Quantification of trace transformation products of rocket fuel unsymmetrical dimethylhydrazine in sand using vacuum-assisted headspace solid-phase microextraction.

Quantification of unsymmetrical dimethylhydrazine transformation products in solid samples is an important stage in monitoring of environmental pollution caused by heavy rockets launches. The new method for simultaneous quantification of unsymmetrical dimethylhydrazine transformation products in sand samples using vacuum-assisted headspace solid-phase microextraction without addition of water followed by gas chromatography-mass spectrometry is proposed. Decreasing air evacuation time from 120 to 20 s at 23 °C resulted in increased responses of analytes by 25-46% and allowed obtaining similar responses as after evacuation at -30 °C. The best combination of responses of analytes and their relative standard deviations (RSDs) was achieved after air evacuation of a sample (m = 1.00 g) for 20 s at 23 °C, incubation for 30 min at 40 °C, and 30-min extraction at 40 °C by Carboxen/polydimethylsiloxane (Car/PDMS) fiber. The method was validated in terms of linearity (R2=0.9912-0.9938), limits of detection (0.035 to 3.6 ng g-1), limits of quantification (0.12-12 ng g-1), recovery (84-97% with RSDs 1-11%), repeatability (RSDs 3-9%), and reproducibility (RSDs 7-11%). It has a number of major advantages over existing methods based on headspace solid-phase microextraction-lower detection limits, better accuracy and precision at similar or lower cost of sample preparation. The developed method was successfully applied for studying losses of analytes from open vials with model sand spiked with unsymmetrical dimethylhydrazine transformation products. It can be recommended for analysis of trace concentrations of unsymmetrical dimethylhydrazine transformation products when studying their transformation, migration and distribution in contaminated sand.

Quantification of transformation products of rocket fuel unsymmetrical dimethylhydrazine in air using solid-phase microextraction.

Quantification of unsymmetrical dimethylhydrazine transformation products in ambient air is important for assessing the environmental impact of heavy rocket launches. There are very little data of such analyses, which is mainly caused by the low number of analytes covered by the available analytical methods and their complexity. A simple and cost-efficient method for accurate simultaneous determination of seven unsymmetrical dimethylhydrazine transformation products in air using solid-phase microextraction followed by gas chromatography-mass spectrometry was developed. The method was optimized for air sampling and solid-phase microextraction from 20-mL vials, which allows full automation of analysis. The extraction for 5 min by Carboxen/polydimethylsiloxane fiber from amber vials and desorption for 3 min provided the greatest analytes' responses, lowest relative standard deviations, linear calibration (R2 ≥ 0.99), and limits of detection from 0.12 to 0.5 µg/m3 . Samples with concentrations 500 µg/m3 can be stored at 21 ± 1°C without substantial losses (1-11%) for up to 24 h, while air samples with concentrations 10 and 50 µg/m3 stored for up to 24 h can be used for accurate quantification of only two and four out of seven analytes, respectively. The developed method was successfully tested for the analysis of air above real soil samples contaminated with unsymmetrical dimethylhydrazine rocket fuel.

Assessing air quality changes in large cities during COVID-19 lockdowns: The impacts of traffic-free urban conditions in Almaty, Kazakhstan.

Number of cities worlwide experienced air quality improvements during COVID-19 lockdowns; however, such changes may have been different in places with major contributions from nontraffic related sources. In Almaty, a city-scale quarantine came into force on March 19, 2020, which was a week after the first COVID-19 case was registered in Kazakhstan. This study aims to analyze the effect of the lockdown from March 19 to April 14, 2020 (27 days), on the concentrations of air pollutants in Almaty. Daily concentrations of PM2.5, NO2, SO2, CO, O3, and BTEX were compared between the periods before and during the lockdown. During the lockdown, the PM2.5 concentration was reduced by 21% with spatial variations of 6-34% compared to the average on the same days in 2018-2019, and still, it exceeded WHO daily limit values for 18 days. There were also substantial reductions in CO and NO2 concentrations by 49% and 35%, respectively, but an increase in O3 levels by 15% compared to the prior 17 days before the lockdown. The concentrations of benzene and toluene were 2-3 times higher than those during in the same seasons of 2015-2019. The temporal reductions may not be directly attributed to the lockdown due to favorable meteorological variations during the period, but the spatial effects of the quarantine on the pollution levels are evidenced. The results demonstrate the impact of traffic on the complex nature of air pollution in Almaty, which is substantially contributed by various nontraffic related sources, mainly coal-fired combined heat and power plants and household heating systems, as well as possible small irregular sources such as garbage burning and bathhouses.

Optimization of Time-Weighted Average Air Sampling by Solid-Phase Microextraction Fibers Using Finite Element Analysis Software.

Determination of time-weighted average (TWA) concentrations of volatile organic compounds (VOCs) in air using solid-phase microextraction (SPME) is advantageous over other sampling techniques, but is often characterized by insufficient accuracies, particularly at longer sampling times. Experimental investigation of this issue and disclosing the origin of the problem is problematic and often not practically feasible due to high uncertainties. This research is aimed at developing the model of the TWA extraction process and optimization of TWA air sampling by SPME using finite element analysis software (COMSOL Multiphysics, Burlington, MA, USA). It was established that sampling by porous SPME coatings with high affinity to analytes is affected by slow diffusion of analytes inside the coating, an increase of their concentrations in the air near the fiber tip due to equilibration, and eventual lower sampling rate. The increase of a fiber retraction depth (Z) resulted in better recoveries. Sampling of studied VOCs using 23 ga Carboxen/polydimethylsiloxane (Car/PDMS) assembly at maximum possible Z (40 mm) was proven to provide more accurate results. Alternative sampling configuration based on 78.5 × 0.75 mm internal diameter SPME liner was proven to provide similar accuracy at improved detection limits. Its modification with the decreased internal diameter from the sampling side should provide even better recoveries. The results obtained can be used to develop a more accurate analytical method for determination of TWA concentrations of VOCs in air using SPME. The developed model can be used to simulate sampling of other environments (process gases, water) by retracted SPME fibers.

