Methyl Chloroform Research Articles

Environmental Policies and Countermeasures for the Phase-Out of Ozone-Depleting Substances (ODSs) over the Last 30 Years: A Case Study in Taiwan

It is well established that the reaction cycles involving some halogenated alkanes (so-called ozone-depleting substances—ODSs) contribute to the depletion of ozone in the stratosphere, prompting the Montreal Protocol (initially signed in 1987), and later amendments. The Protocol called for the scheduled phase-out of ODSs, including chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), carbon tetrachloride (CCl4), halon, methyl chloroform (CH3CCl3), methyl chloride (CH3Cl), and even hydrofluorocarbons (HFCs). In view of the urgent importance of ozone layer protection to the global ecological environment, the Taiwanese government has taken regulatory actions to reduce ODS consumption since 1993, through the joint venture of the central competent authorities. Under the government’s regulatory requirements, and the industry’s efforts to adopt both alternatives to ODSs and abatement technologies, the phase-out of some ODSs (i.e., CFCs, CCl4, halon, and CH3CCl3) was achieved prior to 2010. The consumption of HCFCs and methyl chloride has significantly declined over the past three decades (1993–2022). However, HFC emissions indicated a V-type variation during this period. Due to local production and extensive use of HFCs in Taiwan, the country’s emissions increased from 663 kilotons of carbon dioxide equivalents (CO2eq) in 1993 to 2330 kilotons of CO2eq in 2001, and then decreased to 373 kilotons of CO2eq in 2011. Since then, the emissions of HFCs largely used as the alternatives to ODSs showed an upward trend, increasing to 1555 kilotons of CO2eq in 2022. To be in compliance with the Kigali Amendment (KA-2015) to the Montreal Protocol for mitigating global warming, the Taiwanese government has taken regulatory actions to reduce the consumption of some HFC substances with high global warming potential (GWP) under the authorization of the Climate Change Response Act in 2023, aiming at an 80% reduction by 2045 of the baseline consumption in 2024.

Resetting tropospheric OH and CH4 lifetime with ultraviolet H2O absorption.

The decay of methyl chloroform, a banned ozone-depleting substance, has provided a clear observational metric of mean tropospheric hydroxyl radical (OH) abundance. Almost all current global chemistry models calculate about 15% too much OH and thus too rapid methane loss. Methane is a short-lived climate forcer, critical to achieving global warming targets, and this error affects our model projections of climate change. New observations of water vapor absorption in the ultraviolet region (290 to 350 nanometers) imply reductions in sunlight with key photolysis rates decreasing by 8 to 12% in the near-surface tropical atmosphere. Incorporation of this new mechanism in a chemistry-transport model reduces OH and methane loss by only 4%, but combined with other proposed mechanisms, such as tropospheric halogen chemistry (7%), we may be able to resolve this conundrum.

Estimation of the atmospheric hydroxyl radical oxidative capacity using multiple hydrofluorocarbons (HFCs)

Abstract. The hydroxyl radical (OH) largely determines the atmosphere's oxidative capacity and, thus, the lifetimes of numerous trace gases, including methane (CH4). Hitherto, observation-based approaches for estimating the atmospheric oxidative capacity have primarily relied on using methyl chloroform (MCF), but as the atmospheric abundance of MCF has declined, the uncertainties associated with this method have increased. In this study, we examine the use of five hydrofluorocarbons (HFCs) (HFC-134a, HFC-152a, HFC-365mfc, HFC-245fa, and HFC-32) in multi-species inversions, which assimilate three HFCs simultaneously, as an alternative method to estimate atmospheric OH. We find robust estimates of OH regardless of which combination of the three HFCs are used in the inversions. Our results show that OH has remained fairly stable during our study period from 2004 to 2021, with variations of < 2 % and no significant trend. Inversions including HFC-32 and HFC-152a (the shortest-lived species) indicate a small reduction in OH in 2020 (1.6±0.9 % relative to the mean over 2004–2021 and 0.6±0.9 % lower than in 2019), but considering all inversions, the reduction was only 0.5±1.1 %, and OH was at a similar level to that in 2019.

