Nitrosamine gases

Other rubber accelerators can be used in place of MBT however, a different cure profile may result with different cured physical properties. These substitutions could also generate higher levels of nitrosamine gases, which could pose a health risk to factory workers. 

TMTM and TMTD are both classified as thiuram rubber accelerators that are very fast curing. Unfortunately, they both generate nitrosamine gases during the curing process, which can pose a health risk to workers. Therefore, thiuram accelerators have decreased in use because of the nitrosamine issue. 

Confirmation of the identities of nitrosamines generally is accompHshed by gas chromatography—mass spectrometry (gc/ms) (46,87). High resolution gc/ms, as well as gc/ms in various single-ion modes, can be used as specific detectors, especially when screening for particular nitrosamines (87) (see Analytical LffiTHODS Trace and residue analysis). 

NGc, Nitrosamines, Nitramines, etc. In this technique, microgram quantities of a sample are added to a column packed with an absorbing medium or phase. Over this is maintained a flow of mobile phase (gas or liq). The sample components separate because of their relative mobility in the absorbing phase, and thus leave the column at different times (See Vol 1,... 

The symposium upon which this volume is based was organized at a turning point in nitrosamine research. Almost all types of commercial products have been tested for volatile nitrosamines, and there have been a number of outstanding accomplishments of combined university-gov-emment-private industry actions to lower or eliminate volatile nitrosamines in those products found to be contaminated. However, there is still a major gap of knowledge with regard to compounds that are not amenable to analysis by gas chromatography, and this is clearly a frontier of current research. There are also many important questions regarding chemistry, mechanism of action, and relation to human disease whose answers lie in the future of research in this field. 

The data in Table I are also significant in terms of the type of analysis to determine the presence of NDMA. In all cases analysis was done using gas chromatography coupled with a Thermal Energy Analyzer, a sensitive, relatively specific nitrosamine detector (12). Further, in six of the studies, the presence of NDMA in several samples was confirmed by gas chromatography-mass spectrometry (GC-MS). The mass spectral data firmly established the presence of NDMA in the beer samples. 

In Smoke. We compared the gas chromatograms of nitrosamines in matching aliquots of mainstream smoke derived from Burley type cigarettes that were identical except for the degree of nitrate fertilization during cultivation (Figure 2). This comparison supports the concept that the nitrate concentration in tobacco is a determining factor for the nitrosamine yields in the smoke. The data in Table II confirm this concept. These studies have... 

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. 

For the AOAC beer samples, a 2 m x 2 mm glass column packed with 8.57o Carbowax 20 M + 0.857, NaOH on 100/120 mesh Chromosorb G was used at 130 C and a helium flow rate of 20 cc/min. Retention times of NDMA and NDPA were 4.5 and 12.2 min, respectively. For the ASBC collaborative study, a 1 m x 2 mm glass column containing 67, Carbowax 20 M-TPA on 100/120 mesh Chromosorb G was operated at 90 C with 20 cc/min helium flow rate. Retention times were 3.6 and 11.3 min for NDMA and NDPA, respectively. For determination of nitrosamines in amines, a 2 m X 2 mm, 107, Carbowax 20 M-TPA on 100/120 mesh Chromosorb G column was operated at 190 C with a carrier gas flow rate of 20 cc/min. Retention times were NPYR, 6.6 min NMOR, 7.4 min. 

Morristown, NJ) for the ion source. No carrier gas separator was used. For determination of nitrosamines and TBDMS derivatives of hydroxy-nitrosamines, columns and operating conditions were identical to those for GC-TEA analyses For most work, the He flow rate was 15 cc/min and the column effluent was split 1 1 between a flame ionization detector and the mass spectrometer. The stainless steel splitter, solvent vent valve (Carle Instruments, Fullerton, CA), and associated plumbing were... 

