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We have analyzed TROPOMI NO2 data over the Copperbelt, a mining region which straddles the Democratic Republic of Congo and Zambia. While the ore mined there is primarily copper, this region is currently of great strategic interest because it is the world’s biggest producer of cobalt. Demand for cobalt, key to clean energy technologies (e.g., electric car batteries), is increasing worldwide and cobalt control is becoming a matter of national and global energy security. The impact of increasing mining-related activities on local air quality (high NOx is harmful to respiratory systems and crops) is unknown.TROPOMI, onboard ESA’s Sentinel-5 Precursor, is an imaging spectrometer in a sun-synchronous orbit at 824 km of altitude which measures concentrations of relevant atmospheric species (trace gases, aerosols, cloud) with quasi-global daily coverage and at high spatial resolution (~ 3.5 x 5.5 km2 in the case of NO2).We show that mining-related activities (such as extraction, smelting, and refining) can be remotely detected based on their TROPOMI NO2 signature, even in the presence of high background NO2 from biomass burning. Annual TROPOMI NO2 means for 2019, 2020, and 2021 show local enrichments consistent with point sources spatially collocated with both mines and large cities where mining-related activities take place. We have identified temporal trends in NO2 from these point sources and, when possible, we have compared those to production figures from the mining companies involved. We have quantified top-down annual NOx (NO+NO2) emissions for each of the point sources identified by applying the divergence method to the TROPOMI retrievals, using ancillary ERA5 meteorological data. Because in situ NOx measurements are not available, we contrast our emission results with emissions from the CAMS-GLOB-ANT v5.1 inventory.Our results show that NOx emissions from mining-related activities can be quantified remotely, which is important in the absence of local air quality monitoring. They also demonstrate that NO2 trend analysis can be a good indicator of mine production. This is particularly relevant for non-publicly traded mining companies, which are not required to publish their production figures. Lack of TROPOMI SO2 enhancements colocated with our NO2 point sources is consistent with SO2 capture and transformation into H2SO4, which is then used in mining-related processes or commercialized.

AirCore in situ vertical profiles sample the atmosphere from near the surface to the lower stratosphere, making them ideal for the validation of satellite tropospheric trace gas data. Here we present intercomparison results of AirCore carbon monoxide (CO) measurements with respect to retrievals from MOPITT (Measurements of Pollution In The Troposphere; version 8) and TROPOMI (TROPOspheric Monitoring Instrument), on board the NASA Terra and ESA Sentinel 5-Precursor satellites, respectively. Mean MOPITT/AirCore total column bias values and their standard deviation (0.4 ± 5.5, 1.7 ± 5.6, and 0.7 ± 6.0 for MOPITT thermal-infrared, near-infrared, and multispectral retrievals, respectively; all in %) are similar to results obtained in MOPITT/NOAA aircraft flask data comparisons from this study and from previous validation efforts. MOPITT CO retrievals are systematically validated using in situ vertical profiles from a variety of aircraft campaigns. Because most aircraft vertical profiles do not sample the troposphere's entire vertical extent, they must be extended upwards in order to be usable in validation. Here we quantify, for the first time, the error introduced in MOPITT CO validation by the use of shorter aircraft vertical profiles extended upwards by analyzing validation results of MOPITT with respect to full and truncated AirCore CO vertical profiles. Our results indicate that the error is small, affects mostly upper tropospheric retrievals (at 300 hPa: ∼ 2.6, 0.8, and 3.2 percent points for MOPITT thermal-infrared, near-infrared, and multispectral, respectively), and may have resulted in the overestimation of MOPITT retrieval biases in that region. TROPOMI can retrieve CO under both clear and cloudy conditions. The latter is achieved by quantifying interfering trace gases and parameters describing the cloud contamination of the measurements together with the CO column; then, the reference CO profiles used in the retrieval are scaled based on estimated above-cloud CO rather than on estimated total CO. We use AirCore measurements as the reference to evaluate the error introduced by this approach in cloudy TROPOMI retrievals over land after accounting for TROPOMI's vertical sensitivity to CO (relative bias and its standard deviation = 2.02 % ± 11.13 %). We also quantify the null-space error, which accounts for differences between the shape of TROPOMI reference profiles and that of AirCore measured profiles (for TROPOMI cloudy enull=0.98 % ± 2.32 %).

