An Instrument to Enable Identification of Anthropogenic CO2 Emissions Using Concurrent CO Measurements

We have developed an instrument concept that will enable the measurement of CO from the top of the atmosphere to the Earth's surface with very high sensitivity and at the high spatial and temporal resolutions required by the NRC Decadal Survey mission Active Sensing of Carbon Dioxide (CO2) over Nights, Days and Seasons (ASCENDS). We are developing an innovative CO sensor that will enable the ASCENDS mission to differentiate between anthropogenic and natural sources and sinks of global carbon. The NRC Decadal Survey places particular emphasis on retrieving CO information for the planetary boundary layer. Measurement made using both the 2.3 micron and 4.7 micron channels are needed to achieve the sensitivity required in the lower atmosphere where the degree of CO - CO2 correlation is indicative of anthropogenic sources of CO2. Measurements made using only the 4.7 micron channel cannot provide sufficient sensitivity to CO in the very lowest layers of the atmosphere. The fundamental method we use is Gas Filter Correlation Radiometry (GFCR), a highly successful technique used in other airborne and space-based missions for detecting trace species in the Earth's atmosphere. Our version of GFCR overcomes many of the limitations encountered by prior and existing instruments, allowing us to measure weak signals from small targets very quickly and with extremely high specificity by employing a new dual beam radiometer concept using a focal plane array. Our design will provide a means to make the desired CO measurements for the ASCENDS mission. A simple change in gas filter cell contents would allow the same hardware to measure CH4 with high precision under the nominal ASCENDS mission spatial and temporal constraints. All critical components in the sensor design are mature, many subsystems tested, and the system has been extensively modeled, bringing it to a present Technology Readiness Level (TRL) of 3 (though some individual components are at TRLs 6-9). We are presently developing critical components for the new spectrometer and advancing our understanding of the measurement requirements for both CO and CH4. This new GFCR technique/sensor will enable measurements of trace gases with high sensitivity while maintaining the inherent robustness and simplicity of the more traditional radiometer hardware. Initial estimates of cost/risk of a spacebased 2-channel GFCR indicate that our design is extremely cost effective and will fit within existing ASCENDS mission budget constraints as determined by the NRC Decadal Survey and a NASA-sponsored mission study

In situ measurements of tropospheric volcanic plumes in Ecuador and Colombia during TC

A NASA DC‐8 research aircraft penetrated tropospheric gas and aerosol plumes sourced from active volcanoes in Ecuador and Colombia during the Tropical Composition, Cloud and Climate Coupling (TC4 ) mission in July–August 2007. The likely source volcanoes were Tungurahua (Ecuador) and Nevado del Huila (Colombia). The TC4 data provide rare insight into the chemistry of volcanic plumes in the tropical troposphere and permit a comparison of SO2 column amounts measured by the Ozone Monitoring Instrument (OMI) on the Aura satellite with in situ SO2 measurements. Elevated concentrations of SO2, sulfate aerosol, and particles were measured by DC‐8 instrumentation in volcanic outflow at altitudes of 3–6 km. Estimated plume ages range from ∼2 h at Huila to ∼22–48 h downwind of Ecuador. The plumes contained sulfate‐rich accumulation mode particles that were variably neutralized and often highly acidic. A significant fraction of supermicron volcanic ash was evident in one plume. In‐plume O3 concentrations were ∼70%–80% of ambient levels downwind of Ecuador, but data are insufficient to ascribe this to O3 depletion via reactive halogen chemistry. The TC4 data record rapid cloud processing of the Huila volcanic plume involving aqueous‐phase oxidation of SO2 by H2O2, but overall the data suggest average in‐plume SO2 to sulfate conversion rates of ∼1%–2% h−1 . SO2 column amounts measured in the Tungurahua plume (∼0.1–0.2 Dobson units) are commensurate with average SO2 columns retrieved from OMI measurements in the volcanic outflow region in July 2007. The TC4 data set provides further evidence of the impact of volcanic emissions on tropospheric acidity and oxidizing capacit

Spatio-Temporal Variability of Atmospheric CO2 as Observed from In-Situ Measurements over North America during NASA Field Campaigns (2004-2008)

