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Reply to Comment by Cole-dai Et Al. on "Climatic Impact of the Long-lasting Laki Eruption: Inapplicability of Mass-independent Sulfur Isotope Composition Measurements"

Here we respond to the comments by Cole-Dai et al. [2014] on our article Schmidt et al. [2012]. Specifically, in response to section 2 of their reply, we argued in Schmidt et al. [2012] that based on previously published estimates of the volatile release height during the 1783-1784 C.E. Laki eruption, the lack of a sulfur massindependent fractionation (MIF) anomaly is expected. In other words, no previous study on Laki ever argued that this eruption emitted SO2 into altitudes >13-15 km. In section 2.3, Cole-Dai et al. [2014] argue that the nonzero Δ33S value of their Laki sample 1 may be explained by a short-lived explosive phase at Laki during which volatiles reached the stratosphere. In Schmidt et al. [2012] in section 2, we argued in agreement with Cole-Dai et al. [2014] (section 3.1) that for a MIF anomaly to be preserved, the Laki volatiles would have had to be emitted in >20 km altitude. Our main point is that eruption column heights >20 km are unlikely based on the historical accounts and plume-rise modeling for the Laki eruption [Stothers et al., 1986; Woods, 1993; Thordarson and Self, 2003]. In Schmidt et al. [2012], we argued that to deduce a short-lived climatic impact of the Laki eruption based on the lack of a MIF anomaly and the length of the sulfate deposition in Greenland ice cores may be misleading because the climatic impact will outlast the radiative forcing of the Laki aerosol cloud. Cole-Dai et al. [2014] acknowledge the latter in their reply in section 4.2. We agreewith Cole-Dai et al. [2014] in that themagnitude and length of the climatic impact during the winter of 1783-1784 depends on the altitude of the volatile release during the eruption (sections 2.3 and 4.2). However, even if we assumed that during Laki all sulfur dioxide (SO2) would have been released in the troposphere, then the aerosol cloud would still be present in the upper troposphere during March 1784, as is evident from independent model simulations of this "tropospheric-only" scenario [Stevenson et al., 2003]. We acknowledge that there is uncertainty on the volatile release height for Laki; however, it is worth considering that those climate model simulations that used an injection altitude between 9 km and 13 km for the Laki SO2 [Highwood and Stevenson, 2003; Oman et al., 2006a, 2006b; Schmidt et al., 2012] best match the observed temperature changes during summer of 1783 [Angell and Korshover, 1985; Brázdil et al., 2010; Briffa et al., 1998; D'Arrigo and Jacoby, 1999; Jacoby et al., 1999; Kington, 1988; Manley, 1974; Parker et al., 1992; Thordarson and Self, 2003]. Based on these model simulations, a climatic impact during the winter of 1783-1784, albeit weaker than during the climactic phases of Laki, is expected (and our argument here does not exclude the role of natural variability in contributing to the cold winter of 1783-1784 as discussed in Schmidt et al. [2012]). Therefore, we continue to argue that for high-latitude eruptions such as Laki, the applicability of sulfur isotopic measurements to interpret the climatic relevance has yet to be demonstrated. Itmay transpire that the interpretation of MIF signals for the climate-relevance of an eruption is valid and unambiguous only for short-lived explosive eruptions in the tropics. In terms of the processes producing a MIF anomaly (section 3.3 in Cole-Dai et al. [2014]), the works by Hattori et al. [2013] and Ono et al. [2013] suggest that there are remaining issues not discussed by Cole-Dai et al. [2014], for instance, self-shielding of SO2 due to high column densities typical for eruptions of Pinatubo-scale and greater, and the preservation of the MIF signature in general.

general circulation model↗

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

evolved gas analysis↗

A Laser-Induced Fluorescence Instrument for Aircraft Measurements of Sulfur Dioxide in the Upper Troposphere and Lower Stratosphere

This work describes the development and testing of a new instrument for in situ measurements of sulfur dioxide (SO2) on airborne platforms in the upper troposphere and lower stratosphere (UTLS). The instrument is based on the laser-induced fluorescence technique and uses the fifth harmonic of a tunable fiber-amplified semiconductor diode laser system at 1084.5 nm to excite SO2 at 216.9 nm. Sensitivity and background checks are achieved in flight by additions of SO2 calibration gas and zero air, respectively. Aircraft demonstration was performed during the NASA Volcano Plume Investigation Readiness and Gas-Phase and Aerosol Sulfur (VIRGAS) experiment, which was a series of flights using the NASA WB-57F during October 2015 based at Ellington Field and Harlingen, Texas. During these flights, the instrument successfully measured SO2 in the UTLS at background (non-volcanic) conditions with a precision of 2 ppt at 10 s and an overall uncertainty determined primarily by instrument drifts of +/- (16% + 0.9 ppt).