The ozone layer and its impact on human health

The formation of life on Earth and the presence of various ecosystems were determined by several factors, and one of the most important among them is the atmosphere. In particular, the ozone layer (O3), located in the second layer of the atmosphere, 12-35 kilometers above the earth's surface, in the stratosphere, where 90% of ozone is present, the remaining amount of ozone, about 10%, is located in the troposphere. Stratospheric ozone is important for environmental protection. At present, uncontrolled industrial activities and other actions have put humanity at great risk, which has resulted in the release of chlorofluorocarbons and other halocarbons into the air. After being released in the stratosphere, molecules of these compounds interact with ultraviolet radiation to release bromine and chlorine. It is a known fact, that one molecule of CFC can destroy as many as 100,000 ozone molecules. Ozone-depleting substances and factors include carbon tetrachloride, methyl chloroform, hydrobromofluorocarbons, methyl bromide, bromochloromethane, nitrogen oxides, space rockets, airplanes flying at 12-15 km overhead, global warming, etc. The previously mentioned reactions and substances caused the depletion of the ozone layer and the so-called occurrence of "Ozone holes", discovered near the poles. It can be said assuredly that the depletion of the ozone layer and its resulting effects, such as premature aging, an increase in the number of skin cancer patients, in particular basal cell cancer and squamous cell cancer, weakening of the immune system, damage to the cornea, conjunctival membrane, crystal and retinal membrane of the eye, and others have become one of the serious challenges of modernity. All of the aforementioned led to the Montreal Protocol, aimed to protect the ozone layer by reducing ozone-depleting gases. Georgia officially joined the "Montreal Protocol" and the "Vienna Convention" in 1996. It is also worth noting that dealing with such a global problem and the experience gained within it will also help us  in the fight against climate change.

Improving the efficiency and stability of in-air fabricated perovskite solar cells using the mixed antisolvent of methyl acetate and chloroform

Antisolvents play a significant role in obtaining high-quality perovskite films during the fabrication process. This paper reports a novel mixture of two antisolvents (methyl acetate and chloroform) that proves effective for fabricating high-quality perovskite films in a high humidity ambient. The results show that the use of methyl acetate alone as the antisolvent enables the fabrication of dense perovskite films (MAPbI 3 ) in a high humidity ambient, but with a rough surface, while mixing methyl acetate with an appropriate amount of chloroform produces not only dense perovskite films but also smooth surfaces. As a result, the power conversion efficiency (PCE) is increased from 17.1% of the devices treated with methyl acetate alone to 18.6% of the devices treated with the mixed antisolvent of methyl acetate (70%) and chloroform (30%). The stability of the devices was also improved significantly for the devices treated with the mixed antisolvent of methyl acetate (85%) and chloroform (15%), which exhibit a slow degradation of 7% in PCE after 552 h of storage, compared to 22% for the devices treated with methyl acetate alone. • Improving the stability of perovskite solar cell by the mixed antisolvent treatment. • Enabling fabrication of high-performance perovskite solar in a high humidity ambient. • Demonstrating the benefit of mixed antisolvent treatment in MAPbI 3 layer preparation.

Improving the Efficiency and Stability of In-Air Fabricated Perovskite Solar Cells Using the Mixed Antisolvent of Methyl Acetate and Chloroform

Improving the Efficiency and Stability of In-Air Fabricated Perovskite Solar Cells Using the Mixed Antisolvent of Methyl Acetate and Chloroform

Thermodynamic Study on Hydrotropic Aggregation Behavior of Theophylline

Abstract: Objectives: A systematic study is required to enhance the solubility of insoluble fluid drugs that are only sparingly soluble. Hydrotropy may be a distinctive development to reinforce the liquid solubility of poorly water-soluble drugs. Materials and Methods: The term hydrotropic has been wont to designate the rise in the solubility of assorted substances in water because of the presence of enormous amounts of additives. Sodium salicylate, sodium benzoate, and resorcinol are utilized to reinforce the liquid solubility of many poorly soluble drugs. Varied organic solvents like methyl alcohol, chloroform, alcohol, dimethylformamide, and benzene are utilized for the solubilization of poorly soluble drugs. Theophylline drug was accessories to numerous hydrotrope concentrations (0-3 mol/L) and also the non-inheritable sample for a solubility determination was analyzed in an exploitation UV spectrophotometer. Results: The solubility of theophylline has been specifically found to improve with an increase in hydrotrope concentration and also with a device temperature likely to be close to that of other organic compounds and drugs. Conclusion: To initiate substantial solubilization of the theophylline compound, a minimum hydrotrope concentration (MHC) in the aqueous phase was needed. As a consequence of the improvement in the solubilization of theophylline, the coefficient of mass transfer was also observed to expand with an increase in the hydrotropic concentration at 303 K. To have a substantial enhancement within the mass transfer coefficient, a threshold value equivalent to MHC is to be maintained. For all sets of experiments, the maximal enhancement factor, which is the value ratio between the presence and absence of a hydrotrope, has been calculated. Thermodynamic parameters such as Gibb’s free energy, enthalpy, and entropy of theophylline were calculated to determine the hydrotropic aggregation activity of theophylline. With an increase in system temperature, Gibb’s free energy declines. It was found that the aggregation of hydrotropes was exothermic and preferred by a positive entropy value. Key words: Hydrotropy, Theophylline, Solubility, Enhancement Factor, Aggregation Properties.