Simple and accurate quantification of BTEX in ambient air by SPME and GC-MS.

Benzene, toluene, ethylbenzene and xylenes (BTEX) comprise one of the most ubiquitous and hazardous groups of ambient air pollutants of concern. Application of standard analytical methods for quantification of BTEX is limited by the complexity of sampling and sample preparation equipment, and budget requirements. Methods based on SPME represent simpler alternative, but still require complex calibration procedures. The objective of this research was to develop a simpler, low-budget, and accurate method for quantification of BTEX in ambient air based on SPME and GC-MS. Standard 20-mL headspace vials were used for field air sampling and calibration. To avoid challenges with obtaining and working with 'zero' air, slope factors of external standard calibration were determined using standard addition and inherently polluted lab air. For polydimethylsiloxane (PDMS) fiber, differences between the slope factors of calibration plots obtained using lab and outdoor air were below 14%. PDMS fiber provided higher precision during calibration while the use of Carboxen/PDMS fiber resulted in lower detection limits for benzene and toluene. To provide sufficient accuracy, the use of 20mL vials requires triplicate sampling and analysis. The method was successfully applied for analysis of 108 ambient air samples from Almaty, Kazakhstan. Average concentrations of benzene, toluene, ethylbenzene and o-xylene were 53, 57, 11 and 14µgm(-3), respectively. The developed method can be modified for further quantification of a wider range of volatile organic compounds in air. In addition, the new method is amenable to automation.

Quantification of benzene, toluene, ethylbenzene and o-xylene in internal combustion engine exhaust with time-weighted average solid phase microextraction and gas chromatography mass spectrometry.

A new and simple method for benzene, toluene, ethylbenzene and o-xylene (BTEX) quantification in vehicle exhaust was developed based on diffusion-controlled extraction onto a retracted solid-phase microextraction (SPME) fiber coating. The rationale was to develop a method based on existing and proven SPME technology that is feasible for field adaptation in developing countries. Passive sampling with SPME fiber retracted into the needle extracted nearly two orders of magnitude less mass (n) compared with exposed fiber (outside of needle) and sampling was in a time weighted-averaging (TWA) mode. Both the sampling time (t) and fiber retraction depth (Z) were adjusted to quantify a wider range of Cgas. Extraction and quantification is conducted in a non-equilibrium mode. Effects of Cgas, t, Z and T were tested. In addition, contribution of n extracted by metallic surfaces of needle assembly without SPME coating was studied. Effects of sample storage time on n loss was studied. Retracted TWA-SPME extractions followed the theoretical model. Extracted n of BTEX was proportional to Cgas, t, Dg, T and inversely proportional to Z. Method detection limits were 1.8, 2.7, 2.1 and 5.2 mg m(-3) (0.51, 0.83, 0.66 and 1.62 ppm) for BTEX, respectively. The contribution of extraction onto metallic surfaces was reproducible and influenced by Cgas and t and less so by T and by the Z. The new method was applied to measure BTEX in the exhaust gas of a Ford Crown Victoria 1995 and compared with a whole gas and direct injection method.

Transformation products of 1,1-dimethylhydrazine and their distribution in soils of fall places of rocket carriers in Central Kazakhstan.

In our research, three fall places of first stages of Proton rockets have been studied for the presence and distribution of transformation products of 1,1-dimethylhydrazine (1,1-DMH). Results of identification of transformation products of 1,1-DMH in real soil samples polluted due to rocket fuel spills allowed to detect 18 earlier unknown metabolites of 1,1-DMH being formed only under field conditions. According to the results of quantitative analyses, maximum concentrations of 1-methyl-1H-1,2,4-triazole made up 57.3, 44.9 and 13.3 mg kg(-1), of 1-ethyl-1H-1,2,4-triazole - 5.45, 3.66 and 0.66 mg kg(-1), of 1,3-dimethyl-1H-1,2,4-triazole - 24.0, 17.8 and 4.9 mg kg(-1) in fall places 1, 2 and 3, respectively. 4-Methyl-4H-1,2,4-triazole was detected only in fall places 2 and 3 where its maximum concentrations made up 4.2 and 0.66 mg kg(-1), respectively. The pollution of soils with transformation products of 1,1-DMH was only detected in epicenters of fall places having a diameter of 8 to10 m where rocket boosters landed. The results of a detailed study of distribution of 1,1-DMH transformation products along the soil profile indicate that transformation products can migrate down to the depth of 120 cm, The highest concentrations of 1,1-DMH transformation products were detected, as a rule, at the depth 20 to 60 cm. However, this index can vary depending on the compound, humidity and physical properties of soil, landscape features and other conditions. In the surface layer, as a rule, only semi-volatile products of transformation were detected which was caused by fast evaporation and biodegradation of volatile metabolites.