tunable fiber-amplified semiconductor diode laser ↗

Chain Formation as a Mechanism for Mass-Independent Fractionation of Sulfur Isotopes in the Archean Atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this 'mass-independent' fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negative ∆(sup 33) S values and positive ∆(sub 36) S values in elemental sulfur-just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive ∆(sup 33) S and negative ∆(sup 36) S. Positive ∆(sup 33) S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

Great Oxidation Event↗

Sulfur-bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from ~450 to 800degC during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2 (~3-22 μmol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (~41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (~1-5nmol) and CS2 (~0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

Gale Crater↗

Chain Formation as a Mechanism for Mass-Independent Fractionation of Sulfur Isotopes in the Archean Atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this ‘mass-independent’ fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negative Δ(exp 33)S values and positive Δ(exp 33)S values in elemental sulfur—just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive Δ(exp 33)S and negative Δ(exp 33)S. Positive Δ(exp 33)S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

C. E. Harman↗

Assessment of Natural and Anthropogenic Aerosol Air Pollution In the Middle East Using MERRA-2, CAMS Data Assimilation Products, and High-Resolution WRF-Chem Model Simulations

Modern-Era Retrospective analysis for Research and Applications v.2 (MERRA-2), Copernicus Atmosphere Monitoring Service Operational Analysis (CAMS-OA), and a high-resolution regional Weather Research and Forecasting model coupled with chemistry (WRF-Chem) were used to evaluate natural and anthropogenic particulate matter (PM) air pollution in the Middle East (ME) during 2015–2016. Two Moderate Resolution Imaging Spectrometer (MODIS) retrievals – combined product Deep Blue and Deep Target (MODIS-DB&DT) and Multi-Angle Implementation of Atmospheric Correction (MAIAC) – and Aerosol Robotic Network (AERONET) aerosol optical depth (AOD) observations as well as in situ PM measurements for 2016 were used for validation of the WRF-Chem output and both assimilation products. MERRA-2 and CAMS-OA assimilate AOD observations. WRF-Chem is a free-running model, but dust emission in WRF-Chem is tuned to fit AOD and aerosol volume size distributions obtained from AERONET. MERRA-2 was used to construct WRF-Chem initial and boundary conditions both for meteorology and chemical and aerosol species. SO2 emissions in WRF-Chem are based on the novel OMI-HTAP SO2 emission dataset. The correlation with the AERONET AOD is highest for MERRA-2 (0.72–0.91), MAIAC (0.63–0.96), and CAMSOA (0.65–0.87), followed by MODIS-DB&DT (0.56–0.84) and WRF-Chem (0.43–0.85). However, CAMS-OA has a relatively high positive mean bias with respect to AERONET AOD. The spatial distributions of seasonally averaged AODs from WRF-Chem, assimilation products, and MAIAC are well correlated with MODIS-DB&DT AOD product. MAIAC has the highest correlation (R = 0.8), followed by MERRA-2 (R = 0.66), CAMS-OA (R = 0.65), and WRF-Chem (R = 0.61). WRF-Chem, MERRA-2, and MAIAC underestimate and CAMS-OA overestimates MODIS-DB&DT AOD. The simulated and observed PM concentrations might differ by a factor of 2 because it is more challenging for the model and the assimilation products to reproduce PM concentration measured within the city. Although aerosol fields in WRF-Chem and assimilation products are entirely consistent, WRF-Chem is preferable for analysis of regional air quality over the ME due to its higher spatial resolution and better SO2 emissions. The WRF-Chem’s PM background concentrations exceed the World Health Organization (WHO) guidelines over the entire ME. Mineral dust is the major contributor to PM (≈ 75%–95%) compared to other aerosol types. Near and downwind from the SO2 emission sources, non-dust aerosols (primarily sulfate) contribute up to 30% to PM(sub 2.5). The contribution of sea salt to PM in coastal regions can reach 5%. The contributions of organic matter, black carbon and organic carbon to PM over the Middle East are insignificant. In the major cities over the Arabian Peninsula, the 90th percentile of PM(sub 10) and PM(sub 2.5) (particles with diameters less than 10 and 2.5 μm, respectively) daily mean surface concentrations exceed the corresponding Kingdom of Saudi Arabia air quality limits. The contribution of the non-dust component to PM(sub 2.5) is < 25%, which limits the emission control effect on air quality. The mitigation of the dust effect on air quality requires the development of environment-based approaches like growing tree belts around the cities and enhancing in-city vegetation cover. The WRF-Chem configuration presented in this study could be a prototype of a future air quality forecast system that warns the population against air pollution hazards.

