮肤暴露于肉桂酸烯丙酯可能会引起皮肤刺激。一些对氨基苯甲酸(PABA)酯是自然产生的,因为用于它们合成的游离化合物PABA是维生素B复合物的一个复杂部分。PABA酯类在实验动物中表现出低阶急性毒性。在人类中,局部使用苯佐卡因或普鲁卡因后出现高铁血红蛋白血症的病例已有报道。含有PABA酯的防晒剂偶尔会产生过敏性光敏。邻氨基苯甲酸酯(邻氨基苯甲酸酯)比对氨基苯甲酸酯刺激性更小,引起致敏的可能性更小,但治疗效果较差。它们被用于一些防晒乳液中。邻氨基苯甲酸酯具有低毒性。甘油酯的长链脂肪酸可被一个或多个乙酰基取代,生成单乙酰、二乙酰或三乙酰。醋酸酯、丙酸酯和丁酸酯用作食品添加剂、溶剂或增塑剂以及表面活性剂。现有证据表明,这些药剂的毒性较低。通常情况下,吸入或直接皮肤接触不会产生刺激性作用。奇数碳链脂肪酸(C5-C11)的高甘油酯在各种生物体中自然存在的数量非常少,偶数(C12-C24)酯是常见的营养成分。它们被用作食品、工业原料或非酸性洗涤剂的乳化剂。一些关于C5和C8化合物的毒性数据是可用的。偶数的C12-C18甘油是无毒的。关于间苯二酚酯化合物的毒理学信息很少。没食子酸盐在化学上是三羟基苯甲酸酯。它们通常用作抗氧化剂,而没食子酸酯丙酯、没食子酸酯辛酯和没食子酸酯十二烷基已被批准作为食品添加剂。没食子酸酯在实验动物中表现出较低的急性和慢性毒性。大量证据表明它们不会致癌或致畸。草酸盐、丙二酸盐、戊二酸盐和琥珀酸盐是高闪、高沸腾的液体。草酸盐和丙二酸盐主要用作树脂的溶剂或化学中间体。
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引用次数: 3
Aromatic Amino and Nitro–Amino Compounds and Their Halogenated Derivatives 芳香氨基和硝基氨基化合物及其卤化衍生物
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX058.PUB2
Y. Woo, D. Lai
Aromatic amines are organic compounds that contain at least one amino group attached directly to an aryl moiety. Aromatic amines represent one of the most important classes of industrial and environmental chemicals. Many aromatic amines have been shown to be potent carcinogens, mutagens, skin sensitizers, and/or hematotoxicants capable of inducing methemoglobinemia. Since the introduction of substituted anilines and naphthylamines as intermediates for the manufacture of azo dyes in the mid-1800s, aromatic amines have found numerous uses in various industries. Substantial worker exposure to aromatic amines with subsequent induction of bladder cancer occurred before preventive measures were instituted. Beyond occupational exposure, humans may also be exposed to aromatic amines through environmental sources. At least three carcinogenic aromatic amines (4-aminobiphenyl, 2-naphthylamine, and o-toluidine) have been detected in cigarette smoke. Many commonly used pharmaceuticals contain or are aromatic amines. Owing to their hazard potential, aromatic amines have been the subject of many biomonitoring studies, making them model compounds in molecular dosimetry and epidemiology studies. Since extensive information is available on the metabolic pathways and, to a lesser extent, the mechanism(s) of action, aromatic amines have also become targets for genetic polymorphism studies with ultimate goals of identifying susceptible subpopulations and designing of strategies for cancer prevention and intervention. The multifaceted interest in aromatic amines has continued to attract a tremendous amount of scientific studies and attention. Since the publication of the previous edition of Patty's on aromatic amines, many reviews and important research articles on aromatic amines and halogenated nitroaromatics have been published. In addition, a number of heterocyclic aromatic amines have attracted increasing attention as carcinogens of environmental significance. In this chapter, we present an overview of the aromatic amine class as a whole with emphasis on recent studies, followed by an updated description on individual chemicals grouped into eight subgroups of structurally related compounds. Keywords: Aromatic amino compounds; carcinogenicity; halogenated derivatives; hemoglobin binding; mechanism of action; methemoglobinemia; mutagenicity; nitro–amino compounds; skin sensitization; teratogenicity
芳香胺是含有至少一个直接连接到芳基部分的氨基的有机化合物。芳香胺是工业和环境化学品中最重要的一类。许多芳香胺已被证明是强致癌物、诱变剂、皮肤致敏剂和/或能够诱导高铁血红蛋白血症的血液毒物。自从19世纪中期引入取代苯胺和萘胺作为制造偶氮染料的中间体以来,芳香胺在各种工业中得到了广泛的应用。在采取预防措施之前,大量工人接触芳香胺并随后诱发膀胱癌。除了职业接触外,人类还可能通过环境来源接触芳香胺。在香烟烟雾中已检出至少三种致癌芳香胺(4-氨基联苯、2-萘胺和邻甲苯胺)。许多常用的药物含有或就是芳香胺。由于其潜在的危害,芳香胺已成为许多生物监测研究的主题,使其成为分子剂量学和流行病学研究的模型化合物。由于关于代谢途径的广泛信息以及在较小程度上的作用机制,芳香胺也成为遗传多态性研究的目标,其最终目标是确定易感亚群并设计癌症预防和干预策略。芳香族胺的研究引起了广泛的科学研究和关注。自上一期《Patty’s on aromatic amines》出版以来,出现了许多关于芳香胺和卤代硝基芳烃的综述和重要研究文章。此外,一些杂环芳香胺作为具有环境意义的致癌物越来越受到人们的关注。在本章中,我们概述了芳香胺类作为一个整体,重点介绍了最近的研究,其次是对单个化学物质的更新描述,分为结构相关化合物的八个亚群。关键词:芳香族氨基化合物;致癌性;卤代衍生物;血红蛋白绑定;作用机理;高铁血红蛋白症;诱变;nitro-amino化合物;皮肤敏化;致畸性
