nitrogen-dioxide and morpholine

Amine-based technologies are emerging as the prime contender for postcombustion CO2 capture. However, concerns have arisen over the health impacts of amine-based CO2 capture associated with the release of nitrosamines and nitramines, which are byproducts from the reactions between flue gas NOx and solvent amines. In this study, flue gas compositions were systematically varied to evaluate their effects on the formation of nitrosamines and nitramines in a lab-scale CO2 capture reactor with morpholine as a model solvent amine. The accumulation of N-nitrosomorpholine in both the absorber and washwater increased linearly with both NO and NO2 for concentrations up to ∼20 ppmv. These correlations could be extrapolated to estimate N-nitrosomorpholine accumulation at extremely low NOx levels (0.3 ppmv NO2 and 1.5 ppmv NO). NO played a particularly important role in driving N-nitrosomorpholine formation in the washwater, likely following partial oxidation to NO2 by O2. The accumulation of N-nitromorpholine in both the absorber and washwater positively correlated with flue gas NO2 concentration, but not with NO concentration. Both N-nitrosomorpholine and N-nitromorpholine accumulated fastest in the absence of CO2. Flue gas humidity did not affect nitrosamine accumulation in either the absorber or the washwater unit. These results provide a basis for estimating the effects of flue gas composition on nitrosamine and nitramine accumulation in postcombustion CO2 capture systems.

Topics: Aniline Compounds; Carbon Dioxide; Gases; Morpholines; Nitric Oxide; Nitrites; Nitrobenzenes; Nitrogen Dioxide; Nitrosamines; Oxygen; Solvents; Time Factors; Water

Male CD-1 mice were exposed to an nominal concentration of 20 p.p.m. of 15N-nitrogen dioxide (15NO2) for 6 h/day for 4 days and for 2 h on the day 5, and to 1 g morpholine/kg body wt by gavage daily for five consecutive days. N-Nitrosomorpholine (NMOR) was found in whole mice, stomachs, skins with hair, and remains. The sum of individual tissue concentrations measured separately was 3421 ng/tissue, where the average skin weighed 4.3 g, the average stomach weighed 1.0 g and the average remains weighed 22.2 g. The average whole mouse weighed 27.7 g and contained a total of 3903 ng of NMOR. The concentration of NMOR was highest in the skin, next highest in the stomach, and lowest in the remains. However, the total quantity of NMOR per tissue, while highest in the skin (83%), was next highest in the remains (14.8%) and lowest in the stomach (2.2%). GC-MS analysis served to distinguish between the NMOR of 15NO2 origin and that of other origin. All of the NMOR in the whole mouse homogenates was identified as 15NMOR. In the stomach 73% was identified as 14NMOR, representing 1.6% of the total NMOR in the mouse, and 27% as 15NMOR, representing 0.6% of the total NMOR in the mouse. N-Nitrosamine formation in vivo is discussed as a possibly ongoing mammalian process.

Topics: Administration, Inhalation; Animals; Carcinogens; Gas Chromatography-Mass Spectrometry; Male; Mice; Mice, Inbred Strains; Morpholines; Nitrogen Dioxide; Nitrogen Isotopes; Nitrosamines

Skin lipids of mice exposed to NO2 contain lipid-soluble nitrosating agent(s) (NSA) that react in vitro with amines to produce nitrosamines. To test whether this reaction occurs in skin, we exposed mice to 50 ppm NO2 for 4 h and, 20 h later, applied 25 mg morpholine or N-methylaniline to the skin, which was then analyzed for the corresponding nitrosamine. When morpholine was applied, mean N-nitrosomorpholine yield was only 0.3 nmol/mouse (not significant). When N-methylaniline was applied and mice were killed after 10-40 min, N-nitroso-N-methylaniline yield in the skin was 13-21 nmol/mouse of which 87% occurred in the hair. NSA formation when mice were exposed to 6.5 ppm NO2 was only 0.15% of that for exposure to 50 ppm NO2. NSA occurred mostly in surface lipids of the skin and its in vitro reaction to give nitrosamines was not inhibited by alpha-tocopherol. When morpholine was painted and mice were then exposed to 55 ppm NO2 for 30 min, the skins contained 19 nmol N-nitrosomorpholine/mouse, attributed to a direct reaction between NO2 and the amine. We concluded that nitrosamine formation in skin by this direct reaction may be more important than the reaction of amines with NO2-derived NSA.