Alexander Ukhov↗

High resolution assimilation of multiple satellite retrievals with emissions adjustment to improve air quality forecasting with WRF-Chem/DART

We will present results from medium (15km, 6hr cycling) and high (4 km, 6 hr cycling) spatiotemporal resolution applications of the WRF-Chem/DART ensemble, regional, air quality (AQ) forecast/assimilation system.The medium-resolution setup is applied to the Discover AQ/Front Range Air Pollution and Photochemistry Experiment (FRAPPE) domain from July 14 to July 29, 2014. The high-resolution setup is applied to a Colorado domain from July 14 to July 29, 2020. For the FRAPPE application, we assimilate MOPITT CO; IASI CO;MODIS AOD; OMI O3, NO2; and AirNow CO, O3, NO2, SO2, PM10, and PM2.5. For the Colorado application, we assimilate the same MOPITT, MODIS, and AirNow constituents as in the FRAPPE application and TROPOMI CO, O3, NO2; and synthetic TEMPO O3and NO2. WRF-Chem/DART integrates the Weather Research and Forecast (WRF) model with on-line chemistry (WRF-Chem) into the Data Assimilation Research Testbed (DART). It assimilates AirNow CO, O3, NO2, SO2, PM10, and PM2.5 measurements, MOPITT CO; IASI CO, O3; OMI O3, NO2, SO2; TROPOMI CO, O3, NO2, SO2; MODIS AOD; and synthetic TEMPO O3 and NO2 total/partial column and/or profile retrievals.WRF-Chem/DART uses: (i) the state augmentation method for adjusting emissions; (ii) state-space localization; and (iii) a near-real time scripting system. We use the medium-resolution FRAPPE application to demonstrate the incremental benefits from assimilating OMI observations with emissions adjustment and the high-resolution Colorado application to demonstrate the incremental benefits from assimilating syntheticTEMPO observations with emissions adjustment. For both applications, we expect that: (i) assimilating chemical observations will increaseAQ forecast skill; (ii) including emissions adjustment will increase forecast skill/predictability; and (iii) including assimilation of synthetic TEMPO observations will further increase forecast skill/predictability.

High resolution↗

Multi-Spectral Lidar Observations and Balloon Borne Validation of SO 2 -O 3 During the SOWLETS Campaign: An Examination of Local Incinerator Plume

The Langley Mobile O3 Lidar (LMOL) was stationed at NASA's Langley Research Center for the initiation of the SO 2 -O 3 Water Land Environment study (SOWLETS). The primary focus of the campaign was to examine the capabilities of a novel four-wavelength detection technique to measure the concentrations of sulfur dioxide (SO2) and ozone (O3). The exact location of the lidar, near the NASA/CAPABLE site, was optimized to intercept the plume emissions from a proximate incinerator facility using historical weather data for the month of the campaign. A novel four-wavelength lidar technique focused on the detection of sulfur dioxide (SO2) and ozone (O3) was employed, and its capabilities were thoroughly examined. The technique is built upon the standard DIAL. While 3 wavelengths would be enough to retrieve both SO2 and O3, the 4 wavelengths allow to provide data on aerosol backscattering. In parallel, SO 2 -O 3 sondes were launched and installed in the nearby NASA Landing and Impact research facility, providing validation for the lidar's atmospheric measurements. In conclusion, this campaign offers an improved understanding of SO2 emissions in the local environment and a validation of a novel technique to facilitate pollution observations. It shows the promise of this new kind of lidar to better understand and validate the observations by NASA/TEMPO ("Tropospheric Emissions: Monitoring of Pollution").

