CO2 Mixing Ratios Research Articles

The friagem event in the central Amazon and its influence on micrometeorological variables and atmospheric chemistry

Abstract. In the period between 9 and 11 July 2014, a friagem event reached the Amazon region. On 11 July, the southwest flow related to the friagem converged with the easterly winds in the central Amazon. The interaction between these two distinct air masses formed a convection band, which intensified over the Manaus region and the Amazon Tall Tower Observatory (ATTO) site. The satellite images show the evolution of convective activity on 11 July, which led to 21 mm of precipitation at the ATTO site. Moreover, the arrival of the friagem caused a sudden drop in temperature and a predominance of southerly winds, which could be seen in Porto Velho between 7 and 8 July and in Manaus and the ATTO site from 9 to 11 July. The results of ERA-Interim reanalysis and Brazilian developments on the Regional Atmospheric Modeling System (BRAMS) simulations show that this friagem event coming from the southwest, carries a mass of air with higher O3 and NO2 mixing ratios and lower CO mixing ratio compared to the air masses present in the central Amazon. At Lake Balbina, the friagem intensifies the local circulations, such as the breeze phenomena. In the Manaus region and at the ATTO site, the main effects of the friagem event are a decrease in the incoming solar radiation (due to intense cloud formation), a large temperature drop and a distinct change in surface O3 and CO2 mixing ratios. As the cold air of the friagem was just in the lower 500 m the most probable cause of this change is that a cold pool above the forest prevented vertical mixing causing accumulation of CO2 from respiration and very low O3 mixing ratio due to photochemistry reduction and limited mixing within the boundary layer.

Systematic investigation of CO2 : NH3 ice mixtures using mid-IR and VUV spectroscopy – part 2: electron irradiation and thermal processing

Many experimental parameters determine the chemical and physical properties of interstellar ice analogues, each of which may influence the molecular synthesis that occurs in such ices. In part 1, James et al., RSC Adv., 2020, 10, 37517, we demonstrated the effects that the stoichiometric mixing ratio had on the chemical and physical properties of CO2 : NH3 mixtures and the impact on molecular synthesis induced by thermal processing. Here, in part 2, we extend this to include 1 keV electron irradiation at 20 K of several stoichiometric mixing ratios of CO2 : NH3 ices followed by thermal processing. We demonstrate that not all stoichiometric mixing ratios of CO2 : NH3 ice form the same products. Not only did the 4 : 1 ratio form a different residue after thermal processing, but O3 was observed after electron irradiation at 20 K, which was not observed in the other ratios. For the other ratios, the residue formed from a thermal reaction similar to the work shown in Part 1. However, conversion of ammonium carbamate to carbamic acid was hindered due to electron irradiation at 20 K. Our results demonstrate the need to systematically investigate stoichiometric mixing ratios to better characterise the chemical and physical properties of interstellar ice analogues to further our understanding of the routes of molecular synthesis under different astrochemical conditions.

Spatial and Temporal Distributions of Atmospheric CO2 in East China Based on Data from Three Satellites

East China (23.6°–38.4°N, 113.6°–122.9°E) is the largest developed region in China. Based on CO2 products retrieved from the Greenhouse Gases Observing Satellite (GOSAT), the spatial and temporal distributions of CO2 mixing ratios in East China during 2014–17 are discussed, and the retrieved CO2 from AIRS (Atmospheric Infrared Sounder) and OCO-2 (Orbiting Carbon Observatory-2), as well as WLG (Waliguan) background station observations, are compared with those of GOSAT. The annual CO2 retrieved from GOSAT in East China ranged from 398.96 ± 0.24 ppm in 2014 to 407.39 ± 0.20 ppm in 2017, with a growth rate of 2.82 ± 0.15 ppm yr−1, which were higher than in other regions of China. The seasonal cycle presented a maximum in spring and a minimum in summer or autumn. Higher values were mainly concentrated in the coastal areas of Zhejiang Province, and lower values were concentrated in Jiangxi and the north of Fujian Province. CO2 observed in Fujian and parts of Jiangxi increased by less than 1.0 ppm during 2014–15, but enhanced significantly by more than 5.0 ppm during 2015–16, perhaps influenced by local emissions and global impacts. We calculated year-to-year CO2 enhancements in the Yangtze River Delta region during 2014–17 that were relatively low and stable, due to the region’s carbon emissions control and reduction policies. The annual and seasonal amplitudes of CO2 retrieved from AIRS were lower than those from GOSAT in East China, probably owing to the CO2 retrieved from AIRS better reflecting the characteristics of the mid-troposphere, while GOSAT is more representative of near-surface CO2. The spatial and temporal distribution characteristics of CO2 retrieved from OCO-2 were close to those from GOSAT in East China.