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引用次数: 65
Tuberculosis and Other Mycobacteria 结核和其他分枝杆菌
Pub Date : 2012-08-17 DOI: 10.1002/0471435139.TOX021.PUB2
J. Yadav, R. Kapoor
Mycobacteria are a group of microbial pathogens associated with tuberculosis (TB), one of the world's most prevalent human disease and several nontuberculous diseases in humans. Another major human infection caused by this genus is leprosy. TB is predominantly a pulmonary disease infecting lungs but extrapulmonary TB is also prevalent and includes lymphatic, pleural, meningeal, pericardial, skeletal, gastrointestinal, genitourinary, or miliary form. The genus Mycobacterium comprises of about 130 species that are groupable into two major categories: (A) the Mycobacterium tuberculosis complex: it comprises of two obligate pathogenic species, namely M. tuberculosis (the agent of tuberculosis) and Mycobacterium leprae (the agent of leprosy). This complex contains four other species of mycobacteria that also cause TB viz., Mycobacterium bovis, Mycobacterium africanum, Mycobacterium microti, and Mycobacterium canetti. (B) The nontuberculous mycobacteria (also called atypical mycobacteria or environmental mycobacteria): this group comprises of a large number of saprophytic species that live freely in the environment such as in soils, water, and other organic matrices. These organisms may be inhaled via dust particles or ingested via drinking water or food and produce various syndromes. Nontuberculous mycobacteria (NTM) are increasingly being recognized to cause human infections, frequently in immunosuppressed individuals such as those who have organ transplants, individuals being treated for leukemia or cancer, and patients suffering from AIDS. The range of infections caused by NTM species is very broad and includes pulmonary infections (symptoms often indistinguishable from TB), cervical lymphadenitis, skin infections, bone and soft tissue infections, and nosocomial infections. An occupational disease in machinists, designated hypersensitivity pneumonitis (HP) has also been associated with NTM species (Mycobacterium immunogenum and Mycobacterium chelonae) that have the ability to colonize metalworking fluids in occupational environments. Although this chapter focuses primarily on tuberculosis, nontuberculous mycobacteria that are associated with human disease are also discussed. It includes discussions on taxonomy, growth requirements, as well as the morphological characteristics, physiology, pathogenicity, and the metabolic activity of these organisms. Keywords: epidemiology; exposure; Mycobacterium tuberculosis; nontuberculous mycobacteria; prevention; risk factors; treatment; tuberculosis
分枝杆菌是一组与结核病相关的微生物病原体,结核病是世界上最普遍的人类疾病之一,也是人类的几种非结核性疾病。由该属引起的另一种主要人类感染是麻风病。结核主要是一种肺部疾病,但肺外结核也很普遍,包括淋巴、胸膜、脑膜、心包、骨骼、胃肠道、泌尿生殖系统或军事性结核。分枝杆菌属包括约130种,可分为两大类:(A)结核分枝杆菌复合体:它包括两种专性致病性物种,即结核分枝杆菌(结核病的病原体)和麻风分枝杆菌(麻风的病原体)。这个复体包含另外四种也引起结核的分枝杆菌,即牛分枝杆菌、非洲分枝杆菌、微分枝杆菌和卡内蒂分枝杆菌。(B)非结核分枝杆菌(也称为非典型分枝杆菌或环境分枝杆菌):该组由大量腐生菌组成,它们自由地生活在环境中,如土壤、水和其他有机基质中。这些微生物可通过灰尘颗粒吸入或通过饮用水或食物摄入,并产生各种综合征。非结核分枝杆菌(NTM)被越来越多地认识到可引起人类感染,通常发生在免疫抑制的个体,如器官移植患者、白血病或癌症治疗患者和艾滋病患者。NTM物种引起的感染范围非常广泛,包括肺部感染(症状通常与结核病难以区分)、宫颈淋巴结炎、皮肤感染、骨骼和软组织感染以及医院感染。作为机械师的一种职业病,超敏性肺炎(HP)也与NTM物种(免疫原分枝杆菌和chelon分枝杆菌)有关,它们有能力在职业环境中定植金属加工液。虽然本章主要关注结核病,但也讨论了与人类疾病相关的非结核分枝杆菌。它包括对这些生物的分类、生长要求以及形态特征、生理学、致病性和代谢活性的讨论。关键词:流行病学;接触;结核分枝杆菌;nontuberculous分枝杆菌;预防;风险因素;治疗;肺结核
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引用次数: 1
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Patty's Toxicology
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