G. Gronoff↗

Expanding the Capabilities of the JPL Electronic Nose for an International Space Station Technology Demonstration

An array-based sensing system based on polymer/carbon composite conductometric sensors is under development at JPL for use as an environmental monitor in the International Space Station. Sulfur dioxide has been added to the analyte set for this phase of development. Using molecular modeling techniques, the interaction energy between SO2 and polymer functional groups has been calculated, and polymers selected as potential SO2 sensors. Experiment has validated the model and two selected polymers have been shown to be promising materials for SO2 detection.

electronic noses↗

Space-Based Detection of Missing Sulfur Dioxide Sources of Global Air Pollution

Sulfur dioxide is designated a criteria air contaminant (or equivalent) by virtually all developed nations. When released into the atmosphere, sulfur dioxide forms sulfuric acid and fine particulate matter, secondary pollutants that have significant adverse effects on human health, the environment and the economy. The conventional, bottom-up emissions inventories used to assess impacts, however, are often incomplete or outdated, particularly for developing nations that lack comprehensive emission reporting requirements and infrastructure. Here we present a satellite-based, global emission inventory for SO2 that is derived through a simultaneous detection, mapping and emission-quantifying procedure, and thereby independent of conventional information sources. We find that of the 500 or so large sources in our inventory, nearly 40 are not captured in leading conventional inventories. These missing sources are scattered throughout the developing world-over a third are clustered around the Persian Gulf-and add up to 7 to 14 Tg of SO2 yr(exp -1), or roughly 6-12% of the global anthropogenic source. Our estimates of national total emissions are generally in line with conventional numbers, but for some regions, and for SO2 emissions from volcanoes, discrepancies can be as large as a factor of three or more. We anticipate that our inventory will help eliminate gaps in bottom-up inventories, independent of geopolitical borders and source types.

OMI↗

Chemical Climatology of Atmospheric Pollutants in the Eastern United States: Seasonal/Diurnal Cycles and Contrast Under Clear/Cloudy Conditions for Remote Sensing

We statistically assessed temporal variations of observed concentrations of eight atmospheric pollutants (SO2, NO, NO2, NO(y), O3, CO, NH3, and HNO3) at three urban sites and one rural site in the eastern United States for a ten-year period (4 years for NH3). Diurnal/seasonal patterns of observed mean concentrations and their decade-scale trends under different weather conditions were evaluated. Concentrations of pollutants decreased consistently during the observation period (as long as 1997–2013), although nighttime ozone during winter appears to increase because of reduced NO-O3 titration. This study shows that the decay time of major air pollutant concentrations such as SO2 and NO(x) can be short as a few hours to one day. We also identified substantial differences between the mean concentrations of pollutants at clear sky and overcast conditions that could introduce biases into satellite observations. Surface concentrations of SO2 and CO are distinctly higher under cloud free than under overcast conditions by ∼30% and ∼20% respectively. NO2 shows a complex pattern, but demonstrates lower daytime concentrations under cloud-free skies. All of these estimates are important for understanding the chemical climatology of these atmospheric pollutants, especially their diurnal/seasonal cycles under different weather conditions. For four-year measurements, NH3 shows a substantial difference, with clear sky observations roughly a factor of two higher than those under overcast conditions. To track changes in the future, the full daily cycle of atmospheric pollutants monitored by geostationary satellite such as the future TEMPO mission may better capture patterns and trends.

TEMPO↗

Performance of Wrought Superalloys in Extreme Environments

As power generation systems move towards higher efficiency operation above 700 °C, wrought superalloys are the leading structural alloy candidates, including precipitation strengthened (PS) alloys 740 and 282 for the highest temperatures. To evaluate the performance of these alloys for these applications, a range of 500–5000 h evaluations have been conducted in environments including steam, supercritical CO2 (sCO2) and simulated combustion exhaust with H2O and/or SO2 at 700–800 °C and compared to baseline exposures in laboratory air and 1 bar CO2. These alloys primarily rely on the formation of an external Cr-rich oxide layer or scale for environmental protection and the reaction rates in all of these conditions are similar and relatively low. However, compared to a conventional solid solution strengthened alloy, like 625, the mass gains are higher for PS alloys due to the internal oxidation of the γ' forming additions, Al and Ti. Post-exposure characterization has quantified the reaction products and the depth of internal oxidation is not a concern and does not appear to increase above the baseline behavior in laboratory air. Likewise, there is no indication of internal carburization in the sCO2 environment at 750 °C/300 bar. The addition of 0.1% SO2 in CO2-10% H2O at 800 °C actually suppressed the internal oxidation at 1 bar but SO2 may be a concern when the total pressure is higher.