Characteristics of the Version 9 (V9) MOPITT ("Measurements of Pollution in the Troposphere") satellite retrieval product for tropospheric carbon monoxide (CO) are described. The new V9 product includes many CO retrievals over land which, in previous MOPITT product versions, would have been discarded by the cloud detection algorithm. Globally, the number of daytime MOPITT retrievals over land has increased by 30–40 % relative to the Version 8 product, although the increase in retrieval coverage exhibits significant geographical variability. Areas benefiting from the improved cloud detection performance include (but are not limited to) source regions often characterized by high aerosol concentrations. The V9 MOPITT product also incorporates a modified calibration strategy for the MOPITT near-infrared (NIR) CO channels, resulting in greater temporal consistency for the NIR-only and thermal infrared-near infrared (TIR-NIR) retrieval variants. Validation results based on in-situ CO profiles acquired from aircraft in a variety of contexts indicate that retrieval biases for V9 are typically within the range of ±5 % and are generally comparable to results for the V8 product.

Following past studies to quantify decadal trends in global carbon monoxide (CO) using satellite observations, we update estimates and find a CO trend in column amounts of about −0.50 % per year between 2002 to 2018, which is a deceleration compared to analyses performed on shorter records that found −1 % per year. Aerosols are co-emitted with CO from both fires and anthropogenic sources but with a shorter lifetime than CO. A combined trend analysis of CO and aerosol optical depth (AOD) measurements from space helps to diagnose the drivers of regional differences in the CO trend. We use the long-term records of CO from the Measurements of Pollution in the Troposphere (MOPITT) and AOD from the Moderate Resolution Imaging Spectroradiometer (MODIS) instrument. Other satellite instruments measuring CO in the thermal infrared, AIRS, TES, IASI, and CrIS, show consistent hemispheric CO variability and corroborate results from the trend analysis performed with MOPITT CO. Trends are examined by hemisphere and in regions for 2002 to 2018, with uncertainties quantified. The CO and AOD records are split into two sub-periods (2002 to 2010 and 2010 to 2018) in order to assess trend changes over the 16 years. We focus on four major population centers: Northeast China, North India, Europe, and Eastern USA, as well as fire-prone regions in both hemispheres. In general, CO declines faster in the first half of the record compared to the second half, while AOD trends show more variability across regions. We find evidence of the atmospheric impact of air quality management policies. The large decline in CO found over Northeast China is initially associated with an improvement in combustion efficiency, with subsequent additional air quality improvements from 2010 onwards. Industrial regions with minimal emission control measures such as North India become more globally relevant as the global CO trend weakens. We also examine the CO trends in monthly percentile values to understand seasonal implications and find that local changes in biomass burning are sufficiently strong to counteract the global downward trend in atmospheric CO, particularly in late summer., SCOPUS: ar.j, info:eu-repo/semantics/published

We have analyzed TROPOspheric Monitoring Instrument (TROPOMI) carbon monoxide (CO) data acquired between November 2017 and March 2019 with respect to other satellite (MOPITT, Measurement Of Pollution In The Troposphere) and airborne (ATom, Atmospheric Tomography mission) datasets to better understand TROPOMI's contribution to the global tropospheric CO record (2000 to present). MOPITT and TROPOMI are two of only a few satellite instruments to ever derive CO from solar-reflected radiances. Therefore, it is particularly important to understand how these two datasets compare. Our results indicate that TROPOMI CO retrievals over land show excellent agreement with respect to MOPITT: relative biases and their SD (i.e., accuracy and precision) are on average -3.73%±11.51%, -2.24%±12.38%, and -3.22%±11.13% compared to the MOPITT TIR (thermal infrared), NIR (near infrared), and TIR + NIR (multispectral) products, respectively. TROPOMI and MOPITT data also show good agreement in terms of temporal and spatial patterns. Despite depending on solar-reflected radiances for its measurements, TROPOMI can also retrieve CO over bodies of water if clouds are present by approximating partial columns under cloud tops using scaled, model-based reference CO profiles. We quantify the bias of TROPOMI total column retrievals over bodies of water with respect to colocated in situ ATom CO profiles after smoothing the latter with the TROPOMI column averaging kernels (AKs), which account for signal attenuation under clouds (relative bias and its SD =3.25%±11.46 %). In addition, we quantify enull (the null-space error), which accounts for differences between the shape of the TROPOMI reference profile and that of the ATom true profile (enull=2.16%±2.23 %). For comparisons of TROPOMI and MOPITT retrievals over open water we compare TROPOMI total CO columns to their colocated MOPITT TIR counterparts. Relative bias and its SD are 2.98 %±15.71 % on average. We investigate the impact of discrepancies between the a priori and reference CO profiles (used by MOPITT and TROPOMI, respectively) on CO retrieval biases by applying a null-space adjustment (based on the MOPITT a priori) to the TROPOMI total column values. The effect of this adjustment on MOPITT and TROPOMI biases is minor, typically 1–2 percentage points.

