Loeppky R N, Hansen T J, Keefer L K
Food Chem Toxicol. 1983 Oct;21(5):607-13. doi: 10.1016/0278-6915(83)90148-5.
In simulated metalworking coolants that contained both nitrite and di- or triethanolamine at pH 9, N-nitrosodiethanolamine formed at an initial rate of 11 or 6 ppm/wk, respectively. This rate was increased on heating the fluids, on acidification or by the addition of paraformaldehyde, 1,3,5-trimethylhexahydro-s-triazine, ferricyanide or ferric ethylenediaminetetraacetate. N-Nitrosodiethanolamine also formed when nitrite-free coolants containing either of the two amines above were exposed to nitric oxide in air. No nitrosamines were detected in fluids containing primary amines in place of the secondary and tertiary amines, except that N-nitrosooxazolidine was formed in the fluid containing monoethanolamine after addition of formaldehyde-releasing agents, and N-nitrosodiethanolamine and N-nitrosomorpholine were found in fluid containing diglycolamine (HOCH2CH2OCH2CH2NH2) after the fluid was heated at 100 degrees C for 48 hr. These data suggest several steps by which nitrosamine formation in commercial cutting fluids might be substantially reduced: avoiding acid-splitting as a disposal procedure; removing nitrite from the fluid and/or scavenging adventitious nitrosating agents; avoiding unnecessary heating; adding preservatives to the diluted fluid rather than to the commercial concentrate; replacing inherently nitrosatable amine additives by substitutes which are resistant to nitrosamine formation; minimizing concentrations of catalytically active metal complexes.
在pH值为9且同时含有亚硝酸盐和二乙醇胺或三乙醇胺的模拟金属加工冷却液中,N-亚硝基二乙醇胺的初始生成速率分别为11 ppm/周或6 ppm/周。加热这些流体、酸化或添加多聚甲醛、1,3,5-三甲基六氢-s-三嗪、铁氰化物或乙二胺四乙酸铁会加快生成速率。当含有上述两种胺中任何一种的无亚硝酸盐冷却液暴露于空气中的一氧化氮时,也会生成N-亚硝基二乙醇胺。在含有伯胺而非仲胺和叔胺的流体中未检测到亚硝胺,但在添加甲醛释放剂后,含有单乙醇胺的流体中生成了N-亚硝基恶唑烷,并且在将含有二甘醇胺(HOCH2CH2OCH2CH2NH2)的流体在100℃加热48小时后,发现其中含有N-亚硝基二乙醇胺和N-亚硝基吗啉。这些数据表明了几个可以大幅减少商业切削液中亚硝胺形成的步骤:避免将酸分解作为处置程序;从流体中去除亚硝酸盐和/或清除偶然的亚硝化剂;避免不必要的加热;在稀释后的流体中添加防腐剂而非在商业浓缩液中添加;用抗亚硝胺形成的替代品替代固有可亚硝化的胺添加剂;尽量减少催化活性金属络合物的浓度。