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At least 1,099 records · Page 61

Marine Atmospheric Corrosion of Additively Manufactured Stainless Steels

Additively manufactured (AM) stainless steels exhibit numerous microstructural differences compared to their wrought counterparts, such as Cr enriched dislocation cell structures. The influence these unique features have on a SSs corrosion resistance are still under investigation with most current works limited to laboratory experiments. The work herein shows the first documented study of AM 304L and 316L exposed to a severe marine environment on the eastern coast of Florida with comparisons made to wrought counterparts. Coupons were exposed for 21 months and resulted in significant pitting corrosion to initiate after 1 month of exposure for all conditions. At all times, the AM coupons exhibited lower average and maximum pit depths than their wrought counterparts. After 21 months, pits on average were 4 μm deep for AM 316L specimen and 8 μm deep for wrought specimen. Pits on the wrought samples tended to be nearly hemispherical and polished with some pits showing crystallographic attack while pits on AM coupons exhibited preferential attack at melt pool boundaries and the cellular microstructure.

36 MATERIALS SCIENCE↗

Atmospheric processing and aerosol aging responsible for observed increase in absorptivity of long-range-transported smoke over the southeast Atlantic

Biomass burning aerosol (BBA) from agricultural fires in southern Africa contributes about one-third of the global carbonaceous aerosol load. These particles have strong radiative effects in the southeast Atlantic (SEA), which depend in part on the radiative contrast between the aerosol layer in the free troposphere (FT) and the underlying cloud layer. However, there is large disagreement in model estimates of aerosol-driven climate forcing due to uncertainties in the vertical distribution, optical properties, and life cycle of these particles. This study applies a novel method combining remote sensing observations with regional model outputs to investigate the aging of the BBA and its impact on the optical properties during transatlantic transport from emission sources in Africa to the SEA. Results show distinct variations in extinction Ångström exponent (EAE) and single-scattering albedo (SSA) as aerosols age. Near the source, fresh aerosols are characterized by low mean SSA (0.84) and high EAE (1.85), indicating smaller, highly absorbing particles. By isolating marine contributions from the total column during BBA transport across the SEA, our analysis reveals an initial decrease in BBA absorptivity, with mean FT SSA of 0.87 after 6–7 d, followed by increased absorptivity with mean FT SSA of 0.84 after 10 d, suggesting enhanced absorption due to chemical aging. These findings indicate that BBA becomes more absorbing during extended transport across the SEA, with implications for reducing model uncertainties. Our remote-sensing-based results agree well with previous in situ studies and offer new insights into aerosol–radiation interactions and the energy balance over the SEA.

54 ENVIRONMENTAL SCIENCES↗

Using an Absolute Cavity Pyrgeometer to Validate the Calibration of a Transfer Standard Pyrgeometer Outdoors, Independent from the Reference Value of the Atmospheric Longwave Irradiance

A unique method of pyrgeometer calibration has been developed to improve the measurement uncertainty [1]. The results of this method yielded irradiance values within ±3 W/m2 of those traceable to the World InfraRed Standard Group (WISG). The ACPs and pyrgeometer model PIR were deployed outdoors, and the irradiance measured by the PIR was compared against the irradiance measured by ACP95F3. Based on the results it is possible to achieve an uncertainty of ± 3.51 W/m2. These results suggest that the PIR calibration method might be useful in addressing the international need for a secondary standard pyrgeometer traceable to SI.

absolute cavity pyrgeometer↗

Water Catalysis of the Reaction of Methanol with OH Radical in the Atmosphere is Negligible

Abstract Faced with the contradictory results of two recent experimental studies [Jara‐Toro et al., Angew. Chem. Int. Ed . 2017 , 56 , 2166 and Chao et al., Angew. Chem. Int. Ed . 2019 , 58 , 5013] of the possible catalytic effect of water vapor on CH 3 OH + OH reaction, we report calculations that corroborate the conclusion made by Chao et al. and extend the rate constant evaluation down to 200 K. The rate constants of the CH 3 OH + OH reaction catalyzed by a water molecule are computed as functions of temperature and relative humidity using high‐level electronic structure and kinetics calculations. The Wuhan–Minnesota Scaling (WMS) method is used to provide accurate energetics to benchmark a density functional for direct dynamics. Both high‐frequency and low‐frequency anharmonicities are included. Variational and tunneling effects are treated by canonical variational transition state theory with multidimensional small‐curvature tunneling. And, most significantly, we include multistructural effects in the rate constant calculations. Our calculations show that the catalytic effect of water vapor is not observable at 200–400 K.