Measurements made by the MOPITT (“Measurements of Pollution in the Troposphere”) instrument on the NASA Terra polar-orbiting platform enable the retrieval of tropospheric carbon monoxide (CO) concentrations. As determined by the Terra orbit and MOPITT swath width, the frequency of MOPITT observations at a specific location, or measurement sampling frequency, is typically about once every three to four days. However, because the MOPITT retrieval algorithm is only applicable to clear-sky scenes, MOPITT retrieval sampling frequency strongly depends on regional cloudiness and can be much smaller than the measurement sampling frequency. Moreover, highly polluted scenes, characterized by high aerosol optical depths, can be confused with cloudy scenes and thus be discarded unnecessarily by the MOPITT cloud detection algorithm. Herein are described revisions to this algorithm which substantially increase retrieval sampling over land in varying pollution conditions. The performance of the revised cloud detection algorithm is evaluated through validation, case studies, and continental-scale maps of retrieval sampling frequency. Presented case studies illustrate (1) why the current operational MOPITT cloud detection algorithm excludes extended areas of potentially valuable cloud-free MOPITT observations and (2) how, for the same scenes, improved retrieval coverage benefits analyses of regional CO variability. Maps of retrieval sampling frequency for South America and Asia exhibit well-defined improvements, especially in regions with poor sampling frequency in the current product.

The MOPITT (Measurements of Pollution in the Troposphere) satellite instrument has been making observations of atmospheric carbon monoxide since 2000. Recent enhancements to the MOPITT retrieval algorithm have resulted in the release of the version 7 (V7) product. Improvements include (1) representation of growing atmospheric concentrations of N2O, (2) use of meteorological fields from the MERRA-2 (Modern-Era Retrospective Analysis for Research and Applications) reanalysis for the entire MOPITT mission (instead of MERRA), (3) use of the MODIS (Moderate-Resolution Imaging Spectroradiometer) Collection 6 cloud mask product (instead of Collection 5), (4) a new strategy for radiance-bias correction and (5) an improved method for calibrating MOPITT's near-infrared (NIR) radiances. Statistical comparisons of V7 validation results with corresponding V6 results are presented, using aircraft in situ measurements as the reference. Clear improvements are demonstrated for V7 products with respect to overall retrieval biases, bias variability and bias drift uncertainty.

The performance of the Measurements of Pollution in the Troposphere (MOPITT) retrievals over urban regions has not been validated systematically, even though MOPITT observations are widely used to study CO over urban regions. Here we validate MOPITT products over urban regions using aircraft measurements from DISCOVER-AQ, SEAC4RS, ARIAs, A-FORCE, and KORUS-AQ campaigns. Overall, MOPITT performs reasonably well over both urban and non-urban regions, overall biases for V8J and V8T vary from −0.7 % to 0.0 %, and from 2.0 % to 3.5 %, respectively. The evaluation statistics of MOPITT V8J and V8T over non-urban regions are better than that over urban regions with smaller biases and higher correlation coefficients. We find that the performance of MOPITT V8J and V8T at high CO concentrations is not as good as that at low CO concentrations, although CO variability may tend to exaggerate retrieval biases in heavily-polluted scenes. We test the sensitivities of validation results to assumptions and data filters applied during the comparisons of MOPITT retrievals and in-situ profiles. The results at the surface are insensitive to the model-based profile extension (required due to aircraft altitude limitations) whereas the results at levels with limited aircraft observations are more sensitive to the model-based profile extension. The validation results are insensitive to the allowed maximum time difference as criteria for co-location (12 hours, 6 hours, 3 hours, and 1 hour), and are generally insensitive to the radius for co-location, except for the case where the radius is small (25 km) and hence the MOPITT retrievals included in the validation become very small. Daytime MOPITT products have overall smaller biases than nighttime MOPITT products when comparing both MOPITT daytime and nighttime retrievals to the daytime aircraft observations. However, it would be premature to draw conclusions on the performance of MOPITT nighttime retrievals without nighttime aircraft observations. Applying signal-to-noise ratio (SNR) filters does not necessarily improve the overall agreement between MOPITT retrievals and in-situ profiles, likely due to the reduced number of MOPITT retrievals that result for comparison. Comparisons of MOPITT retrievals and in-situ profiles over complex urban or polluted regimes are inherently challenging due to spatial and temporal variabilities of CO within MOPITT retrieval pixels (i.e., footprints). We demonstrate the some of that errors are due to CO representativeness with these sensitivity tests, but further quantification of validation errors due to CO variability within the MOPITT footprint will require future work.