A three-dimensional-model inversion of methyl chloroform to constrain the atmospheric oxidative capacity

Abstract. Variations in the atmospheric oxidative capacity, largely determined by variations in the hydroxyl radical (OH), form a key uncertainty in many greenhouse and other pollutant budgets, such as that of methane (CH4). Methyl chloroform (MCF) is an often-adopted tracer to indirectly put observational constraints on large-scale variations in OH. We investigated the budget of MCF in a 4DVAR inversion using the atmospheric transport model TM5, for the period 1998–2018, with the objective to derive information on large-scale, interannual variations in atmospheric OH concentrations. While our main inversion did not fully converge, we did derive interannual variations in the global oxidation of MCF that bring simulated mole fractions of MCF within 1 %–2 % of the assimilated observations from the NOAA-GMD surface network at most sites. Additionally, the posterior simulations better reproduce aircraft observations used for independent validation compared to the prior simulations. The derived OH variations showed robustness with respect to the prior MCF emissions and the prior OH distribution over the 1998 to 2008 period. Although we find a rapid 8 % increase in global mean OH concentrations between 2010 and 2012 that quickly declines afterwards, the derived interannual variations were typically small (< 3 %/yr), with no significant long-term trend in global mean OH concentrations. The inverse system found strong adjustments to the latitudinal distribution of OH, relative to widely used prior distributions, with systematic increases in tropical and decreases in extra-tropical OH concentrations (both up to 30 %). These spatial adjustments were driven by intrahemispheric biases in simulated MCF mole fractions, which have not been identified in previous studies. Given the large amplitude of these adjustments, which exceeds spread between literature estimates, and a residual bias in the MCF intrahemispheric gradients, we suggest a reversal in the extratropical ocean sink of MCF in response to declining atmospheric MCF abundance (as hypothesized in Wennberg et al., 2004). This ocean source provides a more realistic explanation for the biases, possibly complementary to adjustments in the OH distribution. We identified significant added value in the use of a 3D transport model, since it implicitly accounts for variable transport and optimizes the observed spatial gradients of MCF, which is not possible in simpler models. However, we also found a trade-off in computational expense and convergence problems. Despite these convergence problems, the derived OH variations do result in an improved match with MCF observations relative to an interannually repeating prior for OH. Therefore, we consider that variations in OH derived from MCF inversions with 3D models can add value to budget studies of long-lived gases like CH4.

Methyl Chloroform Continues to Constrain the Hydroxyl (OH) Variability in the Troposphere

AbstractTrends and variability in tropospheric hydroxyl (OH) radicals influence budgets of many greenhouse gases, air pollutant species, and ozone depleting substances. Estimations of tropospheric OH trends and variability based on budget analysis of methyl chloroform (CH3CCl3) and process‐based chemistry transport models often produce conflicting results. Here we use a previously tested transport model to simulate atmospheric CH3CCl3 for the period 1985–2018. Based on mismatches between model output and observations, we derive consistent anomalies in the inverse lifetime of CH3CCl3 (KG) using measurements from two independent observational networks (National Oceanic and Atmospheric Administration and Advanced Global Atmospheric Gases Experiment). Our method allows a separation between “physical” (transport, temperature) and “chemical” (i.e., abundance) influences on OH + CH3CCl3 reaction rate in the atmosphere. Small increases in KG due to “physical” influences are mostly driven by increases in the temperature‐dependent reaction between OH and CH3CCl3 and resulted in a smoothly varying increase of 0.80% decade−1. Chemical effects on KG, linked to global changes in OH sources and sinks, show larger year‐to‐year variations (∼2%–3%), and have a negative correlation with the El Niño Southern Oscillation. A significant positive trend in KG can be derived after 2001, but it persists only through 2015 and only if we assume that CH3CCl3 emissions decayed more slowly over time than our best estimate suggests. If global CH3CCl3 emissions dropped below 3 Gg year−1 after 2015, recent CH3CCl3 measurements indicate that the 2015–2018 loss rate of CH3CCl3 due to reaction with OH is comparable to its value 2 decades ago.

