Solving the mystery of the Chukotka stinky gray whales.

Gray whales (Eschrichtius robustus) constitute an important part of the diet of Chukotka Native population, reaching 30% of consumed food for the inland Chukchas. Over one hundred licenses for whale hunting are issued on an annual basis. After the USSR collapse natives had to hunt whales near the shore from the small boats. The problem of "stinky" whales arose immediately, as the meat of some harvested species possessed a strong medicinal/chemical odour. The hypotheses explaining the phenomenon ranged from biotoxins, to oil spills. To understand the problem, various tissues of normal and stinky Gray whales were collected in 2020-2021 and analyzed using headspace solid phase microextraction with Gas Chromatography - Mass Spectrometry. Here, we show that dozens of smelly organic compounds were identified among over 500 compounds detected in the samples. The most interesting analytes related to the off odour are bromophenols. The most probable suspect is 2,6-dibromophenol with strong iodoformic odour, perfectly matching that of the "stinky" whales. Quantitative results demonstrated its levels were up to 500-fold higher in the "stinky" whales' tissues. The source of 2,6-dibromophenol is likely polychaetes, producing 2,6-dibromophenol and colonising near shore waters where whales feed. Therefore, the mystery of the stinky whales may be considered resolved.

Modeling the effect of temperature on solid-phase microextraction of volatile organic compounds from air by polydimethylsiloxane coating using finite element analysis.

A development of analytical methods based on solid-phase microextraction (SPME) is a very time- and labor-consuming task. The finite element methods have found a wide application in SPME modeling for faster and more accurate optimization of analytical methods. In this work, a computational model for predicting the effect of temperature on extraction of VOCs from air onto SPME coating based on polydimethylsiloxane (PDMS) has been developed using COMSOL Multiphysics® (CMP) software. Most suitable methods and models for estimating the diffusion coefficients of analytes in air and coating, and coating-air distribution constants of the analytes at different extraction temperatures were chosen. The Fuller method was chosen for calculating diffusion coefficients of analytes in air due to its simplicity and reliability. Coating-air distribution constants at different temperatures were estimated using van't Hoff equation. A combination of inverse gas chromatography on a capillary column with a similar stationary phase for estimating diffusion coefficients and linear temperature programmed retention indices (LTPRI) for estimating coating-air distribution constants at initial temperature were chosen for modeling purposes because in most cases it provided lowest values of root-mean-square difference from experimental extraction profiles from 125 mL bulb at 25 and 40 °C. The developed model can be recommended for faster and simpler optimization of the methods of air sampling using PDMS SPME fiber. It can also be used for obtaining extraction profiles at fluctuating temperatures.

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.