Nitrosamine environmental

The most important sources of preformed environmental nitrosamines according to present knowledge, are given in Table I. 

Possible exposure to pesticide-derived N,-nitroso compounds depends on environmental processes that influence formation, movement, and degradation of the compounds. Although laboratory studies have shown the feasibility of environmental nitrosamine formation, there has been little evidence that it is an important process. Nitrosamines vary greatly in their environmental stabilities, but all seem to be susceptible to one or more modes of decomposition including photolysis, microbiological degradation, and plant metabolism. 

Relative Risks of Nitrosamines. The mere existence of reproducible variations in carcinogenicity from one nitrosamine to another is directly relevant to the question of potential human health hazards from environmental nitrosamines. The problem of nitrosamines in cooked bacon is a simple and straightforward example. 

In summary, it appears that the differences in carcinogenic potency for both cyclic and acyclic N-nitrosodialkylamines are real and systematic, and that the potencies of environmental nitrosamines should be considered in assessing the relative hazards associated with these compounds. In addition, it can be shown that the carcinogenicity of nitrosamines can be associated... 

Cohen JB, Bachman JD. 1978. Measurement of environmental nitrosamines. lARC Sci Publ 19 357-372. 

Reactions. The chemistry of the /V-nitrosamines is extensive and will be only summarized here (8,35,42). Most of the reactions of the nitrosamines, with respect to thek biological or environmental behavior, involve one of two main reactive centers, either the nitroso group itself or the C—H bonds adjacent (a) to the amine nitrogen. The nitroso group can be removed readily by a reaction which is essentially the reverse of the nitrosation reaction, or by oxidation or reduction (68,69). 

Cyclic nitrosamines are among the most potent and environmentally significant nitrosamine carcinogens. Like the acyclic nitrosamines, metabolism is necessary for their carcinogenicity. Elucidation of the specific metabolic pathways of cyclic nitrosamine activation and detoxification is a challenging problem, and considerable progress has been achieved in recent years. In this chapter, we will review metabolic studies on N-nitrosopyrrolidine (NPYR), N -nitrosonornicotine (NNN), N-nitrosopiperidine (NPIP), N-nitrosohexamethyleneimine (NHEX), N-nitrosomorpholine (NMOR),... 

The complex pattern of human exposure to environmental N-nitroso compounds is summarized. Recent results are given in three areas, where a significant reduction of human exposure has been achieved after elucidation of its causes 1, N-Nitrosodimethylamine in beer. 2, Volatile N-nitrosamines in baby nipples and pacifiers and 3. occupational exposure in the rubber industry. 

Carcinogenicity of NDELA. Our special interest in NDELA as a constituent of tobacco products and as an environmental agent relates to the observation that this nitrosamine induces carcinoma of the liver as well as of the kidney in rats (21,22) and carcinoma of the nasal cavity and papillomas of the trachea in hamsters (23). Recently, Lijinsky reported that NDELA admini-... 

Reliable analytical methods are available for determination of many volatile nitrosamines at concentrations of 0.1 to 10 ppb in a variety of environmental and biological samples. Most methods employ distillation, extraction, an optional cleanup step, concentration, and final separation by gas chromatography (GC). Use of the highly specific Thermal Energy Analyzer (TEA) as a GC detector affords simplification of sample handling and cleanup without sacrifice of selectivity or sensitivity. Mass spectrometry (MS) is usually employed to confirm the identity of nitrosamines. Utilization of the mass spectrometer s capability to provide quantitative data affords additional confirmatory evidence and quantitative confirmation should be a required criterion of environmental sample analysis. Artifactual formation of nitrosamines continues to be a problem, especially at low levels (0.1 to 1 ppb), and precautions must be taken, such as addition of sulfamic acid or other nitrosation inhibitors. The efficacy of measures for prevention of artifactual nitrosamine formation should be evaluated in each type of sample examined. 

Reliable methods are available for determination of nitrosamines, especially volatile nitrosamines, in a variety of foods, environmental samples, commercial products, blood and animal tissues. Reviews of these methods are available (1, 2) and descriptions of some state-of-the-art procedures are included in papers on nitrosamine occurrence in this volume. This paper is not intended to be a comprehensive review of historical developments or of the many variations of procedures... 

An internal standard is desirable in any quantitative trace environmental analysis. The ideal internal standard should behave in a manner identical to that of the analyte in all the procedures followed for isolation, purification, and determination without producing interference. This is a difficult requirement to meet for nitrosamines, especially for NDMA. 

The effort required to establish identity of a nitrosamine in an environmental sample depends on the nature of the problem and the specificity of the primary detection system. TEA response is much stronger evidence of identity than response from a flame ionization or nitrogen-specific detector. If TEA response is supported by chemical (9) or ultraviolet photolysis (8) supporting data, identification is adequate for many... 

Available detection and confirmation methods are adequate for establishing identity and amounts of nitrosamines in most environmental and biological samples. The validity of analytical results, especially at levels in the part-per-billion and lower range, depends upon the experience and skill of the analyst in preventing or detecting contamination or artifactual formation of nitrosamines. 

Egan, H. Preussmann, R. Walker, E.A. Castegnaro, M. Wasserman, A.E. Eds. "Environmental Carcinogens Selected Methods of Analysis Vol. 1 - Analysis of Volatile Nitrosamines in Food." lARC Scientific Publications No. 18. International Agency for Research on Cancer Lyon, 1978. Walker, E.A. Griciute, L. Castegnaro, M. Borzsonyi, M., Eds. "N-Nitroso Compounds Analysis Formation and Occurrence" lARC Scientific Publications No. 31. International Agency for Research on Cancer Lyon, 1980. Hedler, L. Schurr, C. Marquadt, P. J. Am. Oil Chem. Soc. 1979, 681-684. 