The acidic reagents vary widely In their ability to lower NDPA levels In trifluralin The concentration of the acid Is critical to produce the desired effect In some Instances, the acid promoted additional nitrosamine formation, e g 10% hydrochloric acid, 40% phosphoric acid, ascorbic acid, etc Hydrochloric acid and hydrogen chloride gas were the most efficient at destroying NDPA Impurity ... 

In solution photochemistry in the presence of acids, the primary process is also the same except that both NND and the aminyl radical are protonated the recombination of the aminium radical and NO to give 295A is too slow to compete with bond scissions174 (Scheme 11). The failure of oxygen to quench nitrosamine photoreactions in either solution (see below) or gas phases under various conditions must also mean a very short lifetime of singlet excited nitrosamines, in agreement with the fast dissociation159,160. 

Various gas chromatographic techniques combined with plentiful detection methods were used to separate and quantify volatile V-nitrosamines. Preconcentration methods were usually applied for separating these compounds. Thus, a method was developed for determination of V-nitrosodimethylamine (278a) in minced fish or frankfurters, based on SPE followed by GC-CLD-TEA RSD was 0.56 to 2.25%569. This method has been adopted by AOAC. A similar GC method using NPD was described for the determination of 278a in fish products570. Steam distillation can also be used to isolate volatile... 

Munch JW, Bassett MV (2004) EPA Method 521. Determination of nitrosamines in drinking water by sohd-phase extraction and capillary column gas chromatography with large volume injection and chemical ionization tandem mass spectrometry (MS/MS), U.S. EPA, Cincinnati, OH. Available at www.epa.gov/nerlcwww/m 521.pdf... 

Because N-nitroso compounds can have such a wide variety of physical and chemical properties, and because they can be formed from a wide variety of precursors. analysis at the trace level is difficult. The most widely used technique is the use of a nitrosamine specific detector, called a TEA, which can be interfaced to either a gas chromatograph (GC) or a high pressure liquid chromatograph (HPLC) (31,32). General screening procedures which have been designed to detect all N-nitroso compounds have been developed (33,34). Structural confirmation of N-nitroso compounds is gen-... 

The prototype of the tobacco specific nitrosamines, NNN, has been detected in both tobacco smoke and unburned tobacco. Various analytical methods have been used including gas chromatography (GLC) (13,14,15,16) combined GLC-mass spectrometry (17), thin layer chromatography (18) high pressure liquid chromatography (HPLC) (19,20), and combined HPLC-thermal energy analysis (21). 

V-Nitrosodiethanolamine has been found in many complex matrices such as cutting and grinding fluids and cosmetics. Analysis for V-nitrosodiethanolamine is complicated by the matrix and a clean-up technique with derivatization is typically required before quantitation of the analyte to achieve adequate sensitivity and selectivity. Ammonium sulfamate may be added to the sample to prevent the artifactual formation ofV-nitrosamines. Derivatives of V-nitrosodiethanolamine have been prepared by acylation, trifluoroacylation, trimethylsilylation and methylation. The derivatives have been analysed by gas chromatography using flame ionization and mass spectro-metric detectors (Occupational Safety and Health Administration, 1990). 

The GC-TEA conditions used for the detection of volatile nitrosamines have been described by Fine and Rounbehler (8). A 14 x 1/8" stainless steel column packed with 5% Carbowax 20M containing 2% NaOH on Chromosorb W HP (80-100 mesh) was operated at 175°C with argon gas as the carrier at a flow rate of 15 mL/min. A TEA was used as the detector with dry ice/ethanol as the cold trap. The HPLC-TEA was constructed by sequentially connecting a high pressure pump (Altex, model 110), an injector (Waters, model U6K), a yPorasil column (Waters), and a TEA. The operation of HPLC-TEA has been described by Fine, et al.( ). 

Methyl-phenyl nitrosamine separates as a yellow oil, which solidifies on cooling (M.P. 12°—15°). 2 gms. methyl-phenyl nitrosamine are dissolved in 4 gms. ether and 8 gms. absolute alcohol which have been saturated with hydrochloric acid gas then added. After a time needles separate out which are filtered and washed with a mixture of alcohol and ether. 

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