Trends in global tropospheric hydroxyl radical and methane lifetime since 1850 from AerChemMIP

Abstract. We analyse historical (1850–2014) atmospheric hydroxyl (OH) and methane lifetime data from Coupled Model Intercomparison Project Phase 6 (CMIP6)/Aerosols and Chemistry Model Intercomparison Project (AerChemMIP) simulations. Tropospheric OH changed little from 1850 up to around 1980, then increased by around 9 % up to 2014, with an associated reduction in methane lifetime. The model-derived OH trends from 1980 to 2005 are broadly consistent with trends estimated by several studies that infer OH from inversions of methyl chloroform and associated measurements; most inversion studies indicate decreases in OH since 2005. However, the model results fall within observational uncertainty ranges. The upward trend in modelled OH since 1980 was mainly driven by changes in anthropogenic near-term climate forcer emissions (increases in anthropogenic nitrogen oxides and decreases in CO). Increases in halocarbon emissions since 1950 have made a small contribution to the increase in OH, whilst increases in aerosol-related emissions have slightly reduced OH. Halocarbon emissions have dramatically reduced the stratospheric methane lifetime by about 15 %–40 %; most previous studies assumed a fixed stratospheric lifetime. Whilst the main driver of atmospheric methane increases since 1850 is emissions of methane itself, increased ozone precursor emissions have significantly modulated (in general reduced) methane trends. Halocarbon and aerosol emissions are found to have relatively small contributions to methane trends. These experiments do not isolate the effects of climate change on OH and methane evolution; however, we calculate residual terms that are due to the combined effects of climate change and non-linear interactions between drivers. These residual terms indicate that non-linear interactions are important and differ between the two methodologies we use for quantifying OH and methane drivers. All these factors need to be considered in order to fully explain OH and methane trends since 1850; these factors will also be important for future trends.

Biodiesel production from microalgae by direct transesterification using green solvents

Abstract This study evaluated the production of biodiesel from the microalgae Chlorella pyrenoidosa by direct transesterification using 2-methyltetrahydrofuran or cyclopentyl methyl ether co-solvents as an alternative to chloroform. Acid-catalyzed transesterification using hydrochloric acid was developed for biodiesel production. Biodiesel was purified by column chromatography using one of the two green solvents as eluents. The highly ecological biodiesel quality was compared to the biodiesel produced using chloroform as co-solvent. A 33 factorial design was conducted to optimize the production of fatty acid methyl esters, being the independent variables investigated: solvent and catalyst volume, solvent and catalyst ratio (methanol:co-solvent:hydrochloric acid), and temperature, with a reaction time of 150 min. Biodiesel production was mainly influenced by temperature increase. The achieved yields using cyclopentyl methyl ether, 2-methyltetrahydrofuran, and chloroform were 71–92%, 67–91%, and 61–76%, respectively. The fatty acid methyl esters profile of biodiesel produced with 2-methyltetrahydrofuran and cyclopentyl methyl ether consisted of approximately 45% polyunsaturated components. The biodiesel obtained was within the ASTM D6751 and EN 14214 standards. The replacement of fossil solvents used in direct transesterification of biomass with a green solvent resulted in a further ecological biodiesel production process towards a circular bioeconomy.

Efficacy and Cytotoxicity of Binary Mixtures as Root Canal Filling Solvents.