Avaliação da Similaridade entre as flutuações turbulentas de escalares em ambiente de lago

This paper presents an evaluation of scalar similarity and scalar flux similarity of measurements above the water surface of the Itaipu hydroelectric reservoir. The scalars studied were: CO2 mixing ratio (rc), air temperature (θ), specific air humidity (q) and the vertical wind velocity (w). With the variance method it was found that the vertical wind velocity is in agreement with Monin-Obukhov Similarity Theory. On the other hand, the other scalars presented larger deviations in relation to the theoretical prediction. The worst results were for air temperature and mixing ratio of CO2. The most similar scalars were θ and q, with the most frequent correlation coefficient varying in the range [0.55:0.64] for measurements in unstable atmospheric conditions and in the [−0.85:−0.75] range for measurements under stable atmospheric conditions. Regarding the scalar fluxes, they presented greater similarity to each other than the scalars themselves.

Isotope composition of carbon dioxide and methane in a tropical urban atmosphere

ABSTRACT This work presents a weekly carbon isotope composition analysis (June 2017–January 2018) of carbon dioxide (CO2) and methane (CH4) in a tropical urban atmosphere (Central Valley, Costa Rica). δ13C values of CO2 and CH4 ranged from –12.2 to –5.9 ‰, and from –51.6 to –46.3 ‰, respectively. Mixing ratios of CO2 and CH4 varied from 384.2 to 528.5 ppmv, and from 1.860 to 2.613 ppmv, respectively. δ13C spatial variation and mixing ratios of CO2 and CH4 were influenced by the atmospheric stability and air circulation patterns in the metropolitan area. Low δ13C values and large mixing ratios were observed in the southwestern area of the valley during the rainiest period (September–November). Preliminary linear relationships between reciprocal CO2 mixing ratios and δ13C values indicate that CO2 emissions in the Central Valley are probably related to respiration processes and fossil fuel combustion, although CO2 enriched in 13C from volcanic degassing was also detected. Under stable atmospheric conditions, CH4 data seems to reflect the influence of emissions near the sampling sites. These preliminary results based on the carbon isotope technique demonstrate potential for carrying out atmospheric studies at tropical urban locations with different terrain characteristics and atmospheric mixing conditions.

Evaluation of a field-deployable Nafion™-based air-drying system for collecting whole air samples and its application to stable isotope measurements of CO<sub>2</sub>

Abstract. Atmospheric flask samples are either collected at atmospheric pressure by opening a valve of a pre-evacuated flask or pressurized with the help of a pump to a few bar above ambient pressure. Under humid conditions, there is a risk that water vapor in the sample leads to condensation on the walls of the flask, notably at higher than ambient sampling pressures. Liquid water in sample flasks is known to affect the CO2 mixing ratios and also alters the isotopic composition of oxygen (17O and 18O) in CO2 via isotopic equilibration. Hence, for accurate determination of CO2 mole fractions and its stable isotopic composition, it is vital to dry the air samples to a sufficiently low dew point before they are pressurized in flasks to avoid condensation. Moreover, the drying system itself should not influence the mixing ratio and the isotopic composition of CO2 or that of the other constituents under study. For the Airborne Stable Isotopes of Carbon from the Amazon (ASICA) project focusing on accurate measurements of CO2 and its singly substituted stable isotopologues over the Amazon, an air-drying system capable of removing water vapor from air sampled at a dew point lower than −2 ∘C, flow rates up to 12 L min−1 and without the need for electrical power was needed. Since to date no commercial air-drying device that meets these requirements has been available, we designed and built our own consumable-free, power-free and portable drying system based on multitube Nafion™ gas sample driers (Perma Pure, Lakewood, USA). The required dry purge air is provided by feeding the exhaust flow of the flask sampling system through a dry molecular sieve (type 3A) cartridge. In this study we describe the systematic evaluation of our Nafion™-based air sample dryer with emphasis on its performance concerning the measurements of atmospheric CO2 mole fractions and the three singly substituted isotopologues of CO2 (16O13C16O, 16O12C17O and 16O12C18O), as well as the trace gas species CH4, CO, N2O and SF6. Experimental results simulating extreme tropical conditions (saturated air at 33 ∘C) indicated that the response of the air dryer is almost instantaneous and that approximately 85 L of air, containing up to 4 % water vapor, can be processed staying below a −2 ∘C dew point temperature (at 275 kPa). We estimated that at least eight flasks can be sampled (at an overpressure of 275 kPa) with a water vapor content below −2 ∘C dew point temperature during a typical flight sampling up to 5 km altitude over the Amazon, whereas the remaining samples would stay well below 5 ∘C dew point temperature (at 275 kPa). The performance of the air dryer on measurements of CO2, CH4, CO, N2O, and SF6 and the CO2 isotopologues 16O13C16O and 16O12C18O was tested in the laboratory simulating real sampling conditions by compressing humidified air from a calibrated cylinder, after being dried by the air dryer, into sample flasks. We found that the mole fraction and the isotopic composition difference between the different test conditions (including the dryer) and the base condition (dry air, without dryer) remained well within or very close to, in the case of N2O, the World Meteorological Organization recommended compatibility goals for independent measurement programs, proving that the test condition induced no significant bias on the sample measurements.

