Atmospheric Observation and Emission of HFC-134a in China and Its Four Cities.

1,1,1,2-Tetrafluoroethane (HFC-134a) is widely used as a refrigerant to replace dichlorodifluoromethane (CFC-12), and a small amount of it is used in the foam and medical aerosol sectors, with a high global warming potential and fast-increasing atmospheric concentration. The emission of HFC-134a in China has been growing at an average annual growth rate of 14.4% since 2009, reaching 53.0 (47.5-58.7) kt yr-1 in 2020. Among the five emission sources, emissions from the mobile air conditioning (MAC) sector accounted for the highest proportion of 65% on average of the total, followed by the commercial air conditioning (CAC) sector (25%), the medical aerosols sector (8%), the foam sector (2%), and leakage emission from the production (less than 0.1%). The emissions of HFC-134a in four cities in China (Beijing, Guangzhou, Hangzhou, and Lanzhou) were also estimated and discussed. Beijing had the highest HFC-134a emission of 2.2 kt yr-1 in 2020, and Lanzhou had the lowest emission of only 0.2 kt yr-1. In Beijing and Guangzhou, emissions from the CAC sector surpassed those from the MAC sector, becoming the most important source of HFC-134a. The average annual growth rate of HFC-134a's emissions during 2009-2019 was close to its concentration enhancement growth rate of 12.7%, and the emissions also showed significant correlations with the concentration enhancements in both China and four cities. This indicates the importance of the muti-city and long-term observations for the verification of HFC-134a's emission estimates at a regional scale.

Acute, repeated inhalation toxicity, respiratory system irritation, and mutagenicity studies of 1,1,2,2-tetrafluoroethane (HFC-134) as the impurity in the pharmaceutical propellant 1,1,1,2-tetrafluoroethane (HFA-134a).

HFC-134 is the main impurity of HFA-134a. In order to verify the rationality of HFC-134 limits in HFA-134a and ensure the safety of HFA-134a as propellant in pharmaceutical metered-dose inhalers, acute inhalation toxicity, seven-day repeat dose inhalation irritation study, 21-day repeat dose inhalation toxicity study and reverse mutation assay of HFC-134 were tested to evaluate its inhalation safety. In acute inhalation studies, Sprague-Dawley rats were exposed nose-only to HFC-134 at levels of 100 000, 200 000, 400 000, 600 000, and 800 000 ppm for 4 h. Based on the mortality incidence, the calculated four-hour LC50 value for HFC-134 is 532 069 ppm for males and 502 058 ppm for females and acute inhalation toxicity is manifested as the lung lobes turn dark red. Exposures to 836 ± 67 ppm for 4 hours/day 7 days/week continuously did not induce local irritation of the respiratory system in Sprague-Dawley rats. Sprague-Dawley rats were exposed nose-only to HFC-134 at levels of 0 (control), 203 929 ppm and 394 871 ppm 2 h/day for 21 consecutive days, no significant treatment-related adverse effects was noted. Results from Ames studies demonstrated that HFC-134 was not mutagenic. Although HFC-134 has a very low acute inhalation toxicity, considering that its acute inhalation toxicity is higher than that of HFA-134a, and due to the high frequency of use of MDI by asthma patients, acceptance criteria of HFC-134 as the impurity in aerosol propellant HFA-134a should be lower than 8-h TWA WEEL value of 1000 ppm to ensure the safety of the MDI.

Global emissions of refrigerants HCFC-22 and HFC-134a: unforeseen seasonal contributions.

HCFC-22 (CHClF2) and HFC-134a (CH2FCF3) are two major gases currently used worldwide in domestic and commercial refrigeration and air conditioning. HCFC-22 contributes to stratospheric ozone depletion, and both species are potent greenhouse gases. In this work, we study in situ observations of HCFC-22 and HFC-134a taken from research aircraft over the Pacific Ocean in a 3-y span [HIaper-Pole-to-Pole Observations (HIPPO) 2009-2011] and combine these data with long-term ground observations from global surface sites [National Oceanic and Atmospheric Administration (NOAA) and Advanced Global Atmospheric Gases Experiment (AGAGE) networks]. We find the global annual emissions of HCFC-22 and HFC-134a have increased substantially over the past two decades. Emissions of HFC-134a are consistently higher compared with the United Nations Framework Convention on Climate Change (UNFCCC) inventory since 2000, by 60% more in recent years (2009-2012). Apart from these decadal emission constraints, we also quantify recent seasonal emission patterns showing that summertime emissions of HCFC-22 and HFC-134a are two to three times higher than wintertime emissions. This unforeseen large seasonal variation indicates that unaccounted mechanisms controlling refrigerant gas emissions are missing in the existing inventory estimates. Possible mechanisms enhancing refrigerant losses in summer are (i) higher vapor pressure in the sealed compartment of the system at summer high temperatures and (ii) more frequent use and service of refrigerators and air conditioners in summer months. Our results suggest that engineering (e.g., better temperature/vibration-resistant system sealing and new system design of more compact/efficient components) and regulatory (e.g., reinforcing system service regulations) steps to improve containment of these gases from working devices could effectively reduce their release to the atmosphere.

