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石墨电极生产厂中多环芳烃的职业暴露:1-羟基芘和菲单羟基代谢物的生物监测

Occupational exposure to polycyclic aromatic hydrocarbons in a graphite-electrode producing plant: biological monitoring of 1-hydroxypyrene and monohydroxylated metabolites of phenanthrene.

作者信息

Angerer J, Mannschreck C, Gündel J

机构信息

Institute and Clinic of Occupational, Social and Environmental Medicine, University of Erlangen Nürnberg, Germany.

出版信息

Int Arch Occup Environ Health. 1997;69(5):323-31. doi: 10.1007/s004200050155.

Abstract

OBJECTIVE

The objective of this study was to assess external and internal exposure to polycyclic aromatic hydrocarbons (PAHs) of workers who are employed in a graphite-electrode producing plant. Additionally we wanted to contribute to the question of biological limit values in order to reduce exposure to tolerable levels.

METHODS

At five different working places 12 stationary and 16 personal air measurements were carried out to determine the concentrations of phenanthrene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[a]pyrene and dibenz[a, h]anthracene in air. In addition, we investigated the excretion of 1-, 2 + 9-, 3- and 4-hydroxyphenanthrene and of 1-hydroxypyrene in the urine of 67 workers by a very sensitive and practical high-performance liquid chromatographic (HPLC) method with fluorescence detection; 2- and 9-hydroxyphenanthrene could not be separated with our analytical method.

RESULTS

During the production of graphite electrodes significantly higher PAH exposures were found in the baking and impregnation area than in the crushing, graphitisation and conditioning area. The results of personal air measurements (mean values of the sum of eight PAHs) are: 29.3 (baking), 23.4 (impregnation), 5.2 (crushing), 1.3 (graphitisation) and 0.4 microgram/m3 (conditioning). Stationary air measurements yielded similar concentrations. Workers employed in the baking and impregnation areas excreted the highest amount of PAH metabolites in urine. The 1-hydroxypyrene concentrations (median) were: 23.4 (baking), 22.0 (impregnation), 9.6 (crushing), 1.8 (graphitisation) and 2.3 micrograms/g creatinine (conditioning). The corresponding concentrations of the sum of monohydroxylated phenanthrene metabolites (median) were: 23.1, 36.0, 10.4, 4.6 and 7.6 micrograms/g creatinine. Within the monohydroxylated phenanthrene metabolites 3-hydroxyphenanthrene predominates with a percentage of 43%. Our results showed that a benzo[a]pyrene concentration in air of 2 micrograms/m3 would lead to 1-hydroxypyrene concentrations in urine of 20-74 micrograms/g creatinine. That means that corresponding values in the literature which lie between 4.4 and 6.2 micrograms/g creatinine are due to other conditions of exposure and cannot be applied to graphite-electrode producing plants.

CONCLUSIONS

Although to date there are no obligatory biological exposure limits for metabolites of PAHs in urine, it must be concluded that the internal PAH exposure is too high at some work places in this plant, as is generally the case in graphite-electrode producing plants. This is probably caused by skin absorption of PAHs. So for the prevention of health hazards by PAH, internal exposure must be measured using biological monitoring. Although it has not been possible to establish biological exposure limits for PAHs until now, we suggest a reduction in skin contact with these substances and thereafter use of the 90th percentile of the results of biological monitoring as "action levels" for corrective measures.

摘要

目的

本研究的目的是评估石墨电极生产厂工人多环芳烃(PAHs)的内、外暴露情况。此外,我们希望为生物限值问题提供参考,以便将暴露降低到可耐受水平。

方法

在五个不同工作地点进行了12次定点和16次个人空气测量,以测定空气中菲、荧蒽、芘、苯并[a]蒽、 Chrysene、苯并[b]荧蒽、苯并[a]芘和二苯并[a,h]蒽的浓度。此外,我们采用一种非常灵敏且实用的带荧光检测的高效液相色谱(HPLC)方法,对67名工人尿液中1-、2 + 9-、3-和4-羟基菲以及1-羟基芘的排泄情况进行了调查;我们的分析方法无法分离2-和9-羟基菲。

结果

在石墨电极生产过程中,发现焙烧和浸渍区域的PAH暴露明显高于破碎、石墨化和调湿区域。个人空气测量结果(8种PAHs总和的平均值)为:29.3(焙烧)、23.4(浸渍)、5.2(破碎)、1.3(石墨化)和0.4微克/立方米(调湿)。定点空气测量得到了类似的浓度。在焙烧和浸渍区域工作的工人尿液中PAH代谢物排泄量最高。1-羟基芘浓度(中位数)为:23.4(焙烧)、22.0(浸渍)、9.6(破碎)、1.8(石墨化)和2.3微克/克肌酐(调湿)。单羟基菲代谢物总和的相应浓度(中位数)为:23.1、36.0、10.4、4.6和7.6微克/克肌酐。在单羟基菲代谢物中,3-羟基菲占主导,比例为43%。我们的结果表明,空气中苯并[a]芘浓度为2微克/立方米时,尿液中1-羟基芘浓度将达到20-74微克/克肌酐。这意味着文献中4.4至6.2微克/克肌酐之间的相应值是由于其他暴露条件导致的,不适用于石墨电极生产厂。

结论

尽管目前尿液中PAH代谢物尚无强制性生物暴露限值,但必须得出结论,该工厂某些工作地点的PAH内暴露过高,石墨电极生产厂通常都是如此。这可能是由于PAHs经皮肤吸收所致。因此,为预防PAH对健康的危害,必须采用生物监测来测量内暴露。尽管目前尚未确定PAHs的生物暴露限值,但我们建议减少皮肤与这些物质的接触,然后将生物监测结果的第90百分位数用作采取纠正措施的“行动水平 ”。

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