Monthly resolved modelled oceanic emissions of carbonyl sulfide and carbon disulfide for the period 2000–2019

Carbonyl sulfide (OCS) is the most abundant, long-lived sulphur gas in the atmosphere and a major supplier of sulfur to the stratospheric sulfate aerosol layer. The short-lived gas carbon disulfide (CS2) is oxidized to OCS and constitutes a major indirect source to the atmospheric OCS budget. The atmospheric budget of OCS is not well constrained due to a large missing source needed to compensate for substantial evidence that was provided for significantly higher sinks. Oceanic emissions are associated with major uncertainties. Here we provide a first, monthly resolved ocean emission inventory of both gases for the period 2000–2019 (available at https://doi.org/10.5281/zenodo.4297010) (Lennartz et al., 2020a). Emissions are calculated with a numerical box model (resolution 2.8° × 2.8° at equator, T42 grid) for the surface mixed layer. We find that interannual variability in OCS emissions is smaller than seasonal variability, and is mainly driven by variations in chromophoric dissolved organic matter (CDOM), which influences both photochemical and light-independent production. A comparison with a global database of more than 2500 measurements reveals overall good agreement. Emissions of CS2 constitute a larger sulfur source to the atmosphere than OCS, and equally show interannual variability connected to variability of CDOM. The emission estimate of CS2 is associated with higher uncertainties, as process understanding of the marine cycling of CS2 is incomplete. We encourage the use of the data provided here as input for atmospheric modelling studies to further assess the atmospheric OCS budget and the role of OCS in climate

Direct radiative effect of aerosols emitted by transport from road, shipping and aviation

Aerosols and their precursors are emitted abundantly by transport activities. Transportation constitutes one of the fastest growing activities and its growth is predicted to increase significantly in the future. Previous studies have estimated the aerosol direct radiative forcing from one transport sub-sector, but only one study to our knowledge estimated the range of radiative forcing from the main aerosol components (sulphate, black carbon (BC) and organic carbon) for the whole transportation sector. In this study, we compare results from two different chemical transport models and three radiation codes under different hypothesis of mixing: internal and external mixing using emission inventories for the year 2000. The main results from this study consist of a positive direct radiative forcing for aerosols emitted by road traffic of +20±11 mW m−2 for an externally mixed aerosol, and of +32±13 mW m−2 when BC is internally mixed. These direct radiative forcings are much higher than the previously published estimate of +3±11 mW m−2. For transport activities from shipping, the net direct aerosol radiative forcing is negative. This forcing is dominated by the contribution of the sulphate. For both an external and an internal mixture, the radiative forcing from shipping is estimated at −26±4 mW m−2. These estimates are in very good agreement with the range of a previously published one (from −46 to −13 mW m−2) but with a much narrower range. By contrast, the direct aerosol forcing from aviation is estimated to be small, and in the range −0.9 to +0.3 mW m−2

The empirical equilibrium structure of diacetylene

High-level quantum-chemical calculations are reported at the MP2 and CCSD(T) levels of theory for the equilibrium structure and the harmonic and anharmonic force fields of diacetylene, HCCCCH. The calculations were performed employing Dunning's hierarchy of correlation-consistent basis sets cc-pVXZ, cc-pCVXZ, and cc-pwCVXZ, as well as the ANO2 basis set of Almloef and Taylor. An empirical equilibrium structure based on experimental rotational constants for thirteen isotopic species of diacetylene and computed zero-point vibrational corrections is determined (r_e^emp: rC-H=1.0615 A, rCtripleC=1.2085 A, rC-C = 1.3727 A) and in good agreement with the best theoretical structure (CCSD(T)/cc-pCV5Z: rC-H=1.0617 Angstrom, rCtripleC=1.2083 A, rC-C=1.3737 A). In addition, the computed fundamental vibrational frequencies are compared with the available experimental data and found in satisfactory agreement.Comment: 12 pages, accepted for publication in J. Mol. Spectros

Broadband classification and statistics of echoes from aggregations of fish measured by long-range, mid-frequency sonar