Effect of Overfilled Solvent and Storage Time of Subcritical Extraction of Jasminum sambac on Yield, Antioxidant Activity, Antimicrobial Activity and Tentative Volatile Compounds.

Essential oil from Jasminum sambac flowers has demonstrated the potential of antioxidant and antimicrobial properties. However, jasmine flowers contain only a small amount of essential oil; therefore, subcritical fluid extraction (SFE) with HFC-134a, one of the effective extraction methods for flower extraction, was performed in this study. The percentage of overfilled solvent and storage time of the flowers were varied during the extraction. Antioxidant potential, antimicrobial potential and tentative volatile compounds were investigated in this study to observe the quality of the essential oil. It was discovered that a greater amount of overfilled solvent resulted in thicker essential oil and a longer storage time resulted in a lower amount of total oil yield. It could be seen that almost all extraction conditions did not have any significant difference in antioxidant and antimicrobial potential. The essential oil contained primary compounds such as indole, 9-tricosene, α-farnesene, muurolene, and benzyl alcohol. This study led to the conclusion that the amount of overfilled solvent from SFE affected the thickness of jasmine essential oil and its tentative volatile compounds. The longer storage time caused the significantly lower essential oil yield, but changing the extraction conditions had no significant effect on antioxidant or antimicrobial potential.

A Comparative Analysis of Phenolic Content, Antioxidant Activity, Antimicrobial Activity, and Chemical Profile of Coffea robusta Extracts Using Subcritical Fluid Extraction and Supercritical Carbon Dioxide Extraction.

In this study, extracts of Robusta-roasted coffee were obtained using various extraction techniques, including subcritical fluid extractions using HFC-134a and HCFC-22 under room-temperature batch extraction, frozen-temperature batch extraction, and continuous extraction conditions. Additionally, supercritical carbon dioxide (SCCO2) extraction was performed using ethanol and tetrahydrofuran as co-solvents. These extractions were performed due to the presence of potent antioxidants and antibacterial substances in the extracts. Extraction machines were built to process the extraction. The antioxidant potential of the extracts was evaluated using total phenolic content and DPPH and FRAP assays, while antibacterial potential was identified using the disk diffusion method. The results showed that HCFC-22 extraction produced the highest yield compared to other extraction methods, but HFC-134a extraction had the highest antioxidant potential values. The yield and antioxidant potential of the extracts obtained using room-temperature batch extraction were slightly higher than those obtained using frozen-temperature batch extraction and continuous extraction. The yield and antioxidant potential of the extracts obtained using SCCO2 extraction were similar to those obtained using HFC-134a and HCFC-22 extractions, and co-solvents slightly improved the extraction performance. The extracts were found to be more effective as inhibitors of Gram-positive bacteria than Gram-negative bacteria. Caffeine was the most prominent tentative chemical compound in all coffee extracts. This research study provides a better understanding of various extraction techniques using HFC-134a, HCFC-22, and SCCO2 when applied to roasted Robusta coffee beans, with a focus on yield, antioxidant potential, antimicrobial potential, and tentative chemical profiles.

Kinetic and thermodynamic investigations on the HF elimination reactions from neutral and ionized CF3CH2F.

This work discusses the possible HF formation routes via recombination reactions from CF3CH2F (R-134a) and its cation. The molecular properties of the main reagents were first evaluated at the M06-2X/cc-pVTZ level. Then, changes in energy (ΔE) for all reactions comprising a possible HF formation from the studied systems were evaluated at the CCSD(T)/CBS//M06-2X/cc-pVTZ level. With the aid of Intrinsic Reaction Coordinate (IRC) calculations for each path, it is found that the HF formation reaction takes place majorly through the "1,2" elimination, resulting in an olefin as the secondary product. In turn, the IRC associated with "2,2" reactions allowed to find a post-barrier complex between the carbene :CHCF3 and HF in its exit channel, with dissociation energy of ∼4 kcal mol-1. Similarly, the cationic system exhibits favoritism towards the "1,2" elimination, and an ion-dipole post-barrier complex is found. The ΔE of such a complex production is negative in both directions, indicating this complex (25.5 kcal/mol more stable than CF3CH2F+) should be a minimum on the R-134a cation surface. However, unlike the neutral "2,2" path, there is no F atom migration transition state for the 2,2-HF elimination from CF3CH2F+. Hence, the F migration is expected to occur simultaneously with the rest of the structural changes towards the ion-dipole complex. The rate coefficients computed at the current level of theory, including corrections for anharmonicity and hindered rotations, showed a reasonable agreement with the available experimental data, inspiring confidence in our predictions for the cationic system.

A novel solar-powered milk cooling refrigeration unit with cold thermal energy storage for rural application.