Assessment of Ventilation Efficiency in School Classrooms Based on Indoor–Outdoor Particulate Matter and Carbon Dioxide Measurements

The concentration of indoor suspended particulate matter is considered to be one of the main factors that affect health and quality of life. In Poland, in response to the pressure of public opinion, a few thousand air purifiers have been installed in public buildings where children spend time. However, another factor that also impacts upon the quality of indoor air, namely increased CO2 mixing ratios, is frequently overlooked. The only way to remove CO2 excess from interiors is through intensive ventilation. This is often an action at odds with the need to maintain low concentrations of particulate matter in indoor air. Two methods are presented to assess the rate of air exchange using CO2 or particulate matter as a tracer. One of the methods using indoor/outdoor PM (particulate matter) concentrations is based on the use of box models for analysis. The second one uses indoor CO2 concentration change analysis. At the tested locations, they showed large deviations of the determined values of the air exchange coefficients from its limits. Both methods showed consistent ventilation parameters estimation.

The use of the 1.27 µm O<sub>2</sub> absorption band for greenhouse gas monitoring from space and application to MicroCarb

Abstract. Monitoring CO2 from space is essential to characterize the spatiotemporal distribution of this major greenhouse gas and quantify its sources and sinks. The mixing ratio of CO2 to dry air can be derived from the CO2∕O2 column ratio. The O2 column is usually derived from its absorption signature on the solar reflected spectra over the O2 A band (e.g. Orbiting Carbon Observatory-2 (OCO-2), Thermal And Near infrared Sensor for carbon Observation (TANSO)/Greenhouse Gases Observing Satellite (GOSAT), TanSat). As a result of atmospheric scattering, the atmospheric path length varies with the aerosols' load, their vertical distribution, and their optical properties. The spectral distance between the O2 A band (0.76 µm) and the CO2 absorption band (1.6 µm) results in significant uncertainties due to the varying spectral properties of the aerosols over the globe. There is another O2 absorption band at 1.27 µm with weaker lines than in the A band. As the wavelength is much closer to the CO2 and CH4 bands, there is less uncertainty when using it as a proxy of the atmospheric path length to the CO2 and CH4 bands. This O2 band is used by the Total Carbon Column Observing Network (TCCON) implemented for the validation of space-based greenhouse gas (GHG) observations. However, this absorption band is contaminated by the spontaneous emission of the excited molecule O2*, which is produced by the photo-dissociation of O3 molecules in the stratosphere and mesosphere. From a satellite looking nadir, this emission has a similar shape to the absorption signal that is used. In the frame of the CNES (Centre National d'Études Spatiales – the French National Centre for Space Studies) MicroCarb project, scientific studies have been performed in 2016–2018 to explore the problems associated with this O2* airglow contamination and methods to correct it. A theoretical synthetic spectrum of the emission was derived from an approach based on A21 Einstein coefficient information contained in the line-by-line high-resolution transmission molecular absorption (HITRAN) 2016 database. The shape of our synthetic spectrum is validated when compared to O2* airglow spectra observed by the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY)/Envisat in limb viewing. We have designed an inversion scheme of SCIAMACHY limb-viewing spectra, allowing to determine the vertical distribution of the volume emission rate (VER) of the O2* airglow. The VER profiles and corresponding integrated nadir intensities were both compared to a model of the emission based on the Reactive Processes Ruling the Ozone Budget in the Stratosphere (REPROBUS) chemical transport model. The airglow intensities depend mostly on the solar zenith angle (both in model and data), and the model underestimates the observed emission by ∼15 %. This is confirmed with SCIAMACHY nadir-viewing measurements over the oceans: in such conditions, we have disentangled and retrieved the nadir O2* emission in spite of the moderate spectral resolving power (∼860) and found that the nadir SCIAMACHY intensities are mostly dictated by solar zenith angle (SZA) and are larger than the model intensities by a factor of ∼1.13. At a fixed SZA, the model airglow intensities show very little horizontal structure, in spite of ozone variations. It is shown that with the MicroCarb spectral resolution power (25 000) and signal-to-noise ratio (SNR), the contribution of the O2* emission at 1.27 µm to the observed spectral radiance in nadir viewing may be disentangled from the lower atmosphere/ground absorption signature with a great accuracy. Indeed, simulations with 4ARCTIC radiative transfer inversion tool have shown that the CO2 mixing ratio may be retrieved with the accuracy required for quantifying the CO2 natural sources and sinks (pressure-level error ≤1 hPa; XCO2 accuracy better than 0.4 ppmv) with the O2 1.27 µm band only as the air proxy (without the A band). As a result of these studies (at an intermediate phase), it was decided to include this band (B4) in the MicroCarb design, while keeping the O2 A band for reference (B1). Our approach is consistent with the approach of Sun et al. (2018), who also analysed the potential of the O2 1.27 µm band and concluded favourably for GHG monitoring from space. We advocate for the inclusion of this O2 band on other GHG monitoring future space missions, such as GOSAT-3 and EU/European Space Agency (ESA) CO2-M missions, for a better GHG retrieval.