Pint, Bruce A.↗

Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

We consider several spin-unrestricted random-phase approximation (RPA) variants for calculating correlation energies, with and without range separation, and test them on datasets of atomization energies and reaction barrier heights. We show that range separation greatly improves the accuracy of all RPA variants for these properties. Moreover, we show that a RPA variant with exchange, hereafter referred to as RPAx-SO2, first proposed by Szabo and Ostlund [J. Chem. Phys. 67, 4351 (1977)] in a spin-restricted closed-shell formalism, and extended here to a spin-unrestricted formalism, provides on average the most accurate range-separated RPA variant for atomization energies and reaction barrier heights. Since this range-separated RPAx-SO2 method had already been shown to be among the most accurate range-separated RPA variants for weak intermolecular interactions [J. Toulouse et al., J. Chem. Phys. 135, 084119 (2011)], this works confirms range-separated RPAx-SO2 as a promising method for general chemical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The last decade of global anthropogenic sulfur dioxide: 2000-2011 emissions

Evolution of global and regional anthropogenic SO2 emissions in the last decade has been estimated through a bottom-up calculation for recent years. After a strong increase in emissions that peaked about 2006, we estimate a declining trend continuing until 2011. However, there is a strong spatial variability with North America and Europe continuing to reduce emissions with an increasing role of Asia and international shipping. China remains a key contributor but the introduction of stricter emission limits followed by an ambitious program of installing flue gas desulfurization on power plants resulted in significant decline in emissions from energy sector and stabilization of Chinese SO2 emissions. Comparable mitigation strategies are not yet present in several other Asian countries and industrial sectors in general, while emissions from international shipping are expected to start declining soon following agreed reduction of sulfur content of fuel oil. Estimated trends in global SO2 emissions are within the range of RCP projections and uncertainty calculated for the year 2005.

Klimont, Z↗

Materials Data on KCS2N(O2F)2 by Materials Project

(K(SO2)2)2N2(CF2)2 crystallizes in the orthorhombic Pna2_1 space group. The structure is three-dimensional and consists of eight ammonia molecules, eight difluoromethane molecules, and one K(SO2)2 framework. In the K(SO2)2 framework, there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of K–O bond distances ranging from 2.78–3.03 Å. In the second K1+ site, K1+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of K–O bond distances ranging from 2.80–3.00 Å. There are four inequivalent S2+ sites. In the first S2+ site, S2+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both S–O bond lengths are 1.45 Å. In the second S2+ site, S2+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both S–O bond lengths are 1.45 Å. In the third S2+ site, S2+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.45 Å) and one longer (1.46 Å) S–O bond length. In the fourth S2+ site, S2+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both S–O bond lengths are 1.45 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S2+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one S2+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S2+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S2+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S2+ atom. In the sixth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S2+ atom. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S2+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S2+ atom.

36 MATERIALS SCIENCE↗

Materials Data on AgH9C7S2(OF)4 by Materials Project

AgC5H9(SO2)2(CF2)2 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of four difluoromethane molecules and one AgC5H9(SO2)2 cluster. In the AgC5H9(SO2)2 cluster, Ag1+ is bonded in a 5-coordinate geometry to two S2- and three O2- atoms. Both Ag–S bond lengths are 2.49 Å. There are a spread of Ag–O bond distances ranging from 2.72–2.98 Å. There are five inequivalent C+0.86+ sites. In the first C+0.86+ site, C+0.86+ is bonded in a trigonal non-coplanar geometry to three H1+ and one S2- atom. There is one shorter (1.09 Å) and two longer (1.10 Å) C–H bond length. The C–S bond length is 1.81 Å. In the second C+0.86+ site, C+0.86+ is bonded in a trigonal non-coplanar geometry to three H1+ and one S2- atom. All C–H bond lengths are 1.10 Å. The C–S bond length is 1.81 Å. In the third C+0.86+ site, C+0.86+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.24 Å) and one longer (1.28 Å) C–O bond length. In the fourth C+0.86+ site, C+0.86+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.31 Å) C–O bond length. In the fifth C+0.86+ site, C+0.86+ is bonded in a distorted water-like geometry to two H1+ and two S2- atoms. Both C–H bond lengths are 1.10 Å. There is one shorter (1.80 Å) and one longer (1.82 Å) C–S bond length. There are nine inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. In the fifth H1+ site, H1+ is bonded in a linear geometry to two O2- atoms. There is one shorter (1.06 Å) and one longer (1.47 Å) H–O bond length. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.86+ atom. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to one Ag1+ and two C+0.86+ atoms. In the second S2- site, S2- is bonded in a trigonal non-coplanar geometry to one Ag1+ and two C+0.86+ atoms. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one Ag1+ and one C+0.86+ atom. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Ag1+, one C+0.86+, and one H1+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one Ag1+ and one C+0.86+ atom. In the fourth O2- site, O2- is bonded in a water-like geometry to one C+0.86+ and one H1+ atom.

36 MATERIALS SCIENCE↗