The MOPITT (Measurements of Pollution in the Troposphere) satellite instrument has been making nearly continuous observations of atmospheric carbon monoxide (CO) since 2000. Satellite observations of CO are routinely used to analyze emissions from fossil fuels and biomass burning, as well as the atmospheric transport of those emissions. Recent enhancements to the MOPITT retrieval algorithm have resulted in the release of the version 8 (V8) product. V8 products benefit from updated spectroscopic data for water vapor and nitrogen used to develop the operational radiative transfer model and exploit a new method for minimizing retrieval biases through parameterized radiance bias correction. In situ datasets used for algorithm development and validation include the NOAA (National Oceanic and Atmospheric Administration) and HIPPO (HIAPER Pole-to-Pole Observations) datasets used for earlier MOPITT validation work in addition to measurements from the ACRIDICON-CHUVA (Aerosol, Cloud, Precipitation, and Radiation Interactions and Dynamics of Convective Cloud Systems – Cloud processes of the main precipitation systems in Brazil: A contribution to cloud resolving modeling and to the GPM (Global Precipitation Measurement)), KORUS-AQ (The Korea-United States Air Quality Study), and ATom (The Atmospheric Tomography Mission) programs. Validation results illustrate clear improvements with respect to long-term bias drift and geographically variable retrieval bias. For example, whereas bias drift for the V7 thermal-infrared (TIR)-only product exceeded 0.5 % yr−1 for levels in the upper troposphere (e.g., at 300 hPa), bias drift for the V8 TIR-only product is found to be less than 0.1 % yr−1 at all levels. Also, whereas upper-tropospheric (300 hPa) retrieval bias in the V7 TIR-only product exceeded 10 % in the tropics, corresponding V8 biases are less than 5 % (in terms of absolute value) at all latitudes and do not exhibit a clear latitudinal dependence.

We analyze satellite retrievals of carbon monoxide from the MOPITT (Measurements of Pollution in the Troposphere) instrument over the Amazon Basin, focusing on the MOPITT Version 6 "multispectral" retrieval product (exploiting both thermal-infrared and near-infrared channels). Validation results based on in situ vertical profiles measured between 2010 and 2013 are presented for four sites in the Amazon Basin. Results indicate a significant negative bias in retrieved lower-tropospheric CO concentrations. The possible influence of smoke aerosol as a source of retrieval bias is investigated using collocated Aerosol Robotic Network (AERONET) aerosol optical depth (AOD) measurements at two sites but does not appear to be significant. Finally, we exploit the MOPITT record to analyze both the mean annual cycle and the interannual variability of CO over the Amazon Basin since 2002.

The Measurements of Pollution in the Troposphere (MOPITT) Version 6 (V6) product for carbon monoxide (CO) incorporates several enhancements which will benefit many users of MOPITT data. V6 algorithm improvements are described in detail, and V6 validation results are presented. First, a geolocation bias related to the orientation of the MOPITT instrument relative to the TERRA platform was characterized and eliminated. Second, the variable a priori for CO concentrations for V6 is based on simulations performed with the chemical transport model Community Atmosphere Model with Chemistry (CAM-chem) for the years 2000–2009 instead of the model-derived climatology for 1997–2004 used for V5. Third, meteorological fields required for V6 retrieval processing are extracted from the MERRA (Modern-Era Retrospective Analysis For Research And Applications) reanalysis. Finally, a significant latitude-dependent retrieval bias in the upper troposphere in Version 5 products has been substantially reduced.

[1] Validation results are reported for the MOPITT (Measurements of Pollution in the Troposphere) “Version 5” (V5) product for tropospheric carbon monoxide (CO) and are compared to results for the “Version 4” product. The V5 retrieval algorithm introduces (1) a method for reducing retrieval bias drift associated with long-term instrumental degradation, (2) a more exact representation of the effects of random errors in the radiances and, for the first time, (3) the use of MOPITT's near-infrared (NIR) radiances to complement the thermal-infrared (TIR) radiances. Exploiting TIR and NIR radiances together facilitates retrievals of CO in the lowermost troposphere. V5 retrieval products based (1) solely on TIR measurements, (2) solely on NIR measurements and (3) on both TIR and NIR measurements are separately validated and analyzed. Actual retrieved CO profiles and total columns are compared with equivalent retrievals based on in situ measurements from (1) routine NOAA aircraft sampling mainly over North America and (2) the “HIAPER Pole to Pole Observations” (HIPPO) field campaign. Particular attention is focused on the long-term stability and geographical uniformity of the retrieval errors. Results for the retrieved total column clearly indicate reduced temporal bias drift in the V5 products compared to the V4 product, and do not exhibit a positive bias in the Southern Hemisphere, which is evident in the V4 product.