African biomes are most sensitive to changes in CO<sub>2</sub> under recent and near-future CO<sub>2</sub> conditions

Abstract. Current rates of climate and atmospheric change are likely higher than during the last millions of years. Even higher rates of change are projected in CMIP5 climate model ensemble runs for some Representative Concentration Pathway (RCP) scenarios. The speed of ecological processes such as leaf physiology, demography or migration can differ from the speed of changes in environmental conditions. Such mismatches imply lags between the actual vegetation state and the vegetation state expected under prevailing environmental conditions. Here, we used a dynamic vegetation model, the adaptive Dynamic Global Vegetation Model (aDGVM), to study lags between actual and expected vegetation in Africa under a changing atmospheric CO2 mixing ratio. We hypothesized that lag size increases with a more rapidly changing CO2 mixing ratio as opposed to slower changes in CO2 and that disturbance by fire further increases lag size. Our model results confirm these hypotheses, revealing lags between vegetation state and environmental conditions and enhanced lags in fire-driven systems. Biome states, carbon stored in vegetation and tree cover in Africa are most sensitive to changes in CO2 under recent and near-future levels. When averaged across all biomes and simulations with and without fire, times to reach an equilibrium vegetation state increase from approximately 242 years for 200 ppm to 898 years for 1000 ppm. These results have important implications for vegetation modellers and for policy making. Lag effects imply that vegetation will undergo substantial changes in distribution patterns, structure and carbon sequestration even if emissions of fossils fuels and other greenhouse gasses are reduced and the climate system stabilizes. We conclude that modelers need to account for lag effects in models and in data used for model testing. Policy makers need to consider lagged responses and committed changes in the biosphere when developing adaptation and mitigation strategies.

Assessment of spatio-temporal distribution of CO2 over greater Asia using the WRF–CO2 model