Author Posting. © Acoustical Society of America, 2017. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 141 (2017): 4354, doi:10.1121/1.4983446.For horizontal-looking sonar systems operating at mid-frequencies (1–10 kHz), scattering by fish with resonant gas-filled swimbladders can dominate seafloor and surface reverberation at long-ranges (i.e., distances much greater than the water depth). This source of scattering, which can be difficult to distinguish from other sources of scattering in the water column or at the boundaries, can add spatio-temporal variability to an already complex acoustic record. Sparsely distributed, spatially compact fish aggregations were measured in the Gulf of Maine using a long-range broadband sonar with continuous spectral coverage from 1.5 to 5 kHz. Observed echoes, that are at least 15 decibels above background levels in the horizontal-looking sonar data, are classified spectrally by the resonance features as due to swimbladder-bearing fish. Contemporaneous multi-frequency echosounder measurements (18, 38, and 120 kHz) and net samples are used in conjunction with physics-based acoustic models to validate this approach. Furthermore, the fish aggregations are statistically characterized in the long-range data by highly non-Rayleigh distributions of the echo magnitudes. These distributions are accurately predicted by a computationally efficient, physics-based model. The model accounts for beam-pattern and waveguide effects as well as the scattering response of aggregations of fish.This research was supported by the U.S. Office of Naval Research, the National Oceanographic Partnership Program, NOAA, WHOI, and the Oceanographer of the U.S. Navy

Coupled-cluster techniques for computational chemistry: The CFOUR program package

An up-to-date overview of the CFOUR program system is given. After providing a brief outline of the evolution of the program since its inception in 1989, a comprehensive presentation is given of its well-known capabilities for high-level coupled-cluster theory and its application to molecular properties. Subsequent to this generally well-known background information, much of the remaining content focuses on lesser-known capabilities of CFOUR, most of which have become available to the public only recently or will become available in the near future. Each of these new features is illustrated by a representative example, with additional discussion targeted to educating users as to classes of applications that are now enabled by these capabilities. Finally, some speculation about future directions is given, and the mode of distribution and support for CFOUR are outlined

WFPC2 Observations of the Hubble Deep Field-South

The Hubble Deep Field-South observations targeted a high-galactic-latitude field near QSO J2233-606. We present WFPC2 observations of the field in four wide bandpasses centered at roughly 300, 450, 606, and 814 nm. Observations, data reduction procedures, and noise properties of the final images are discussed in detail. A catalog of sources is presented, and the number counts and color distributions of the galaxies are compared to a new catalog of the HDF-N that has been constructed in an identical manner. The two fields are qualitatively similar, with the galaxy number counts for the two fields agreeing to within 20%. The HDF-S has more candidate Lyman-break galaxies at z > 2 than the HDF-N. The star-formation rate per unit volume computed from the HDF-S, based on the UV luminosity of high-redshift candidates, is a factor of 1.9 higher than from the HDF-N at z ~ 2.7, and a factor of 1.3 higher at z ~ 4.Comment: 93 pages, 25 figures; contains very long table

Fresh air in the 21st century?

Ozone is an air quality problem today for much of the world's population. Regions can exceed the ozone air quality standards (AQS) through a combination of local emissions, meteorology favoring pollution episodes, and the clean-air baseline levels of ozone upon which pollution builds. The IPCC 2001 assessment studied a range of global emission scenarios and found that all but one projects increases in global tropospheric ozone during the 21st century. By 2030, near-surface increases over much of the northern hemisphere are estimated to be about 5 ppb (+2 to +7 ppb over the range of scenarios). By 2100 the two more extreme scenarios project baseline ozone increases of >20 ppb, while the other four scenarios give changes of -4 to +10 ppb. Even modest increases in the background abundance of tropospheric ozone might defeat current AQS strategies. The larger increases, however, would gravely threaten both urban and rural air quality over most of the northern hemisphere

Transport impacts on atmosphere and climate: Land transport

Emissions from land transport, and from road transport in particular, have significant impacts on the atmosphere and on climate change. This assessment gives an overview of past, present and future emissions from land transport, of their impacts on the atmospheric composition and air quality, on human health and climate change and on options for mitigation. In the past vehicle exhaust emission control has successfully reduced emissions of nitrogen oxides, carbon monoxide, volatile organic compounds and particulate matter. This contributed to improved air quality and reduced health impacts in industrialised countries. In developing countries however, pollutant emissions have been growing strongly, adversely affecting many populations. In addition, ozone and particulate matter change the radiative balance and hence contribute to global warming on shorter time scales. Latest knowledge on the magnitude of land transport's impact on global warming is reviewed here. In the future, road transport's emissions of these pollutants are expected to stagnate and then decrease globally. This will then help to improve the air quality notably in developing countries. On the contrary, emissions of carbon dioxide and of halocarbons from mobile air conditioners have been globally increasing and are further expected to grow. Consequently, road transport's impact on climate is gaining in importance. The expected efficiency improvements of vehicles and the introduction of biofuels will not be sufficient to offset the expected strong growth in both, passenger and freight transportation. Technical measures could offer a significant reduction potential, but strong interventions would be needed as markets do not initiate the necessary changes. Further reductions would need a resolute expansion of low-carbon fuels, a tripling of vehicle fuel efficiency and a stagnation in absolute transport volumes. Land transport will remain a key sector in climate change mitigation during the next decades