Topics: Aniline Compounds; Animals; Male; Mice; Morpholines; Nitrogen Dioxide; Nitrosamines; Skin

Ascorbate anion and glutathione were found to inhibit the aqueous reaction between nitrogen dioxide (NO2) and morpholine (MOR) and thereby prevented the formation of N-nitrosomorpholine (NMOR) and N-nitromorpholine (NTMOR) at both pH 7.4 and 12.5. These antioxidants are approximately 3 orders of magnitude more reactive towards NO2 than is MOR and may play an important role in the prevention of carcinogen formation in the lung due to inhaled NO2. Ammonium sulfamate was ineffective at preventing nitrosation or nitration by NO2 at either pH 7.4 or 12.5.

Topics: Ascorbic Acid; Glutathione; Hydrogen-Ion Concentration; Morpholines; Nitrogen Dioxide; Vitamin E

The possibility that alpha-tocopherol (vitamin E) inhibits the formation of nitrosomorpholine (NMOR) in vivo was investigated in mice orally pretreated with alpha-tocopherol (2.5-100 mg/kg body wt) once daily for 6 days. Twenty-four hours later, the animals were injected i.p. with 2 mg of morpholine (MOR) per animal followed by exposure to 47 p.p.m. of NO2 for 2 h. Under these conditions, low oral doses of alpha-tocopherol (2.5-5 mg/kg body wt) significantly decreased NMOR formation in vivo. As total body alpha-tocopherol levels increased, in vivo NMOR formation decreased, and a maximal 50-70% inhibition of NMOR formation occurred at alpha-tocopherol levels of 5 micrograms/g body wt. Additional results showed that NMOR was rapidly eliminated in mice, so that studies which measure the levels of NMOR found in animals treated with MOR and then exposed to NO2 may underestimate the amount of NMOR that is actually formed. Finally, oral pretreatment of up to 100 mg of alpha-tocopherol/kg body wt had no effect on NMOR elimination.

Topics: Animals; Dose-Response Relationship, Drug; Male; Mice; Morpholines; Nitrogen Dioxide; Nitrosamines; Vitamin E

The possibility of N-nitrosomorpholine formation was investigated in mice treated with morpholine and then exposed to 45 p.p.m. nitrogen dioxide in an inhalation chamber for 2 h. Following this treatment, the mice were frozen and pulverized in liquid nitrogen and concentrated extracts from the powders of these animals were analyzed for N-nitrosomorpholine using a thermal energy analyzer interfaced to a gas chromatograph. The data indicate that nitrogen dioxide exposure causes the nitrosation of morpholine in vivo. Additional data show that significant levels of artifactually formed N-nitrosomorpholine are found in control animals that are treated with morpholine after exposure to nitrogen dioxide for 2 h unless a combination of L-ascorbic acid and d,1-alpha-tocopherol are used to inhibit nitrosation during the homogenization, extraction, and analysis of the samples. The need for both a lipid phase nitrosation blocker (d,1-alpha-tocopherol) and an aqueous phase nitrosation blocker (L-ascorbic acid) indicates that the nitrosation of morpholine occurs in both a lipid and an aqueous phase in vitro and therefore may occur in both a lipid and an aqueous environment in vivo. The data from this study also demonstrate the importance of adding suitable inhibitors of nitrosation, such as L-ascorbic acid and d,1-alpha-tocopherol to the extraction solution to prevent possible artifactual formation of N-nitrosomorpholine during the extraction and analysis of the samples.

Topics: Animals; Ascorbic Acid; Carcinogens; Kinetics; Male; Mice; Morpholines; Nitrogen Dioxide; Nitrosamines; Vitamin E

We reported previously that mice exposed to atmospheric NO2 contained a nitrosating agent (NSA) that reacted with morpholine in aqueous methanol homogenates of the mice to give N-nitrosomorpholine. We have now found that N-nitrosomorpholine was also produced by reacting morpholine with ether extracts of aqueous homogenates prepared from NO2-exposed mice. After exposure to NO2 for 4 hr, mice contained NSA (5.0 nmol/g tissue, corrected to 50 ppm NO2 and assuming that 1 mol NSA yields 1 mol N-nitrosomorpholine). This is 3.6 times the concentration observed by our previous method. Some NSA (0.6 nmol/g tissue) was also detected in untreated mice. The NSA in ether extracts was nonvolatile and stable on storage at -15 degrees or for short periods in the presence of water at pH 1 to 10, but it was decomposed by a pH 1 solution of nitrite scavengers. It reacted to similar extents with three different secondary amines. Eighty-eight % of the NSA occurred in the skin, one-third of which was in the hair. The high skin concentration occurred when the bodies but not the heads of mice were exposed to NO2, indicating that the major exposure route was the skin. The NSA might consist of alpha-nitro or other activated nitrite esters derived from unsaturated lipids.

Topics: Animals; Biotransformation; Male; Methods; Mice; Morpholines; Nitrogen Dioxide; Nitroso Compounds; Pyrrolidines; Skin; Tissue Distribution