In-depth knowledge of global and regional carbon budget is required for effective policymaking to mitigate the global climate change. However, Asian carbon budget shows large uncertainty due to both lack of sufficient observations and detailed understanding of the existing CO2 observations. A regional air quality model (WRF–CO2) is set up for simulating atmospheric CO2 variations over the greater Asia region (68–124°E, 2°S–45°N) for the period 2010–2012. The WRF–CO2 simulations are compared with observations from nine sites and a global Atmospheric Chemistry Transport Model (ACTM). The comparisons suggest WRF–CO2 simulation is able to capture large scale features in the observed variabilities, with varied ability at fine scales depending on representation of surface fluxes and meteorology around the observation sites. Analysis of CO2 signals from individual flux components suggests that ocean flux has least contribution to the CO2 variation ( 80%). CO2 mixing ratios are found to be maximum in northern hemisphere (NH) winter over East Asia, while they are maximum in NH spring over Indian subcontinent. Observed peak-to-trough seasonal amplitude is lowest (4.5 ppm) for the site Bukit Koto Tabang, Indonesia and highest (29.5 ppm) for Shangdianzi in China. Statistical analysis from monthly mean CO2 time series shows that correlation coefficient and normalised standard deviation with observations, are generally equal or better for the WRF–CO2 than the coarser resolution ACTM. Study of synoptic scale CO2 variations shows that the WRF–CO2 is able to better resolve daytime signatures than those in the night. Year-to-year CO2 variations of seasonal cycle amplitude is highest (~5 ppm) at Nainital, India compared to all other sites.

Processes culminating in the 2015 phreatic explosion at Lascar volcano, Chile, evidenced by multiparametric data

Abstract. Small steam-driven volcanic explosions are common at volcanoes worldwide but are rarely documented or monitored; therefore, these events still put residents and tourists at risk every year. Steam-driven explosions also occur frequently (once every 2–5 years on average) at Lascar volcano, Chile, where they are often spontaneous and lack any identifiable precursor activity. Here, for the first time at Lascar, we describe the processes culminating in such a sudden volcanic explosion that occurred on 30 October 2015, which was thoroughly monitored by cameras, a seismic network, and gas and temperature sensors. Prior to the eruption, we retrospectively identified unrest manifesting as a gradual increase in the number of long-period (LP) seismic events in 2014, indicating an enhanced level of activity at the volcano. Additionally, sulfur dioxide (SO2) flux and thermal anomalies were detected before the eruption. Then, our weather station reported a precipitation event, followed by an increase in steaming and a sudden volcanic explosion at Lascar. The multidisciplinary data exhibited short-term variations associated with the explosion, including (1) an abrupt eruption onset that was seismically identified in the 1–10 Hz frequency band, (2) the detection of a 1.7 km high white-gray eruption column in camera images, and (3) a pronounced spike in SO2 emission rates reaching 55 kg s−1 during the main pulse of the eruption as measured by a mini-differential optical absorption spectroscopy (DOAS) scanner. Continuous carbon dioxide (CO2) and temperature measurements conducted at a fumarole on the southern rim of the Lascar crater revealed a pronounced change in the trend of the relationship between the CO2 mixing ratio and the gas outlet temperature; we speculate that this change was associated with the prior precipitation event. An increased thermal anomaly inside the active crater as observed in Sentinel-2 images and drone overflights performed after the steam-driven explosion revealed the presence of a ∼50 m long fracture truncating the floor of the active crater, which coincides well with the location of the thermal anomaly. This study presents the chronology of events culminating in a steam-driven explosion but also demonstrates that phreatic explosions are difficult to predict, even if the volcano is thoroughly monitored; these findings emphasize why ascending to the summits of Lascar and similar volcanoes is hazardous, particularly after considerable precipitation.

Comparison of Atmospheric Mercury Speciation at a Coastal and an Urban Site in Southeastern Texas, USA

Sixteen months of continuous measurements and the analysis of atmospheric mercury (gaseous elemental mercury GEM, gaseous oxidized mercury GOM, and particulate bound mercury PBM) under urban and coastal settings were conducted in Southeastern Texas. At the urban site, the GEM mean mixing ratio was 185 ppqv, 5%–10% higher than the Northern Hemisphere GEM background level. GOM and PBM mixing ratios were as much as six times higher than their background level. The coastal site GEM mean mixing ratio was 165 ppqv, higher than other coastal sites located in the Northern Hemisphere. GOM and PBM mean mixing ratios at the coastal site were 0.75 ppqv and 0.58 ppqv. The urban site had a higher frequency of high mercury events (>300 ppqv) compared to the coastal site. The diurnal patterns were found for both sites: In the urban environment, GEM accumulated to the maximum mixing ratio just after sunrise and decreased to the minimum mixing ratio in late afternoon. In the coastal environment, GEM decreased at night reaching its minimum mixing ratio before sunrise. The relationship between atmospheric mercury species and meteorological parameters was investigated. An examination of the relationship between atmospheric mercury species and key trace gases was conducted as well, showing that the concurrence of GEM, CO2, CO, CH4, and SO2 maximum mixing ratios was notable and provided evidence they may originate from the same emission source. The coastal site was at times influenced by polluted air from urban Houston and the cleaner Gulf of Mexico marine air at other times.

