Near-IR photodissociation of peroxy acetyl nitrate

Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (Jnear−IR ~3×10^−8 s^−1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with Jnear−IR ~10^−5 s^−1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of 10 freedom in PAN, which make 4[Greek nu]CH the lowest overtone excitation with a high photodissociation yield (as opposed to 2[Greek nu]OH in PNA)

Improvement of the retrieval algorithm for GOSAT SWIR XCO_2 and XCH_4 and their validation using TCCON data

The column-averaged dry-air mole fractions of carbon dioxide and methane (XCO_2 and XCH_4) have been retrieved from Greenhouse gases Observing SATellite (GOSAT) Short-Wavelength InfraRed (SWIR) observations and released as a SWIR L2 product from the National Institute for Environmental Studies (NIES). XCO_2 and XCH_4 retrieved using the version 01.xx retrieval algorithm showed large negative biases and standard deviations (−8.85 and 4.75 ppm for XCO_2 and −20.4 and 18.9 ppb for XCH_4, respectively) compared with data of the Total Carbon Column Observing Network (TCCON). Multiple reasons for these error characteristics (e.g., solar irradiance database, handling of aerosol scattering) are identified and corrected in a revised version of the retrieval algorithm (version 02.xx). The improved retrieval algorithm shows much smaller biases and standard deviations (−1.48 and 2.09 ppm for XCO_2 and −5.9 and 12.6 ppb for XCH_4, respectively) than the version 01.xx. Also, the number of post-screened measurements is increased, especially at northern mid- and high-latitudinal areas

Neural network-based colonoscopic diagnosis using on-line learning and differential evolution

In this paper, on-line training of neural networks is investigated in the context of computer-assisted colonoscopic diagnosis. A memory-based adaptation of the learning rate for the on-line back-propagation (BP) is proposed and used to seed an on-line evolution process that applies a differential evolution (DE) strategy to (re-) adapt the neural network to modified environmental conditions. Our approach looks at on-line training from the perspective of tracking the changing location of an approximate solution of a pattern-based, and thus, dynamically changing, error function. The proposed hybrid strategy is compared with other standard training methods that have traditionally been used for training neural networks off-line. Results in interpreting colonoscopy images and frames of video sequences are promising and suggest that networks trained with this strategy detect malignant regions of interest with accuracy

Derivation of tropospheric methane from TCCON CH₄ and HF total column observations

The Total Carbon Column Observing Network (TCCON) is a global ground-based network of Fourier transform spectrometers that produce precise measurements of column-averaged dry-air mole fractions of atmospheric methane (CH₄). Temporal variability in the total column of CH₄ due to stratospheric dynamics obscures fluctuations and trends driven by tropospheric transport and local surface fluxes that are critical for understanding CH₄ sources and sinks. We reduce the contribution of stratospheric variability from the total column average by subtracting an estimate of the stratospheric CH₄ derived from simultaneous measurements of hydrogen fluoride (HF). HF provides a proxy for stratospheric CH₄ because it is strongly correlated to CH₄ in the stratosphere, has an accurately known tropospheric abundance (of zero), and is measured at most TCCON stations. The stratospheric partial column of CH₄ is calculated as a function of the zonal and annual trends in the relationship between CH₄ and HF in the stratosphere, which we determine from ACE-FTS satellite data. We also explicitly take into account the CH₄ column averaging kernel to estimate the contribution of stratospheric CH₄ to the total column. The resulting tropospheric CH₄ columns are consistent with in situ aircraft measurements and augment existing observations in the troposphere

Impacts of Traffic Reductions Associated With COVID-19 on Southern California Air Quality

On 19 March 2020, California put in place Stay‐At‐Home orders to reduce the spread of SARS‐CoV‐2. As a result, decreases up to 50% in traffic occurred across the South Coast Air Basin (SoCAB). We report that, compared to the 19 March to 30 June period of the last 5 years, the 2020 concentrations of PM_(2.5) and NO_x showed an overall reduction across the basin. O₃ concentrations decreased in the western part of the basin and generally increased in the downwind areas. The NO_x decline in 2020 (approximately 27% basin‐wide) is in addition to ongoing declines over the last two decades (on average 4% less than the −6.8% per year afternoon NO₂ concentration decrease) and provides insight into how air quality may respond over the next few years of continued vehicular reductions. The modest changes in O₃ suggests additional mitigation will be necessary to comply with air quality standards