Objectives: This study reports the efficacy of two solvent mixtures on the dissolution of gutta-percha and AH Plus sealer, together with the cytotoxicity. Methods: Methyl ethyl ketone (MEK), orange oil, tetrachloroethylene, MEK/tetrachloroethylene (1:1), MEK/orange oil (1:1), and chloroform (control) were tested. Twelve groups (n = 15) of standardized stainless-steel molds filled with softened gutta-percha cones and twelve (n = 15) filled with AH Plus were immersed in the corresponding mixture or individual solvent, in an ultrasonic bath, for either 2 or 5 min. The effect of the solvents was assessed qualitatively by a topographical analysis (scanning electron microscopy) and chemical analysis (Fourier transform infrared spectroscopy), and quantitatively by a weight loss and viscoelastic property (dynamic mechanical analysis) evaluation. The cytotoxicity was assessed on MG63 human osteoblastic cells. Results: The mixtures did not show the formation of new compounds. Both presented significantly higher efficacies compared to their individual solvents, suggesting a synergistic effect. Their dissolution efficacy was similar to that of chloroform, showing high cytocompatibility. Conclusions: The proposed strategy, incorporating ultrasound agitation and profiting from the synergy of adequate solvents, might enhance root canal cleanliness allowing a single-step procedure to dissolve gutta-percha and the sealer remnants, while assuring cytocompatibility with the periapical tissues.

Emissions of halocarbons from India inferred through atmospheric measurements

Abstract. As the second most populous country and third fastest growing economy, India has emerged as a global economic power. As such, its emissions of greenhouse and ozone-depleting gases are of global significance. However, unlike neighbouring China, the Indian sub-continent is very poorly monitored by atmospheric measurement networks. India's halocarbon emissions, here defined as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) and chlorocarbons, are not well-known. Previous measurements from the region have been obtained at observatories many hundreds of kilometres from source regions, or at high altitudes, limiting their value for the estimation of regional emission rates. Given the projected rapid growth in demand for refrigerants and solvents in India, emission estimates of these halocarbons are urgently needed to provide a benchmark against which future changes can be evaluated. In this study, we report atmospheric-measurement-derived halocarbon emissions from India. With the exception of dichloromethane, these top-down estimates are the first for India's halocarbons. Air samples were collected at low altitude during an aircraft campaign in June and July 2016, and emissions were derived from measurements of these samples using an inverse modelling framework. These results were evaluated to assess India's progress in phasing out ozone-depleting substances under the Montreal Protocol. India's combined CFC emissions are estimated to be 54 (27–86) Tg CO2 eq. yr−1 (5th and 95th confidence intervals are shown in parentheses). HCFC-22 emissions of 7.8 (6.0–9.9) Gg yr−1 are of similar magnitude to emissions of HFC-134a (8.2 (6.1–10.7) Gg yr−1). We estimate India's HFC-23 emissions to be 1.2 (0.9–1.5) Gg yr−1, and our results are consistent with resumed venting of HFC-23 by HCFC-22 manufacturers following the discontinuation of funding for abatement under the Clean Development Mechanism. We report small emissions of HFC-32 and HFC-143a and provide evidence to suggest that HFC-32 emissions were primarily due to fugitive emissions during manufacturing processes. A lack of significant correlation among HFC species and the small emissions derived for HFC-32 and HFC-143a indicate that in 2016, India's use of refrigerant blends R-410A, R-404A and R-507A was limited, despite extensive consumption elsewhere in the world. We also estimate emissions of the regulated chlorocarbons carbon tetrachloride and methyl chloroform from northern and central India to be 2.3 (1.5–3.4) and 0.07 (0.04–0.10) Gg yr−1 respectively. While the Montreal Protocol has been successful in reducing emissions of many ozone-depleting substances, growth in the global emission rates of the unregulated very short-lived substances poses an ongoing threat to the recovery of the ozone layer. Emissions of dichloromethane are found to be 96.5 (77.8–115.6) Gg yr−1, and our estimate suggests a 5-fold increase in emissions since the last estimate derived from atmospheric data in 2008. We estimate perchloroethene emissions from India and chloroform emissions from northern–central India to be 2.9 (2.5–3.3) and 32.2 (28.3–37.1) Gg yr−1 respectively. Given the rapid growth of India's economy and the likely increase in demand for halocarbons such as HFCs, the implementation of long-term atmospheric monitoring in the region is urgently required. Our results provide a benchmark against which future changes to India's halocarbon emissions may be evaluated.

Liquid-liquid equilibrium study for ternary systems of water + propargyl alcohol + solvents at 308.2 K: Measurement and thermodynamic modelling

The liquid-liquid equilibrium data for the water + propargyl alcohol (PA) + solvents ternary system were measured at 308.2 K under 101.3 kPa, where solvents refer to ethyl acetate, methyl tert-butyl ether, methyl isobutyl carbinol and chloroform. The tie lines were displayed in ternary phase diagrams. The distribution coefficient and separation factor were calculated according to the measured tie-line data and employed to evaluate the capacity of solvents to extract PA from aqueous solution. The calculation results demonstrated that the selectivity was large enough for the extraction application. Meanwhile, the reliability of the experimental data was confirmed using the Othmer-Tobias and Hand equations. The UNIFAC model was applied for a comparison and predicting the LLE behaviors. The results indicated that the calculated data by UNIFAC model cannot agree well with the experimental ones. The NRTL and UNIQUAC models were used to correlate the experimental data and the binary interaction parameters were regressed. The root mean square deviations of the NRTL and UNIQUAC models were less than 0.6%, indicating that the LLE experimental data can be successfully correlated by the models.