Characterization of Trace Gases and Green House Gas in Megacity New Delhi

Air pollution and climate change is serious environmental concern due to its visible negative impact on human health. Around 14 Indian cities are placed among top 20 most polluted cities of the world. Trace gas like O3, NOx, CO and CO2 are important pollutants which is associated with human health, climate change and adverse effect on growth and yield of crops. Stratospheric O3 absorbs ultraviolet light and prevents it from reaching to the ground. Greenhouse effect of O3 and CO2 is prominent, O3 in upper troposphere and ranked 3rd for its radiative potential after the carbon dioxide and methane. The amount of O3 generated by photochemical reaction of air pollutants is much larger than the inflow from the stratosphere. This is indicating that trace gases and GHG are generated by anthropogenic activities. It is significantly high in urban area like megacity Delhi as compared to rural area due to excessive anthropogenic activity. The ground level measurements of surface trace gas like O3, NOx, CO and CO2 were conducted in Delhi-Mathura road near traffic intersection for year 2017, January to December. The daily mean concentration of O3, NOx, CO and CO2 were 23.11±17.26ppb (range 58.38 to 6.42ppb), 26.41±4.24ppb (ranges 48.14 to 24.09ppb), 1.56±4.24ppm (ranges 6.6 to 0.69ppm) and 342.54±33.49 (ranges 508.23 to 323.33ppm), respectively. The mixing ratios of O3 were highest of 32ppbv and lowest 17ppbv during the pre-monsoon and monsoon seasons, respectively. While the mixing ratios of both CO and NOx showed highest and lowest values during the winter and monsoon seasons, respectively. The analysis concluded seasonality of O3, CO and NOx were also governed by the long-range transport, mainly with the summer and winter monsoon circulations over the Indian subcontinent. The mixing ratios of CO and NOx show strong correlations during winter and pre-monsoon seasons, while poor correlation in the monsoon season. The mixing ratios of CO and NOx decreased with the increase in wind speed, while O3 tended to increase with the wind speed.

Diurnal Variations of CO2 Mixing Ratio in the Lower Atmosphere by Three Wavelength DIAL

We have conducted the measurement of high accurate CO2 mixing ratio profiles by measuring the temperature profiles simultaneously using the three wavelength CO2 DIAL. The measurements of CO2 diurnal variation in the lower atmosphere were carried out on sunny and cloudy days respectively. We find out that increasing of the CO2 mixing ratio occurs over the altitude of about 2 km from the surface during nighttime. On the other hand, the CO2 mixing ratio decreases over the lower atmosphere during daytime. In particular, the CO2 mixing ratio decreases earlier on sunny days than on cloudy days after sunrise. This result suggests that CO2 absorption by photosynthesis greatly contributes to the strength of the solar radiation.

Systematic investigation of CO2 : NH3 ice mixtures using mid-IR and VUV spectroscopy - part 1: thermal processing.

The adjustment of experimental parameters in interstellar ice analogues can have profound effects on molecular synthesis within an ice system. We demonstrated this by systematically investigating the stoichiometric mixing ratios of CO2 : NH3 ices as a function of thermal processing using mid-IR and VUV spectroscopy. We observed that the type of CO2 bonding environment was dependent on the different stoichiometric mixing ratios and that this pre-determined the NH3 crystallite structure after phase change. The thermal reactivity of the ices was linked to the different chemical and physical properties of the stoichiometric ratios. Our results provide new details into the chemical and physical properties of the different stoichiometric CO2 : NH3 ices enhancing our understanding of the thermally induced molecular synthesis within this ice system.