Regional-scale measurements were made over the eastern United States (Intercontinental Chemical Transport Experiment - North America (INTEX-NA), summer 2004); Mexico (Megacity Initiative: Local and Global Research Observations (MILAGRO), March 2006); the eastern North Pacific and Alaska (INTEX-B May 2006); and the Canadian Arctic (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), spring and summer 2008). For these field campaigns, instrumentation for the in situ measurement of CO2 was integrated on the NASA DC-8 research aircraft providing high-resolution (1 second) data traceable to the WMO CO2 mole fraction scale. These observations provide unique and definitive data sets via their intermediate-scale coverage and frequent vertical profiles (0.1 - 12 km) for examining the variability CO2 exhibits above the Earth s surface. A bottom-up anthropogenic CO2 emissions inventory (1deg 1deg) and processing methodology has also been developed for North America in support of these airborne science missions. In this presentation, the spatio-temporal distributions of CO2 and CO column values derived from the campaign measurements will be examined in conjunction with the emissions inventory and transport histories to aid in the interpretation of the CO2 observations

The production and persistence of ΣRONO2 in the Mexico City plume

Alkyl and multifunctional nitrates (RONO2, ΣANs) have been observed to be a significant fraction of NOy in a number of different chemical regimes. Their formation is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. ΣANs also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Numerous studies have investigated the role of nitrate formation from biogenic compounds and in the remote atmosphere. Less attention has been paid to the role ΣANs may play in the complex mixtures of hydrocarbons typical of urban settings. Measurements of total alkyl and multifunctional nitrates, NO2, total peroxy nitrates (ΣPNs), HNO3 and a representative suite of hydrocarbons were obtained from the NASA DC-8 aircraft during spring of 2006 in and around Mexico City and the Gulf of Mexico. ΣANs were observed to be 10–20% of NOy in the Mexico City plume and to increase in importance with increased photochemical age. We describe three conclusions: (1) Correlations of ΣANs with odd-oxygen (Ox) indicate a stronger role for ΣANs in the photochemistry of Mexico City than is expected based on currently accepted photochemical mechanisms, (2) ΣAN formation suppresses peak ozone production rates by as much as 40% in the near-field of Mexico City and (3) ΣANs play a significant role in the export of NOy from Mexico City to the Gulf Region

In situ measurements of water uptake by black carbon-containing aerosol in wildfire plumes

Water uptake by black carbon (BC)-containing aerosol was quantified in North American wildfire plumes of varying age (1 to ~40 h old) sampled during the SEAC4RS mission (2013). A Humidified Dual SP2 (HD-SP2) is used to optically size BC-containing particles under dry and humid conditions from which we extract the hygroscopicity parameter, κ, of materials internally mixed with BC. Instrumental variability and the uncertainty of the technique are briefly discussed. An ensemble average κ of 0.04 is found for the set of plumes sampled, consistent with previous estimates of bulk aerosol hygroscopicity from biomass burning sources. The temporal evolution of κ in the Yosemite Rim Fire plume is explored to constrain the rate of conversion of BC-containing aerosol from hydrophobic to more hydrophilic modes in these emissions. A BC-specific κ increase of ~0.06 over 40 h is found, fit well with an exponential curve corresponding to a transition from a κ of 0 to a κ of ~0.09 with an e-folding time of 29 h. Although only a few percent of wildfire particles contain BC, a similar κ increase is estimated for bulk aerosol and the measured aerosol composition is used to infer that the observed κ change is driven by a combination of incorporation of ammonium sulfate and oxidation of existing organic materials. Finally, a substantial fraction of wildfire-generated BC-containing aerosol is calculated to be active as cloud condensation nuclei shortly after emission likely indicating efficient wet removal. These results can constrain model treatment of BC from wildfire sources

HO_x chemistry during INTEX-A 2004: Observation, model calculation, and comparison with previous studies