Phosgene in the Upper Troposphere and Lower Stratosphere: A Marker for Product Gas Injection Due to Chlorine‐Containing Very Short Lived Substances

AbstractPhosgene in the atmosphere is produced via the degradation of carbon tetrachloride, methyl chloroform, and a number of chlorine‐containing very short lived substances (VSLS). These VSLS are not regulated by the Montreal Protocol even though they contribute to stratospheric ozone depletion. While observations of VSLS can quantify direct stratospheric source gas injection, observations of phosgene in the upper troposphere/lower stratosphere can be used as a marker of product gas injection of chlorine‐containing VSLS. In this work we report upper troposphere/lower stratosphere measurements of phosgene made by the ACE‐FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) instrument and compare with results from the TOMCAT/SLIMCAT three‐dimensional chemical transport model to constrain phosgene trends over the 2004–2016 period. The 13‐year ACE‐FTS time series provides the first observational evidence for an increase in chlorine product gas injection. In 2016, VSLS accounted for 27% of modeled stratospheric phosgene, up from 20% in the mid‐2000s.

Constraints and biases in a tropospheric two-box model of OH

Abstract. The hydroxyl radical (OH) is the main atmospheric oxidant and the primary sink of the greenhouse gas CH4. In an attempt to constrain atmospheric levels of OH, two recent studies combined a tropospheric two-box model with hemispheric-mean observations of methyl chloroform (MCF) and CH4. These studies reached different conclusions concerning the most likely explanation of the renewed CH4 growth rate, which reflects the uncertain and underdetermined nature of the problem. Here, we investigated how the use of a tropospheric two-box model can affect the derived constraints on OH due to simplifying assumptions inherent to a two-box model. To this end, we derived species- and time-dependent quantities from a full 3-D transport model to drive two-box model simulations. Furthermore, we quantified differences between the 3-D simulated tropospheric burden and the burden seen by the surface measurement network of the National Oceanic and Atmospheric Administration (NOAA). Compared to commonly used parameters in two-box models, we found significant deviations in the magnitude and time-dependence of the interhemispheric exchange rate, exposure to OH, and stratospheric loss rate. For MCF these deviations can be large due to changes in the balance of its sources and sinks over time. We also found that changes in the yearly averaged tropospheric burden of CH4 and MCF can be obtained within 0.96 ppb yr−1 and 0.14 % yr−1 by the NOAA surface network, but that substantial systematic biases exist in the interhemispheric mixing ratio gradients that are input to two-box model inversions. To investigate the impact of the identified biases on constraints on OH, we accounted for these biases in a two-box model inversion of MCF and CH4. We found that the sensitivity of interannual OH anomalies to the biases is modest (1 %–2 %), relative to the uncertainties on derived OH (3 %–4 %). However, in an inversion where we implemented all four bias corrections simultaneously, we found a shift to a positive trend in OH concentrations over the 1994–2015 period, compared to the standard inversion. Moreover, the absolute magnitude of derived global mean OH, and by extent, that of global CH4 emissions, was affected much more strongly by the bias corrections than their anomalies (∼10 %). Through our analysis, we identified and quantified limitations in the two-box model approach as well as an opportunity for full 3-D simulations to address these limitations. However, we also found that this derivation is an extensive and species-dependent exercise and that the biases were not always entirely resolvable. In future attempts to improve constraints on the atmospheric oxidative capacity through the use of simple models, a crucial first step is to consider and account for biases similar to those we have identified for the two-box model.