Characterization of transport regimes and the polar dome during Arctic spring and summer using in situ aircraft measurements

Abstract. The springtime composition of the Arctic lower troposphere is to a large extent controlled by the transport of midlatitude air masses into the Arctic. In contrast, precipitation and natural sources play the most important role during summer. Within the Arctic region sloping isentropes create a barrier to horizontal transport, known as the polar dome. The polar dome varies in space and time and exhibits a strong influence on the transport of air masses from midlatitudes, enhancing transport during winter and inhibiting transport during summer. We analyzed aircraft-based trace gas measurements in the Arctic from two NETCARE airborne field campaigns (July 2014 and April 2015) with the Alfred Wegener Institute Polar 6 aircraft, covering an area from Spitsbergen to Alaska (134 to 17∘ W and 68 to 83∘ N). Using these data we characterized the transport regimes of midlatitude air masses traveling to the high Arctic based on CO and CO2 measurements as well as kinematic 10 d back trajectories. We found that dynamical isolation of the high Arctic lower troposphere leads to gradients of chemical tracers reflecting different local chemical lifetimes, sources, and sinks. In particular, gradients of CO and CO2 allowed for a trace-gas-based definition of the polar dome boundary for the two measurement periods, which showed pronounced seasonal differences. Rather than a sharp boundary, we derived a transition zone from both campaigns. In July 2014 the polar dome boundary was at 73.5∘ N latitude and 299–303.5 K potential temperature. During April 2015 the polar dome boundary was on average located at 66–68.5∘ N and 283.5–287.5 K. Tracer–tracer scatter plots confirm different air mass properties inside and outside the polar dome in both spring and summer. Further, we explored the processes controlling the recent transport history of air masses within and outside the polar dome. Air masses within the springtime polar dome mainly experienced diabatic cooling while traveling over cold surfaces. In contrast, air masses in the summertime polar dome were diabatically heated due to insolation. During both seasons air masses outside the polar dome slowly descended into the Arctic lower troposphere from above through radiative cooling. Ascent to the middle and upper troposphere mainly took place outside the Arctic, followed by a northward motion. Air masses inside and outside the polar dome were also distinguished by different chemical compositions of both trace gases and aerosol particles. We found that the fraction of amine-containing particles, originating from Arctic marine biogenic sources, is enhanced inside the polar dome. In contrast, concentrations of refractory black carbon are highest outside the polar dome, indicating remote pollution sources. Synoptic-scale weather systems frequently disturb the transport barrier formed by the polar dome and foster exchange between air masses from midlatitudes and polar regions. During the second phase of the NETCARE 2014 measurements a pronounced low-pressure system south of Resolute Bay brought inflow from southern latitudes, which pushed the polar dome northward and significantly affected trace gas mixing ratios in the measurement region. Mean CO mixing ratios increased from 77.9±2.5 to 84.9±4.7 ppbv between these two regimes. At the same time CO2 mixing ratios significantly decreased from 398.16 ± 1.01 to 393.81 ± 2.25 ppmv. Our results demonstrate the utility of applying a tracer-based diagnostic to determine the polar dome boundary for interpreting observations of atmospheric composition in the context of transport history.

Quantifying the Evolution of Molecular Production Rates of Comet 21P/Giacobini–Zinner with iSHELL/NASA-IRTF

Abstract This paper presents results from our molecular characterization of comet 21P/Giacobini–Zinner during its 2018 apparition. We followed the comet during four observing runs, for a total of eight nights. The high-resolution spectra of 21P were acquired using iSHELL—the near-infrared high-resolution immersion echelle spectrograph on NASA/IRTF (Maunakea, Hawaii). We detected many cometary emission lines across four customized iSHELL settings in the (2.9–5.2) μm range. CO abundances relative to water displayed a relatively constant behavior during the observing campaign, suggesting a possible correlation between the outgassing of water and CO. While CO mixing ratios in 21P are consistent with the reference median value for Jupiter family comets (JFCs), ethane was depleted relative to the reference median value for JFCs, except for one observing run (August 8 and 9) in which ethane appeared overabundant. We consider several possible causes: an ethane outburst, decreasing outgassing of water, or a seasonal effect owing to nucleus rotation. In the pre-perihelion runs, methanol was overabundant compared with the reference median value for JFCs, however it decreased steadily to a depleted value during 21P’s post-perihelion phase, suggesting a possible seasonal effect. We report 3σ upper limits for acetylene, formaldehyde, ammonia, and methane. The ratios of our measured 3σ upper limits for acetylene and detections of hydrogen cyanide are consistent with the depletion of C2 relative to CN in 21P observed at optical wavelengths. This result confirms that 21P is depleted in the carbon-chain primary volatile responsible for C2 production.

