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丙烯醛的命运与影响。

Fate and effects of acrolein.

作者信息

Ghilarducci D P, Tjeerdema R S

机构信息

Santa Clara County Central Fire Protection District, Hazardous Materials Program, Los Gatos, CA 95030, USA.

出版信息

Rev Environ Contam Toxicol. 1995;144:95-146. doi: 10.1007/978-1-4612-2550-8_2.

Abstract

Acrolein is a highly toxic, reactive, and irritating aldehyde that occurs as a product of organic pyrolysis, as a metabolite of a number of compounds, and as a residue in water when used for the control of aquatic organisms. It is an intermediate in the production of acrylic acid, DL-methionine, and numerous other agents. Its major direct use is as a biocide for the control of aquatic flora and fauna. It is introduced to the environment from a variety of sources, including organic combustion such as automobile exhaust, cigarette smoke, and manufacturing and cooking emissions, as well as direct biocidal applications. Organic combustion from both fixed and mobile sources is the significant source of acrolein in the atmosphere; it represents up to 8% of the total aldehydes generated from vehicles and residential fireplaces and 13% of total atmospheric aldehydes. This reactive aldehyde also occurs in organisms as a metabolite of allyl alcohol, allylamine, spermine, spermidine, and the anticancer drug cyclophosphamide, and as a product of UV radiation of the skin lipid triolein. Furthermore, small amounts are found in foods; when animal or vegetable fats are overheated, however, large amounts are produced. Most human contact occurs during exposure to smoke from cigarettes, automobiles, industrial processes, and structural and vegetation fires. Besides cigarette smoke, occupational exposures are a common mode of human contact, particularly in industries that involve combustion of organic compounds. Firefighters, in particular, are exposed to extremely high levels during the extinguishment and overhaul phases of their work. Water may contain significant levels of the herbicide. It has been found in paper mill and municipal effluents at 20-200 micrograms/L, and at 30 micrograms/L as far as 64 km downstream from the point of application. The USEPA-recommended water quality criteria for freshwater are only 1.2 micrograms/L (24-hr avg) and 2.7 micrograms/L (maximum ceiling). Acrolein is highly reactive, and intercompartmental transport is limited. However, it is eliminated from aqueous environments by volatilization and hydration to beta-hydroxypropanal, after which biotransformation occurs, with a half-life of 7-10 d. The Koc for acrolein is 24, and it is not likely to be retained in soil; activated carbon adsorbs only 30% from solution. Thus, the aldehyde is either leached extensively in moist soil or volatilizes quickly from dry soil. It is eliminated from air by reaction with .OH (half-life, 0.5-1.2 d), NOx (half-life, 16 d), and O3 (half-life, 59 d), as well as by photolysis and wet deposition. As expected from its high water solubility, bioaccumulation is low. Acrolein is highly toxic by all routes of exposure. The respiratory system is the most common target: exposure causes localized irritation, respiratory distress, pulmonary edema, cellular necrosis, and increased susceptibility to microbial diseases. Additionally, acute inhalation studies verify that it is a severe respiratory irritant that affects respiratory rates. Respiratory rate depression may have a protective effect by minimizing vapor inhalation, thereby explaining the subadditive effect of acrolein when combined with the other toxic combustion by-products CO and HCHO. Liquid contact with the skin and eyes causes severe irritation, opaque or cloudy corneas, and localized epidermal necrosis, but no allergic contact dermatitis. The cardiovascular system is affected, resulting in increased blood pressure, platelet aggregation, and quick cessation of beating in perfused rat hearts. It may also inhibit mitochondrial oxidative phosphorylation in the myocardium. Acute LD50s and LC50s are low. Levels are 7-46 mg/kg and 18-750 mg/m3, respectively, in rats; aquatic organisms are affected above 11.4 micrograms/L.(ABSTRACT TRUNCATED)

摘要

丙烯醛是一种剧毒、具有反应性且有刺激性的醛类物质,它作为有机热解产物、多种化合物的代谢产物以及用于控制水生生物时水中的残留物而存在。它是丙烯酸、DL-蛋氨酸及许多其他制剂生产过程中的中间体。其主要直接用途是作为控制水生动植物的杀生剂。它通过多种来源进入环境,包括汽车尾气、香烟烟雾等有机燃烧,以及制造和烹饪排放物,还有直接的杀生剂应用。固定源和移动源的有机燃烧是大气中丙烯醛的重要来源;它占车辆和住宅壁炉产生的醛类总量的8%,占大气醛类总量的13%。这种具有反应性的醛类物质在生物体内还作为烯丙醇、烯丙胺、精胺、亚精胺及抗癌药物环磷酰胺的代谢产物存在,也是皮肤脂质三油酸甘油酯经紫外线辐射后的产物。此外,在食物中也能发现少量丙烯醛;不过,当动植物油脂过热时,会产生大量丙烯醛。大多数人类接触发生在接触香烟、汽车、工业过程以及建筑物和植被火灾产生的烟雾期间。除香烟烟雾外,职业接触是人类接触的常见方式,尤其是在涉及有机化合物燃烧的行业。特别是消防员,在工作的灭火和检修阶段会接触到极高浓度的丙烯醛。水中可能含有大量这种除草剂。在造纸厂和城市污水中已检测到其含量为20 - 200微克/升,在施药点下游64公里处的水中含量为30微克/升。美国环境保护局推荐的淡水水质标准仅为1.2微克/升(24小时平均值)和2.7微克/升(最高上限)。丙烯醛反应性很强,跨介质传输有限。然而,它可通过挥发和水合作用转化为β-羟基丙醛从而从水环境中消除,之后发生生物转化作用,半衰期为7 - 10天。丙烯醛的有机碳吸附系数(Koc)为24,不太可能保留在土壤中;活性炭仅能从溶液中吸附30%。因此,这种醛类物质要么在潮湿土壤中大量淋溶,要么从干燥土壤中迅速挥发。它通过与·OH(半衰期0.5 - 1.2天)、氮氧化物(半衰期16天)和臭氧(半衰期59天)反应,以及光解和湿沉降作用从空气中消除。正如因其高水溶性所预期的那样,生物累积性较低。丙烯醛通过所有接触途径都具有高毒性。呼吸系统是最常见的靶器官:接触会导致局部刺激、呼吸窘迫、肺水肿、细胞坏死以及对微生物疾病易感性增加。此外,急性吸入研究证实它是一种严重的呼吸道刺激物,会影响呼吸频率。呼吸频率降低可能通过减少蒸汽吸入起到保护作用,从而解释了丙烯醛与其他有毒燃烧副产物一氧化碳和甲醛联合时的亚相加效应。液体接触皮肤和眼睛会导致严重刺激、角膜混浊或不透明以及局部表皮坏死,但不会引起过敏性接触性皮炎。心血管系统也会受到影响,导致血压升高、血小板聚集以及灌注大鼠心脏跳动迅速停止。它还可能抑制心肌中的线粒体氧化磷酸化。大鼠的急性半数致死剂量(LD50)和半数致死浓度(LC50)较低。大鼠的LD50为7 - 46毫克/千克,LC50为18 - 750毫克/立方米;水生生物在浓度高于(11.4)微克/升时会受到影响。(摘要截断)

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