The growth of mega-cities leads to air quality problems directly affecting the citizens. Satellite measurements are becoming of higher quality and quantity, which leads to more accurate satellite retrievals of the enhanced air pollutant concentrations over large cities. In this paper, we compare and discuss both an existing and a new method for estimating urban scale trends in CO emissions using multi-year retrievals from the MOPITT satellite instrument. The first method is mainly based on satellite data, which has the advantage of fewer assumptions, but also comes with uncertainties and limitations as shown in this paper. To improve the reliability of urban to regional scale emission trend estimation, we simulate MOPITT retrievals using the Weather Research and Forecast model with chemistry core (WRF-Chem). The difference between model and retrieval is used to optimize CO emissions in WRF-Chem, focusing on the city of Madrid, Spain. This method has the advantage over the existing method in that it allows both a trend analysis of CO concentrations and a quantification of CO emissions. Our analysis confirms thatMOPITT is capable of detecting CO enhancements overMadrid, although significant differences remain between the yearly averaged model output and satellite measurements (R2 = 0.75) over the city. After optimization, we find Madrid CO emissions to be lower by 48 % for 2002 and by 17 % for 2006 compared with the EdgarV4.2 emission inventory. The MOPITT derived emission adjustments lead to better agreement with the European emission inventory TNO-MAC-III for both years. This suggests that the downward trend in CO emissions over Madrid is overestimated in EdgarV4.2 and more realistically represented in TNO-MAC-III. However, our satellite and model based emission estimates have large uncertainties, around 20 % for 2002 and 50 % for 2006.

Chryse and Acidalia Planitiae show numerous examples of enigmatic landforms previously interpreted to have been influenced by a water/ice-rich geologic history. These landforms include giant polygons bounded by kilometer-scale arcuate troughs, bright pitted mounds, and mesa-like features. To investigate the significance of the last we have analyzed in detail the region between 60°N, 290°E and 10°N, 360°E utilizing HiRISE (High Resolution Imaging Science Experiment) images as well as regional-scale data for context. The mesas may be analogous to terrestrial tuyas (emergent sub-ice volcanoes), although definitive proof has not been identified. We also report on a blocky unit and associated landforms (drumlins, eskers, inverted valleys, kettle holes) consistent with ice-emplaced volcanic or volcano-sedimentary flows. The spatial association between tuya-like mesas, ice-emplaced flows, and further possible evidence of volcanism (deflated flow fronts, volcanic vents, columnar jointing, rootless cones), and an extensive fluid-rich substratum (giant polygons, bright mounds, rampart craters), allows for the possibility of glaciovolcanic activity in the region. Landforms indicative of glacial activity on Chryse/Acidalia suggest a paleoclimatic environment remarkably different from today’s. Climate changes on Mars (driven by orbital/obliquity changes) or giant outflow channel activity could have resulted in ice-sheet-related landforms far from the current polar caps.

We provide an overview of features indicative of the interaction between water and lava and/or magma on Mars as seen by the High Resolution Imaging Science Experiment (HiRISE) camera during the Primary Science Phase of the Mars Reconnaissance Orbiter (MRO) mission. The ability to confidently resolve meter-scale features from orbit has been extremely useful in the study of the most pristine examples. In particular, HiRISE has allowed the documentation of previously undescribed features associated with phreatovolcanic cones (formed by the interaction of lava and groundwater) on rapidly emplaced flood lavas. These include “moats” and “wakes” that indicate that the lava crust was thin and mobile, respectively [Jaeger, W.L., Keszthelyi, L.P., McEwen, A.S., Dundas, C.M., Russel, P.S., 2007. Science 317, 1709–1711]. HiRISE has also discovered entablature-style jointing in lavas that is indicative of water-cooling [Milazzo, M.P., Keszthelyi, L.P., Jaeger, W.L., Rosiek, M., Mattson, S., Verba, C., Beyer, R.A., Geissler, P.E., McEwen, A.S., and the HiRISE Team, 2009. Geology 37, 171–174]. Other observations strongly support the idea of extensive volcanic mudflows (lahars). Evidence for other forms of hydrovolcanism, including glaciovolcanic interactions, is more equivocal. This is largely because most older and high-latitude terrains have been extensively modified, masking any earlier 1–10 m scale features. Much like terrestrial fieldwork, the prerequisite for making full use of HiRISE’s capabilities is finding good outcrops.

The High Resolution Imaging Science Experiment (HiRISE) on the Mars Reconnaissance Orbiter (MRO) acquired 8 terapixels of data in 9137 images of Mars between October 2006 and December 2008, covering ~0.55% of the surface. Images are typically 5–6 km wide with 3-color coverage over the central 20% of the swath, and their scales usually range from 25 to 60 cm/pixel. Nine hundred and sixty stereo pairs were acquired and more than 50 digital terrain models (DTMs) completed; these data have led to some of the most significant science results. New methods to measure and correct distortions due to pointing jitter facilitate topographic and change-detection studies at sub-meter scales. Recent results address Noachian bedrock stratigraphy, fluvially deposited fans in craters and in or near Valles Marineris, groundwater flow in fractures and porous media, quasi-periodic layering in polar and non-polar deposits, tectonic history of west Candor Chasma, geometry of clay-rich deposits near and within Mawrth Vallis, dynamics of flood lavas in the Cerberus Palus region, evidence for pyroclastic deposits, columnar jointing in lava flows, recent collapse pits, evidence for water in well-preserved impact craters, newly discovered large rayed craters, and glacial and periglacial processes. Of particular interest are ongoing processes such as those driven by the wind, impact cratering, avalanches of dust and/or frost, relatively bright deposits on steep gullied slopes, and the dynamic seasonal processes over polar regions. HiRISE has acquired hundreds of large images of past, present and potential future landing sites and has contributed to scientific and engineering studies of those sites. Warming the focal-plane electronics prior to imaging has mitigated an instrument anomaly that produces bad data under cold operating conditions.