OH and HO_2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment-A (INTEX-A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. The HOx results from INTEX-A are compared to those from previous campaigns and to results for other related measurements from INTEX-A. Throughout the troposphere, observed OH was generally 0.95 of modeled OH; below 8 km, observed HO_2 was generally 1.20 of modeled HO_2. This observed-to-modeled comparison is similar to that for TRACE-P, another midlatitude study for which the median observed-to-modeled ratio was 1.08 for OH and 1.34 for HO_2, and to that for PEM-TB, a tropical study for which the median observed-to-modeled ratio was 1.17 for OH and 0.97 for HO_2. HO_2 behavior above 8 km was markedly different. The observed-to-modeled HO_2 ratio increased from ∼1.2 at 8 km to ∼3 at 11 km with the observed-to-modeled ratio correlating with NO. Above 8 km, the observed-to-modeled HO_2 and observed NO were both considerably greater than observations from previous campaigns. In addition, the observed-to-modeled HO_2/OH, which is sensitive to cycling reactions between OH and HO_2, increased from ∼1.5 at 8 km to almost 3.5 at 11 km. These discrepancies suggest a large unknown HO_x source and additional reactants that cycle HO_x from OH to HO_2. In the continental planetary boundary layer, the observed-to-modeled OH ratio increased from 1 when isoprene was less than 0.1 ppbv to over 4 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HO_x sources. Progress in resolving these discrepancies requires a focused research activity devoted to further examination of possible unknown OH sinks and HO_x sources

Comparison of the chemical evolution and characteristics of 495 biomass burning plumes intercepted by the NASA DC-8 aircraft during the ARCTAS/CARB-2008 field campaign

This paper compares measurements of gaseous and particulate emissions from a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS-2008 experiment: ARCTAS-A, based out of Fairbanks, Alaska USA (3 April to 19 April 2008); ARCTAS-B based out of Cold Lake, Alberta, Canada (29 June to 13 July 2008); and ARCTAS-CARB, based out of Palmdale, California, USA (18 June to 24 June 2008). Extensive investigations of boreal fire plume evolution were undertaken during ARCTAS-B, where four distinct fire plumes that were intercepted by the aircraft over a range of down-wind distances (0.1 to 16 hr transport times) were studied in detail. Based on these analyses, there was no evidence for ozone production and a box model simulation of the data confirmed that net ozone production was slow (on average 1 ppbv h−1 in the first 3 h and much lower afterwards) due to limited NOx. Peroxyacetyl nitrate concentrations (PAN) increased with plume age and the box model estimated an average production rate of ~80 pptv h−1 in the first 3 h. Like ozone, there was also no evidence for net secondary inorganic or organic aerosol formation. There was no apparent increase in aerosol mass concentrations in the boreal fire plumes due to secondary organic aerosol (SOA) formation; however, there were indications of chemical processing of the organic aerosols. In addition to the detailed studies of boreal fire plume evolution, about 500 smoke plumes intercepted by the NASA DC-8 aircraft were segregated by fire source region. The normalized excess mixing ratios (i.e. ΔX/ΔCO) of gaseous (carbon dioxide, acetonitrile, hydrogen cyanide, toluene, benzene, methane, oxides of nitrogen (NOx), ozone, PAN) and fine aerosol particulate components (nitrate, sulfate, ammonium, chloride, organic aerosols and water soluble organic carbon) of these plumes were compared

HOx Observation and Model Comparison During INTEX-A 2004

OH and HO2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment - A (INTEX-A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. Throughout the troposphere, observed OH was generally 0.60 of the modeled OH; below 8 km, observed HO2 was generally 0.78 of modeled HO2. If the over-prediction of tropospheric OH is not due to an instrument calibration error, then it implied less global tropospheric oxidation capacity and longer lifetimes for gases like methane and methyl chloroform than currently thought. This discrepancy falls well outside uncertainties in both the OH measurement and rate coefficients for known reactions and points to a large unknown OH loss. If the modeled OH is forced to agree with observed values by introducing of an undefined OH loss that removed HOx (HOx=OH+HO2), the observed and modeled HO2 and HO2/OH ratios are largely reconciled within the measurement uncertainty. HO2 behavior above 8 km was markedly different. The observed-to-modeled ratio correlating with NO. The observed-to-modeled HO2 ratio increased from approximately 1 at 8 km to more than approximately 2.5 at 11 km with the observed-to-modeled ratio correlating with NO. The observed-to-modeled HO2 and NO were both considerably greater than observations from previous campaigns. In addition, the observed-to-modeled HO2/OH, which is sensitive to cycling reactions between OH and HO2, increased from approximately 1.2 at 8 km to almost 4 above 11 km. In contrast to the lower atmosphere, these discrepancies above 8 km suggest a large unknown HOx source and additional reactants that cycle HOx from OH to HO2. In the continental planetary boundary layer, the OH observed-to-modeled ratio increased from 0.6 when isoprene was less than 0.1 ppbv to over 3 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HOx sources. Progress in resolving these discrepancies requires further examinations of possible unknown OH sinks and HOx sources and a focused research activity devoted to ascertaining the accuracy of the OH and HO2 measurements