Monitoring global tropospheric OH concentrations using satellite observations of atmospheric methane

Abstract. The hydroxyl radical (OH) is the main tropospheric oxidant and the main sink for atmospheric methane. The global abundance of OH has been monitored for the past decades using atmospheric methyl chloroform (CH3CCl3) as a proxy. This method is becoming ineffective as atmospheric CH3CCl3 concentrations decline. Here we propose that satellite observations of atmospheric methane in the short-wave infrared (SWIR) and thermal infrared (TIR) can provide an alternative method for monitoring global OH concentrations. The premise is that the atmospheric signature of the methane sink from oxidation by OH is distinct from that of methane emissions. We evaluate this method in an observing system simulation experiment (OSSE) framework using synthetic SWIR and TIR satellite observations representative of the TROPOMI and CrIS instruments, respectively. The synthetic observations are interpreted with a Bayesian inverse analysis, optimizing both gridded methane emissions and global OH concentrations. The optimization is done analytically to provide complete error accounting, including error correlations between posterior emissions and OH concentrations. The potential bias caused by prior errors in the 3-D seasonal OH distribution is examined using OH fields from 12 different models in the ACCMIP archive. We find that the satellite observations of methane have the potential to constrain the global tropospheric OH concentration with a precision better than 1 % and an accuracy of about 3 % for SWIR and 7 % for TIR. The inversion can successfully separate the effects of perturbations to methane emissions and to OH concentrations. Interhemispheric differences in OH concentrations can also be successfully retrieved. Error estimates may be overoptimistic because we assume in this OSSE that errors are strictly random and have no systematic component. The availability of TROPOMI and CrIS data will soon provide an opportunity to test the method with actual observations.

Chloroethene. Documentation of proposed values of occupational exposure limits (OELs)

Chloroethene. Documentation of proposed values of occupational exposure limits (OELs)

Changes in Global Tropospheric OH Expected as a Result of Climate Change Over the Last Several Decades

AbstractThe oxidizing capacity of the troposphere is controlled primarily by the abundance of hydroxyl radical (OH). The global mean concentration of tropospheric OH, [OH]TROP (the burden of OH in the global troposphere appropriate for calculating the lifetime of methane) inferred from measurements of methyl chloroform has remained relatively constant during the past several decades despite rising levels of methane that should have led to a decline. Here we examine other factors that may have affected [OH]TROP such as the changing values of stratospheric ozone, rising tropospheric H2O, varying burden of NOx (=NO+NO2), rising temperatures, and widening of the climatological tropics due to expansion of the Hadley cell. Our analysis suggests the positive trends in [OH]TROP due to H2O, NOx, and overhead O3, and tropical expansion are large enough (Δ [OH]TROP = +0.95 ± 0.18%/decade) to counter almost all of the expected decrease in [OH]TROP due to rising methane (Δ [OH]TROP = −1.01 ± 0.05%/decade) over the period 1980 to 2015, while variations in temperature contribute almost no trend (Δ [OH]TROP = −0.02 ± 0.02%/decade) in [OH]TROP. The approximated impact of Hadley cell expansion on [OH]TROP is also a small but not insignificant factor partially responsible for the steadiness of tropospheric oxidizing capacity over the past several decades, which free‐running models likely do not capture.

Halocarbon Emissions from a Degraded Forested Wetland in Coastal South Carolina Impacted by Sea Level Rise

Tropical- and subtropical-storm surges combined with sea level rise cause saltwater intrusions into low-lying coastal ecosystems along the southeastern coast of the United States, gradually converting freshwater forested wetland into saltmarsh. The transition zone between freshwater and saltwater ecosystems becomes a degraded forested wetland, where the combination of high levels of soil organic matter and elevated concentrations of halide ions creates a dynamic biogeochemical environment that may be a potential hotspot for halocarbon formation such as chloroform, methyl chloride, and methyl bromide. This study conducted field measurements at a transition zone in coastal South Carolina to quantify halocarbon exchange rates and laboratory soil incubations to determine the contributions of biotic versus abiotic processes. The degraded forested wetland showed significant chloroform emission rates (146 ± 129 nmol m–2 d–1). The degraded forested wetland remained a net sink for methyl chloride and a negligible source/sink for methyl bromide, unlike the saltmarsh which was a significant source for both. The laboratory incubations strongly suggest that methyl halide consumption in soils at the field site was biotic and that production of methyl halides and chloroform was largely abiotic and temperature-dependent, although additional experiments are required to rule out possible biotic production involving heat-resistant microbes. The results suggest that sea level rise and more frequent storm surges derived from global climate change, in the long term, may increase emissions of chloroform from coastal degraded forested wetlands and of methyl halides if salt marshes expand, with potential impacts for stratospheric ozone depletion.