Water has supposedly marked the surface of Mars and produced characteristic landforms. To understand the history of water on Mars, we take a close look at key locations with the High-Resolution Imaging Science Experiment on board the Mars Reconnaissance Orbiter, reaching fine spatial scales of 25 to 32 centimeters per pixel. Boulders ranging up to approximately 2 meters in diameter are ubiquitous in the middle to high latitudes, which include deposits previously interpreted as finegrained ocean sediments or dusty snow. Bright gully deposits identify six locations with very recent activity, but these lie on steep (20 degrees to 35 degrees) slopes where dry mass wasting could occur. Thus, we cannot confirm the reality of ancient oceans or water in active gullies but do see evidence of fluvial modification of geologically recent mid-latitude gullies and equatorial impact craters.

The physical factors responsible for the variability observed in OH infrared (IR) fundamentals in dioctahedral phyllosilicates, due to octahedral substitution of Al3+ by Mg2+, Fe2+, and Fe3+, are discussed here. The data analyzed consist of experimental frequencies as well as frequencies modeled using Density Functional Theory (DFT) calculations. The charge of the octahedral cations surrounding the OH is one of the main factors affecting both the OH stretch and the in-plane bend; cationic electronegativity and ionic radius play important roles in the stretch and bend modes, respectively. The mass of the octahedral cations does not affect the OH fundamental vibrations. The nature of the octahedral cations alone can explain most of the variability observed in the OH in-plane bend, making this fundamental vibration the most suitable for assessing octahedral composition. Discrepancies between modeled and experimental OH stretch frequencies indicate the existence of other factors governing this fundamental vibration. Further DFT calculations indicate that apical O atoms of the tetrahedral sheet with unsatisfied charges due to octahedral and/or tetrahedral substitutions can explain these discrepancies. The modeling results are utilized to predict the frequency of the OH stretch and in-plane-bend combination band that occurs near 4545 cm−1 (2.2 μm) in phyllosilicates. This band can be observed in imaging spectrometer data, allowing for the detection and analysis of phyllosilicates and other minerals in large natural systems. The modeling results confirm that the variability observed in the combination band of dioctahedral phyllosilicates reflects octahedral and, to a certain degree, tetrahedral composition, but not interlayer composition.

The infrared (IR) spectra of small clusters of atoms ([MM′(OH)2] and [MM′ (OH)2 (H2O)6], where M, M′ = Al3+, Mg2+, Fe2+, Fe3+) mimicking the environment of the OH group in dioctahedral phyllosilicates have been modeled using ab initio quantum mechanical calculations. These modeling results are relevant to establishing the connections between IR spectra of phyllosilicates and their composition, and to investigate the utility of quantum mechanical models for calculating IR frequencies of minerals. This study focused on the OH stretch and in-plane bend fundamentals, because they give rise to a combination band near 4545 cm−1 (2.2 μm) that can be observed in imaging spectrometer or hyperspectral remote sensing data. A comparison among results obtained using both ab initio [Hartree-Fock (HF) and Density Functional Theory (DFT)], and semi-empirical [PM3(tm)] methods, showed that the DFT model approaches IR frequency experimental values most closely. IR spectra of phyllosilicates were modeled using the DFT method. The modeled frequencies were scaled using a mode-dependent linear transformation, and experimental frequencies were reproduced satisfactorily. The modeling results show that most of the variability observed in the OH in-plane bend fundamental of dioctahedral phyllosilicates can be explained by the effects of neighboring octahedral cations alone. Discrepancies between modeling and experimental results in the case of the OH stretch point to the existence of factors other than the nature of the neighboring octahedral cations, such as tetrahedral substitution, affecting this fundamental mode.