Photochemistry in biomass burning plumes and implications for tropospheric ozone over the tropical South Atlantic

Photochemistry occuring in biomass burning plumes over the tropical south Atlantic is analyzed using data collected during the Transport and Atmospheric Chemistry Near the Equator‐Atlantic aircraft expedition conducted during the tropical dry season in September 1992 and a photochemical point model. Enhancement ratios (ΔY/ΔX, where Δ indicates the enhancement of a compound in the plume above the local background mixing ratio, Y are individual hydrocarbons, CO, O3, N2O, HNO3, peroxyacetyl nitrate (PAN), CH2O, acetone, H2O2, CH3OOH, HCOOH, CH3COOH or aerosols and X is CO or CO2) are reported as a function of plume age inferred from the progression of Δnon‐methane hydrocarbons/ΔCO enhancement ratios. Emission, formation, and loss of species in plumes can be diagnosed from progression of enhancement ratios from fresh to old plumes. O3 is produced in plumes over at least a 1 week period with mean ΔO3/ΔCO = 0.7 in old plumes. However, enhancement ratios in plumes can be influenced by changing background mixing ratios and by photochemical loss of CO. We estimate a downward correction of ∼20% in enhancement ratios in old plumes relative to ΔCO to correct for CO loss. In a case study of a large persistent biomass burning plume at 4‐km we found elevated concentrations of PAN in the fresh plume. The degradation of PAN helped maintain NOx mixing ratios in the plume where, over the course of a week, PAN was converted to HNO3. Ozone production in the plume was limited by the availability of NOx, and because of the short lifetime of O3 at 4‐km, net ozone production in the plume was negligible. Within the region, the majority of O3 production takes place in air above median CO concentration, indicating that most O3 production occurs in plumes. Scaling up from the mean observed ΔO3/ΔCO in old plumes, we estimate a minimum regional O3 production of 17×1010molecules O3 cm−2 s−1. This O3 production rate is sufficient to fully explain the observed enhancement in tropospheric O3 over the tropical South Atlantic during the dry season

Method for Balancing Detector Output to a Desired Level of Balance at a Frequency

A multi-gas sensor is provided which modulates a polarized light beam over a broadband of wavelengths between two alternating orthogonal polarization components. The two orthogonal polarization components of the polarization modulated beam are directed along two distinct optical paths. At least one optical path contains one or more spectral discrimination elements, with each spectral discrimination element having spectral absorption features of one or more gases of interest being measured. The two optical paths then intersect, and one orthogonal component of the intersected components is transmitted and the other orthogonal component is reflected. The combined polarization modulated beam is partitioned into one or more smaller spectral regions of interest where one or more gases of interest has an absorption band. The difference in intensity between the two orthogonal polarization components is then determined in each partitioned spectral region of interest as an indication of the spectral emission/absorption of the light beam by the gases of interest in the measurement path. The spectral emission/absorption is indicative of the concentration of the one or more gases of interest in the measurement path. More specifically, one embodiment of the present invention is a gas filter correlation radiometer which comprises a polarizer, a polarization modulator, a polarization beam splitter, a beam combiner, wavelength partitioning element, and detection element. The gases of interest are measured simultaneously and, further, can be measured independently or non-independently. Furthermore, optical or electronic element are provided to balance optical intensities between the two optical paths