Although the word nitrosamine may at times be used loosely to include other classes of ji-nitroso compounds, most of the nitroso compounds, with the exception of occasional reference to nitrosocarbamates, discussed in this paper are in fact nitrosamines. Beyond that they are structurally quite variable, and their environmental behaviors can be as variable as their structures. 

Several aspects of the problem of herbicides being contaminated with nitrosamines, and the resulting inadvertent introduction of nitrosamines into the environment, will be discussed in other papers in this symposium. Unrecognized until less than five years ago, the situation has inspired intense debate and prompted several of the environmental chemistry studies mentioned in this paper. Like the presumed threat from the in vivo nitros-ation of pesticide residues, discussions sometimes lack the type of anticipated dose and effect calculations just mentioned. Unlike the active ingredients, whose benefits can justify residue tolerances and acceptable daily intakes, nitrosamine contaminents afford no known benefits, and the desirability of minimizing their levels is undisputed. 

Other environmental properties of interest are those that govern movement of chemicals, for these properties can influence not only the possibility of human exposure but also the lifetime and fate of the chemical. Clearly, if a nitrosamine is formed in, or introduced into, the soil and stays there, it presents little threat to man, and its lifetime will depend on the chemical or microbiological properties of the soil. If it should move to the surface and volatilize into the atmosphere, on the other hand, there will exist the possibility of human exposure via inhalation and also the possibility of vapor-phase photodecomposition. If a nitrosamine were to leach from soil into water, it could perhaps be consumed in drinking water alternatively, exposure of the aqueous solution to sunlight could provide another opportunity for photodecomposition. 

The NO + 03 chemiluminescent reaction [Reactions (1-3)] is utilized in two commercially available GC detectors, the TEA detector, manufactured by Thermal Electric Corporation (Saddle Brook, NJ), and two nitrogen-selective detectors, manufactured by Thermal Electric Corporation and Antek Instruments, respectively. The TEA detector provides a highly sensitive and selective means of analyzing samples for A-nitrosamines, many of which are known carcinogens. These compounds can be found in such diverse matrices as foods, cosmetics, tobacco products, and environmental samples of soil and water. The TEA detector can also be used to quantify nitroaromatics. This class of compounds includes many explosives and various reactive intermediates used in the chemical industry [121]. Several nitroaromatics are known carcinogens, and are found as environmental contaminants. They have been repeatedly identified in organic aerosol particles, formed from the reaction of polycyclic aromatic hydrocarbons with atmospheric nitric acid at the particle surface [122-124], The TEA detector is extremely selective, which aids analyses in complex matrices, but also severely limits the number of potential applications for the detector [125-127],... 

In the area of environmental protection the Japanese tyre firm Toyo is doing more as a tyre producer than the law demands. In this article Wilhelm Hoeppner, responsible for publicity at Toyo Reifen GmbH, explains in an interview how Toyo is involved. It looks at rubber mixtures, the problem of nitrosamines, legal environmental stipulations, economic impact and the future efforts by Toyo. 

There are several routes for nitrosamine contamination in pesticides use of contaminated chemicals during synthesis, side reactions, use of nitrite as a preservative and corrosion inhibitor of metal containers and by reactions with environmental nitrosating agents. Over 300 formulations were shown to be contaminated with nitrosamines however, the main contamination was confined to 2,6-dinitroaniline herbicides, dimethylamino salts of phenoxyalkanoic acid herbicide, diethanolamine and triethanolamine salts of acid... 

Hildrum, K., Scanlan, R.A. and Libbey, L.M. (1976). Nitrosamines from the nitrosation of spermidine and spermine, in Walker, E., Bogovski, P. and Griciute. L., Eds., Environmental N-Nitroso Compounds Analysis and Formation, Polytechnical Institute Tallinn, Estonia. 

Letterman RD (ed) (1999) Water quality and treatment A handbook of community water supplies, 5th ed., Amer. Water Works Assoc., McGraw-Hill, New York Lijinsky W, Epstein SS (1970) Nitrosamines as environmental carcinogens. Nature 225 21-23 Lin S, Marshall EG, Davidson GK (1994) Potential parental exposure to pesticides and hmb reduction defects. Scand J Work Environ Health 20 166-179 Linak, E, Lutz, HJ, Nakamura E (1990) Chlorinated Solvents. In Linak E, Lutz HJ, Nakamura E, C2 chlorinated solvents, chemical economics handbook, Stanford Research Institute, Menlo Park, CA, pp. 632.30000a-632.3001z Lindsay WL (1979) Chemical equilibria in soils. John Wiley, New York... 

H. M. Lyle, G. G. Saavedra, J.E. "Electronic Properties of the Nitrosamine Function in Environmental Aspects of N-Nitroso Compounds, Walker, E. A. Castegnaro, M. ... 

Michejda, C. J. Tipton, T. J. Campbell, D. H. Nitrosative dealkylation under oxidative conditions as a possible source of nitrosamines. In Walker, E. A. Bogovski, P. Griciute, L., Eds. "Environmental N-Nitroso Compounds. Analysis and Formation" lARC Scientific Publication No. 

---