ABSTRACT
The paper describes a novel SPME-based approach for sampling and analysis of transformation products of highly reactive and toxic unsymmetrical dimethylhydrazine (UDMH) which is used as a fuel in many Russian, European, Indian, and Chinese heavy cargo carrier rockets. The effects of several parameters were studied to optimize analyte recovery. It was found that the 85 microm Carboxen/polydimethylsiloxane fiber coating provides the highest selectivity for selected UDMH transformation products. Optimal sampling/sample preparation parameters were determined to be 1-h soil headspace sampling time at 40 degrees C. The GC inlet temperature was optimized to 170 degrees C held for 0.1 min, then 1 degrees C s(-1) ramp to 250 degrees C where it was held for 40 min. Temperature programming resulted in a fast desorption along with minimal chemical transformation in the GC inlet. SPME was very effective extracting UDMH transformation products from soil samples contaminated with rocket fuel. The use of SPME resulted in high sensitivity, speed, small labor consumption due to an automation and simplicity of use. It was shown that water addition to soil leads to a significant decrease of recovery of almost all target transformation products of UDMH. The use of SPME for sampling and sample preparation resulted in detection of the total of 21 new compounds that are relevant to the UDMH transformation in soils. In addition, the number of confirmed transformation products of UDMH increased from 15 to 27. This sampling/sample preparation approach can be recommended for environmental assessment of soil samples from areas affected by space rocket activity.
Subject(s)
Dimethylhydrazines/analysis , Soil Pollutants/analysis , Solid Phase Microextraction/methods , Gas Chromatography-Mass Spectrometry , TemperatureABSTRACT
The possible impact of the rocket fuel 1,1-dimethyl hydrazine (heptyl) (1) and its transformation products on human health has been studied using (Quantitative) Structure Activity/Toxicity ((Q)SAR/(Q)STR) modelling, including both ADME models and models for acute toxicity, organ specific adverse haematological effects, the cardiovascular and gastrointestinal systems, the kidneys, the liver and the lungs, as well as a model predicting the biological activity of the compounds. It was predicted that all compounds studied are readily bioavailable through oral intake and that significant amounts of the compounds will be freely available in the systemic circulation. In general, the compounds are not predicted to be acutely toxic apart from hydrogen cyanide, whereas several compounds are predicted to cause adverse organ specific human health effects. Further, several compounds are predicted to exhibit high probabilities for potential carcinogenicity, mutagenicity, teratogenicity and/or embryotoxicity. The compounds were ranked based on their predicted human health impact using partial order ranking methodologies that highlight which compounds on a cumulative basis should receive the major attention, i.e., N-nitroso dimethyl amine, 1,1,4,4-tetramethyl tetrazene, trimethyl, trimethyl hydrazine, acetaldehyde dimethyl hydrazone, 1, 1-formyl 2,2-dimethyl hydrazine and formaldehyde dimethyl hydrazone, respectively.
ABSTRACT
The mutagenic effect of the rocket fuel 1,1-dimethyl hydrazine has been studied experimentally and compared to the well-recognized mutagene N-nitroso dimethylamine. The manifestation of the effect for both compounds was disclosed through a significant increase in the chromosome aberration frequency in the bone marrow cells of intoxicated rats. The levels of chromosome aberrations induced by 1,1-dimetyl hydrazine were studied following both single (1h) and repeated doses (daily for 10 consecutive days) by inhalation (205-1028mg/m(3)) and gavage (5.4-26.8mg/kg) administration, respectively. For comparison N-nitroso dimethylamine were administered by inhalation (2h/daily for 10 consecutive days) and by gavage in concentrations of 2.4-48mg/m(3) and 1-30mg/kg, respectively. A clear dependence of concentration as well of time was disclosed. The BenchMark Dose approach was employed to derive guideline doses for the two compounds, the implications towards human health being discussed.
ABSTRACT
QSAR/QSTR modelling constitutes an attractive approach to preliminary assessment of the impact on environmental health by a primary pollutant and the suite of transformation products that may be persistent in and toxic to the environment. The present paper studies the impact on environmental health by residuals of the rocket fuel 1,1-dimethyl hydrazine (heptyl) and its transformation products. The transformation products, comprising a variety of nitrogen containing compounds are suggested all to possess a significant migration potential. In all cases the compounds were found being rapidly biodegradable. However, unexpected low microbial activity may cause significant changes. None of the studied compounds appear to be bioaccumulating.Apart from substances with an intact hydrazine structure or hydrazone structure the transformation products in general display rather low environmental toxicities. Thus, it is concluded that apparently further attention should be given to tri- and tetramethyl hydrazine and 1-formyl 2,2-dimethyl hydrazine as well as to the hydrazones of formaldehyde and acetaldehyde as these five compounds may contribute to the overall environmental toxicity of residual rocket fuel and its transformation products.