Satellite observations of tropospheric carbon monoxide (CO) are employed in diverse applications including air quality studies, chemical weather forecasting and the characterization of CO emissions through inverse modeling. The TERRA / MOPITT ('Measurements of Pollution in the Troposphere') instrument incorporates a set of gas correlation radiometers to observe CO simultaneously in both a thermal-infrared (TIR) band near 4.7 µm and a near-infrared (NIR) band near 2.3 μm. This multispectral capability is unique to MOPITT. The MOPITT retrieval algorithm for vertical profiles of CO has been refined almost continuously since TERRA was launched at the end of 1999. Retrieval algorithm enhancements are the result of ongoing analyses of instrument performance, improved radiative transfer modeling, and systematic comparisons with correlative data, including in-situ profiles measured from aircraft and products from other satellite instruments. In the following, we describe the methods used to routinely evaluate MOPITT CO profiles. As the satellite instrument with the longest record for CO, methods for assessing the long-term stability are becoming increasingly important.

The Measurements of Pollution in the Troposphere (MOPITT) instrument on the NASA Terra platform has now acquired over thirteen years of global tropospheric carbon monoxide (CO) observations, forming the longest satellite record for an important pollutant. [...]

Atmospheric carbon monoxide (CO) distributions are controlled by anthropogenic emissions, biomass burning, transport and oxidation by reaction with the hydroxyl radical (OH). Quantifying trends in CO is therefore important for understanding changes related to all of these contributions. Here we present a comprehensive record of satellite observations from 2000 through 2011 of total column CO using the available measurements from nadir-viewing thermal infrared instruments: MOPITT, AIRS, TES and IASI. We examine trends for CO in the Northern and Southern Hemispheres along with regional trends for Eastern China, Eastern USA, Europe and India. We find that all the satellite observations are consistent with a modest decreasing trend ∼-1 % yr-1 in total column CO over the Northern Hemisphere for this time period and a less significant, but still decreasing trend in the Southern Hemisphere. Although decreasing trends in the United States and Europe have been observed from surface CO measurements, we also find a decrease in CO over E. China that, to our knowledge, has not been reported previously. Some of the interannual variability in the observations can be explained by global fire emissions, but the overall decrease needs further study to understand the implications for changes in anthropogenic emissions. © 2013 Author(s)., SCOPUS: ar.j, info:eu-repo/semantics/published

Volcanic degassing produces abundant H2O and CO2, as well as SO2, HCl, H2S, S2, H2, HF, CO, and SiF4. Volcanic SO2, HCl, and H2S have been detected from satellites in the past; the remaining species are analyzed in situ or using airborne instruments, with all the consequent limitations in safety and sampling, and at elevated costs. We report identification of high CO concentrations consistent with a volcanic origin (the 2010 Eyjafjallajokull and 2011 Grimsvotn eruptions in Iceland) in data from the Measurements of Pollution in the Troposphere instrument (MOPITT) onboard EOS/Terra. The high CO values coincide spatially and temporally with ash plumes emanating from the eruptive centers, with elevated SO2 and aerosol optical thickness, as well as with high CO values in data from the Infrared Atmospheric Sounding Interferometer (IASI), onboard MetOp-A. CO has a positive indirect radiative forcing; climate models currently do not account for volcanic CO emissions. Given global volcanic CO2 emissions between 130 and 440 Tg/year and volcanic CO:CO2 ratios from the literature, we estimate that average global volcanic CO emissions may be on the order of ∼5.5 Tg/year, equivalent to the CO emissions caused by combined fossil fuel and biofuel combustion in Australia.

Products from the Measurements Of Pollution In The Troposphere (MOPITT) instrument are regularly validated using in situ airborne measurements. However, few of these measurements reach into the upper troposphere, thus hindering MOPITT validation in that region. Here we evaluate upper tropospheric (~500 hPa to the tropopause) MOPITT CO profiles by comparing them to satellite Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) retrievals and to measurements from the High-performance Instrumented Airborne Platform for Environmental Research Pole to Pole Observations (HIPPO) Quantum Cascade Laser Spectrometer (QCLS). Direct comparison of colocated v5 MOPITT thermal infrared-only retrievals, v3.0 ACE-FTS retrievals, and HIPPO-QCLS measurements shows a slight positive MOPITT CO bias within its 10% accuracy requirement with respect to the other two data sets. Direct comparison of colocated ACE-FTS and HIPPO-QCLS measurements results in a small number of samples due to the large disparity in sampling pattern and density of these data sets. Thus, two additional indirect techniques for comparison of noncoincident data sets have been applied: tracer-tracer (CO-O3) correlation analysis and analysis of profiles in tropopause coordinates. These techniques suggest a negative bias of ACE-FTS with respect to HIPPO-QCLS; this could be caused by differences in resolution (horizontal, vertical) or by deficiencies in the ACE-FTS CO retrievals below ~20 km of altitude, among others. We also investigate the temporal stability of MOPITT and ACE-FTS data, which provide unique global CO records and are thus important in climate analysis. Our results indicate that the relative bias between the two data sets has remained generally stable during the 2004–2010 period.