A method for evaluating bias in global measurements of CO_2 total columns from space

We describe a method of evaluating systematic errors in measurements of total column dry-air mole fractions of CO_2 (X_(CO_2)) from space, and we illustrate the method by applying it to the v2.8 Atmospheric CO_2 Observations from Space retrievals of the Greenhouse Gases Observing Satellite (ACOS-GOSAT) measurements over land. The approach exploits the lack of large gradients in X_(CO_2) south of 25° S to identify large-scale offsets and other biases in the ACOS-GOSAT data with several retrieval parameters and errors in instrument calibration. We demonstrate the effectiveness of the method by comparing the ACOS-GOSAT data in the Northern Hemisphere with ground truth provided by the Total Carbon Column Observing Network (TCCON). We use the observed correlation between free-tropospheric potential temperature and X_(CO_2) in the Northern Hemisphere to define a dynamically informed coincidence criterion between the ground-based TCCON measurements and the ACOS-GOSAT measurements. We illustrate that this approach provides larger sample sizes, hence giving a more robust comparison than one that simply uses time, latitude and longitude criteria. Our results show that the agreement with the TCCON data improves after accounting for the systematic errors, but that extrapolation to conditions found outside the region south of 25° S may be problematic (e.g., high airmasses, large surface pressure biases, M-gain, measurements made over ocean). A preliminary evaluation of the improved v2.9 ACOS-GOSAT data is also discussed

Reinforcing the North Atlantic backbone: revision and extension of the composite splice at ODP Site 982

Ocean Drilling Program (ODP) Site 982 represents a key location for understanding the evolution of climate in the North Atlantic over the past 12Ma. However, concerns exist about the validity and robustness of the underlying stratigraphy and astrochronology, which currently limits the adequacy of this site for high-resolution climate studies. To resolve this uncertainty, we verify and extend the early Pliocene to late Miocene shipboard composite splice at Site 982 using high-resolution XRF core scanning data and establish a robust high-resolution benthic foraminiferal stable isotope stratigraphy and astrochronology between 8.0 and 4.5Ma. Splice revisions and verifications resulted in  ∼ 11m of gaps in the original Site 982 isotope stratigraphy, which were filled with 263 new isotope analyses. This new stratigraphy reveals previously unseen benthic δ18O excursions, particularly prior to 6.65Ma. The benthic δ18O record displays distinct, asymmetric cycles between 7.7 and 6.65Ma, confirming that high-latitude climate is a prevalent forcing during this interval. An intensification of the 41kyr beat in both the benthic δ13C and δ18O is also observed  ∼ 6.4Ma, marking a strengthening in the cryosphere–carbon cycle coupling. A large  ∼ 0.7‰ double excursion is revealed  ∼ 6.4–6.3Ma, which also marks the onset of an interval of average higher δ18O and large precession and obliquity-dominated δ18O excursions between 6.4 and 5.4Ma, coincident with the culmination of the late Miocene cooling. The two largest benthic δ18O excursions  ∼ 6.4–6.3Ma and TG20/22 coincide with the coolest alkenone-derived sea surface temperature (SST) estimates from Site 982, suggesting a strong connection between the late Miocene global cooling, and deep-sea cooling and dynamic ice sheet expansion. The splice revisions and revised astrochronology resolve key stratigraphic issues that have hampered correlation between Site 982, the equatorial Atlantic and the Mediterranean. Comparisons of the revised Site 982 stratigraphy to high-resolution astronomically tuned benthic δ18O stratigraphies from ODP Site 926 (equatorial Atlantic) and Ain el Beida (north-western Morocco) show that prior inconsistencies in short-term excursions are now resolved. The identification of key new cycles at Site 982 further highlights the requirement for the current scheme for late Miocene marine isotope stages to be redefined. Our new integrated deep-sea benthic stable isotope stratigraphy and astrochronology from Site 982 will facilitate future high-resolution late Miocene to early Pliocene climate research