Atmospheric CO2 and CO at Jingdezhen station in central China: Understanding the regional transport and combustion efficiency

Greenhouse gas observation networks have been extensively established in eastern, southern, western, and northern China, but are rare in the developing central China. In this study, atmospheric CO2 and CO were measured in-situ at Jingdezhen (JDZ) station (29.37 °N, 117.22 °E, 87.3 m a.s.l) in central China during Dec. 2017–Nov. 2018. The observation data were filtered as regionally representative and polluted conditions, based on the analysis of diurnal CO2 and CO variations and the impacts of wind directions and speeds. The average CO2 and CO mixing ratios of regionally representative compositions during the study period were 416.2 ppm and 294.9 ppb, respectively, relative to 433.8 ppm and 408.9 ppb for the polluted events. Cluster analysis of HYSPLIT backward trajectories indicated that long-distance transport of air masses originating from northwestern China, eastern China and Jiangxi made the main contributions to variability in regionally representative air. The trajectories passing through urban areas of YRD (Yangtze River Delta), Anhui province in central China, and Nanchang in Jiangxi province carried polluted air masses that probably lead to the increase of CO2 and CO mixing ratios. The enhancements of CO2 (△CO2) and CO (△CO) in polluted conditions relative to the regionally representative conditions presented stronger correlations (R = 0.78, p < 0.001) in wintertime relative to the other seasons at JDZ station, suggesting anthropogenic emissions from fossil fuel and biomass combustion significantly affected CO2 atmospheric loading in the cold season. Lower △CO2/△CO ratio (39.0 ppm/ppm) was observed in December 2017 than other months in winter, and the air mass transport mostly originated from northern China in Dec, implying the strong impact of biomass burning emission sources with low combustion efficiency from northern China. The particular polluted event during 18–21 January in 2018 with high slope value (70.7 ppm/ppm) of △CO2 vs △CO was also investigated, and the analysis of air-mass transport routes indicated high combustion efficiency might be found in Central China such as Jiangxi and Hunan provinces.

A pH‐based experimental method for carbon dioxide exchange evaluation in cylindrical hollow fiber membrane oxygenators

AbstractCarbon dioxide transfer rate (CTR) is an important performance characteristic of a hollow fiber membrane oxygenator (HFMO), which is used as an artificial lung in clinical practices. In vitro measurement of CTR through HFMOs is challenging specifically in investigations with natural blood. In this study, a straightforward and applicable method is presented in order to simulate blood CO2 exchange through HFMOs and consequently calculate the corresponding CTR. The method is based on CO2 dissociation in deionized water resulting in pH drop of the aqueous solution. The results of proposed method are then validated comparing with in vitro investigations using native porcine blood (NPB) in two types of commercially available HFMOs. Moreover, an innovative relationship between effective membrane surface area, blood retention time, and mixing ratio of CO2 and N2 gases in pH drop experiment is introduced in order to simulate the CTR of complicated NPB investigations. The results reveal a good agreement between pH‐based calculated CTRs and those investigated conventionally using NPB. This method would be principally applicable not only for other cylindrical HFMOs but also for other configurations of hollow fiber membrane contactors.

Pollution Events at the High-Altitude Mountain Site Zugspitze-Schneefernerhaus (2670 m a.s.l.), Germany

Within the CO2 time series measured at the Environmental Research Station Schneefernerhaus (UFS), Germany, as part of the Global Atmospheric Watch (GAW) program, pollution episodes are traced back to local and regional emissions, identified by δ13C(CO2) as well as ratios of CO and CH4 to CO2 mixing ratios. Seven episodes of sudden enhancements in the tropospheric CO2 mixing ratio are identified in the measurements of mixing/isotopic ratios during five winter months from October 2012 to February 2013. The short-term CO2 variations are closely correlated with changes in CO and CH4 mixing ratios, achieving mean values of 6.0 ± 0.2 ppb/ppm for CO/CO2 and 6.0 ± 0.1 ppb/ppm for CH4/CO2. The estimated isotopic signature of CO2 sources (δs) ranges between −35‰ and −24‰, with higher values indicating contributions from coal combustion or wood burning, and lower values being the result of natural gas or gasoline. Moving Keeling plots with site-specific data selection criteria are applied to detect these pollution events. Furthermore, the HYSPLIT trajectory model is utilized to identify the trajectories during periods with CO2 peak events. Short trajectories are found covering Western and Central Europe, while clean air masses flow from the Atlantic Ocean and the Arctic Ocean.