[1] Fresh-appearing gully deposits are found at tens of sites in the southern hemisphere of Mars. These deposits have latitudinal and azimuthal dependences similar to the overall preferences of southern-hemisphere gullies, suggesting that most gullies can undergo such events. Definite changes are seen at ten sites, including two previously reported. These include visible modification of gully channels and aprons. Those formation intervals constrained to better than one Mars year tend to include winter and exclude summer, suggesting seasonal activity. This seasonal activity is consistent with proposed models for gully formation driven by CO2 frost, although at least some of the new deposits are probably due to dry granular flow with no volatile involvement. As these deposits are capable of effecting distinct topographic changes to gully aprons and channels, they represent a significant component of recent gully evolution.

[1] We analyzed remote-sensing observations of the Isidis Basin, Gusev Crater, and Meridiani Planum landing sites for Beagle II, MER-A Spirit, and MER-B Opportunity spacecraft, respectively. We emphasized the thermophysical properties using daytime and nighttime radiance measurements from the Mars Global Surveyor (MGS) Thermal Emission Spectrometer and Mars Odyssey Thermal Emission Imaging System (THEMIS) and thermal inertias derived from nighttime data sets. THEMIS visible images, MGS Mars Orbiter Camera (MOC) narrow-angle images, and MGS Mars Orbiter Laser Altimeter (MOLA) data are incorporated as well. Additionally, the remote-sensing data were compared with ground-truth at the MER sites. The Isidis Basin surface layer has been shaped by aeolian processes and erosion by slope winds coming off of the southern highlands and funneling through notches between massifs. In the Gusev region, surface materials of contrasting thermophysical properties have been interpreted as rocks or bedrock, duricrust, and dust deposits; these are consistent with a complex geological history dominated by volcanic and aeolian processes. At Meridiani Planum the many layers having different thermophysical and erosional properties suggest periodic deposition of differing sedimentological facies possibly related to clast size, grain orientation and packing, or mineralogy.

[1] The advent of high spatial resolution instruments onboard orbiting Mars missions entails the need for identification of critical regions to be analyzed in further detail. We present the Spectral Variance Index (SVI), a method to detect regions of large surface materials diversity compared to the average of the planet. Such diversity may be indicative of significant active and past geological processes, such as hydrothermal activity, chemical and mechanical sedimentation, pyroclastic volcanism, erosion unveiling layering of diverse composition, and weathering, among others. The SVI was derived from statistical analysis of the Mars Global Surveyor Thermal Emission Spectrometer spectral data set for 5 × 5 degree cells covering the entire planet; global SVI maps depicting surface materials diversity were produced. Regions of elevated SVI occur clustered in low-albedo, high-thermal inertia regions, indicative of rock-dominated surfaces. The surface geology of two regions of anomalously high SVI (Nili Fossae and Mare Tyrrhenum), and one region of low SVI (Amazonis Planitia), was investigated utilizing spectroscopic, thermophysical, and morphological data. The following data-derived spectral end-members were identified in all three regions: atmospheric water-ice, surface dust (both in close spatial relationship), and instrument noise. The high SVI regions show also signatures characteristic of surfaces type 1 and 2, forsterite (Nili), phyllosilicates and/or high-Si glass (Nili), and another end-member most consistent with fayalite (or, alternatively, high-Ca pyroxene) in volcanic materials (Tyrrhenum). The SVI method effectively identifies regions, both previously known and new ones, of surface material diversity on Mars; spectroscopic data of higher spatial resolution will improve our understanding of their compositional diversity.

[1] Gusev Crater, the Mars Exploration Rover Spirit landing site (160 km diameter; 14.5°S, 184.5°W), has been identified in previous studies as a prime site of geological and exobiological interest on the basis of its potential for having hosted a fluviolacustrine environment; such environment may have been favorable for the development of biological activity. The origin and nature of the materials present at the surface of Gusev Crater are still being debated. In previous studies based on geomorphological and thermophysical data, surface materials in the crater have been interpreted as originating from fluviolacustrine, volcanic, or aeolian processes, or combinations thereof. We present results from the analysis of newly compiled thermophysical (Thermal Emission Spectrometer (TES) and Thermal Emission Imaging System (THEMIS)), spectroscopic (TES), and visible (THEMIS and Mars Observer Camera) data for the Gusev region. These data were analyzed using a new mosaicking technique developed to match the values of contiguous scenes and to produce seamless mosaics apt for geological interpretation. Thermophysical, spectroscopic, and morphological evidence point to the presence of local outcrops of lava flows of basaltic composition, materials consistent with a regolith developed from basaltic materials, fine-grained deposits of basaltic composition strongly modified by wind erosion, and wind deposits. According to these findings, we conclude that most of the materials occupying the present surface of Gusev have characteristics consistent with those of volcanic and aeolian deposits. Fluviolacustrine deposits proposed by other authors may exist under the volcanic materials and may be exposed in impact craters.