This experimental study analyzed the use of solar photovoltaic energy for operating a novel twin-circuit DC milk chiller without batteries using water-based cold thermal energy storage for different seasons in Chennai, India. HFC-134a and HC-600a were used as refrigerants in the two individual circuits. For each season, the test was conducted continuously for 18 days to analyze the quantity of generated ice that could be utilized to chill 10 L of milk in the morning and in the evening. The average quantity of ice formed per day in the ice bank during monsoon, winter, and summer seasons was found to be 3.61, 19.75, and 27.97 kg, respectively. Thus, it is evident that the use of solar energy with thermal energy storage is effective for operating the milk chilling unit for two seasons, namely winter and summer. However, the system requires an additional power source for continuous operation during the monsoon season. It is noteworthy to mention that the use of a solar milk chiller instead of a conventional milk chiller resulted in 91.15% lesser CO2 emission with 27.6% less LCC. In this study, solar photovoltaic power was observed to be a good choice for chilling milk in the context of global warming and energy consumption. The use of thermal energy storage also allows the initial cost to be reduced.

Feasibility of regenerative adsorption of a hydrofluorocarbon (HFC-134a) using activated carbon fiber studied by the gaseous flow method.

The adsorption and desorption behavior of the refrigerant HFC-134a on pitch-based activated carbon fibers (ACFs) with various Brunauer-Emmett-Teller surface areas was investigated by the flow method. Fixed-bed adsorption experiments performed at 20, 5, -15, -20, and -25 °C showed that the use of lower temperatures resulted in an increase in the adsorption capacity of the ACF. In particular, the complete adsorption time was dramatically increased at -25 °C. Crucially, even after five cycles of adsorption at -20 °C and desorption at 30 °C of HFC-134a in a electrothermal swing adsorption apparatus, significant decreases in the adsorption capability were not observed. The desorption of HFC-134a from saturated ACF was carried out using electric power directly applied to the ACF itself. The electric heating increased the ACF temperature, causing desorption within several minutes. The results of this study show that the regenerative adsorption of HFC-134a by ACF coupled with electric power is possible.

Rainwater trifluoroacetic acid (TFA) in Guangzhou, South China: levels, wet deposition fluxes and source implication.

The origin of trifluoroacetic acid (TFA) occurring in hydrosphere has long been a controversial issue. Hydrochlorofluorocarbons and hydrofluorocarbons (HCFCs/HFCs) as replacements of chlorofluorocarbons (CFCs) are precursors of TFA in the atmosphere, their contribution to rainwater TFA is a concern as their ambient mixing ratios are continually growing. Here we present rainwater TFA monitored from April 2007 to March 2008 in urban Guangzhou, a central city in south China's highly industrialized and densely populated Pearl River Delta region. Rainwater TFA levels ranged 45.8-974 ng L(-1) with a median of 166 ng L(-1). TFA levels negatively correlated with rainfall amount, the yearly rainfall-weighted average for TFA was 152 ng L(-1). The annual TFA wet deposition flux was estimated to be 229 g km(-2) yr(-1), and the total wet deposition of TFA reached ~1.7 tyr(-1) in Guangzhou. The Two-Box model was applied to estimate attributions of HCFCs/HFCs and fluoropolymers to rainwater TFA assuming TFA generated was proportional to gross domestic product (GDP), gross industrial product (GIP) or number of private cars. The results revealed that the degradation of HCFCs/HFCs and fluoropolymers could explain 131.5-152.4 ng L(-1) rainwater TFA, quite near the observed rainfall-weighted annual mean of 152 ng L(-1), suggesting rainwater TFA in Guangzhou was predominantly originated from these anthropogenic precursors. HCFCs/HFCs accounted for 83.3-96.5% of rainwater TFA observed, while fluoropolymers' contributions were minor (~5%). HFC-134a alone could explain 55.9-90.0% of rainwater TFA, and its contribution would be greatly enhanced with its wide use in mobile air conditioning systems and rapid increase in ambient mixing ratios.

Blood and exhaled air can be used for biomonitoring of hydrofluorocarbon exposure.

Various hydrofluorocarbons (HFCs) have replaced the ozone-depleting chlorofluorocarbons and hydrochlorofluorocarbons during the last decades. The objective of this study was to examine the usefulness of blood and breath for exposure biomonitoring of HFCs. We compared data on blood and exhaled air from a series of experiments where healthy volunteers were exposed to vapors of four commonly used HFCs; 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, and 1,1,1,3,3-pentafluoropropane. All four HFCs had similar toxicokinetic profiles in blood with a rapid initial increase and an apparent steady-state reached within a few minutes. For all HFCs, the inhalation uptake during exposure was low (less than 6%), most of which was exhaled post-exposure. No metabolism could be detected and only minor amounts were excreted unchanged in urine. The observed time courses in blood and breath were well described by physiologically-based pharmacokinetic (PBPK) modeling. Simulations of 8-h exposures show that the HFC levels in both blood and breath drop rapidly during the first minutes post-exposure, whereafter the decline is considerably slower and mainly reflects washout from fat tissues. We conclude that blood and exhaled air can be used for biological exposure monitoring. Samples should not be taken immediately at the end of shift but rather 20-30 min later.