Wu, Junjun↗

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO 2 Capture from Air: Roles of Atmospheric Water

Abstract Direct air capture (DAC) processes for extraction of CO 2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al 2 O 3 , is explored in detail. By combining CO 2 adsorption measurements, oxidative degradation rates, elemental analyses, solid‐state NMR and in situ IR spectroscopic analysis in conjunction with 18 O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.

Carneiro, Juliana S. A.↗

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO 2 Capture from Air: Roles of Atmospheric Water

Direct air capture (DAC) processes for extraction of CO 2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al 2 O 3 , is explored in detail. By combining CO 2 adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with 18 O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. Here we demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Summary of atmospheric characteristics of days with inland penetrating sea breezes from 2015 to 2021

Abstract Sea breezes penetrate inland more than 100 km. Using 7 years of meteorological observations, we have identified 470 cases of deep inland (>100 km) penetrating sea breezes at the Savannah River Site between March and October (27% of days) of 2015–2021. We compared measurements of temperature, dewpoint temperature, incoming solar radiation, cloud fraction, and lightning on days of sea breeze initiation, the day after the sea breeze passage, and all other nonsea breeze (NSB) days for these 8 months over the 7 years. Days of sea breeze initiation were found to have lower cloud fraction, higher temperature, and greater incoming solar radiation compared with NSB days. Variations occurred by time of year as days after the sea breeze passage were found to have higher dewpoint temperature than NSB days in the spring. Lightning density measurements indicated that residual sea breeze conditions could drive earlier initiation of deep convection on days following the sea breeze than normal non sea breeze days. This data set provides a 7‐year record of sea breezes which can be leveraged for future studies.

54 ENVIRONMENTAL SCIENCES↗

Data‐Driven Analysis of Amine‐Based Sorbents for CO 2 Removal from the Atmosphere

Available data on amine-based sorbents used for the direct air capture (DAC) process were gathered and analyzed to identify the correlations between various aspects of these sorbents and the operating conditions they are used in. It is demonstrated that a moderately high temperature (∼ 50 °C) can help with higher CO 2 capture capacity. Furthermore, the effect of sorbent preparation method on its activity and stability was studied. Also, the influence of amine groups and support choice on amine efficiency and CO 2 capture capacity was discussed. The DAC process conditions proved to play a major role in determining the optimal sorbent. An outlook for characteristics to be sought for in future DAC sorbents for CO 2 removal is proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mitigating the allergenicity of peanut allergen Ara h 1 by cold atmospheric pressure argon plasma jet

Abstract BACKGROUND Peanut allergy is recognized as a major food allergy that triggers severe and even fatal symptoms. Avoidance of peanuts in the diet is the main option for current safety management. Processing techniques reducing peanut allergenicity are required to develop other options. Cold plasma is currently considered as a novel non‐thermal approach to alter protein structure and has the potential to alleviate immunoreactivity of protein allergen. RESULTS The application of a cold argon plasma jet to peanut protein extract could reduce the amount of a 64 kDa protein band corresponding to a major peanut allergen Ara h 1 using sodium dodecyl sulfate–polyacrylamide gel electrophoresis, but the overall protein size distribution did not change significantly. A decrease in peanut protein solubility was a possible cause that led to the loss of protein content in the soluble fraction. Immunoblotting and enzyme‐linked immunosorbent assay elucidated that the immunoreactivity of Ara h 1 was significantly decreased with the time treated with plasma. Ara h 1 antigenicity reduced by 38% after five scans (approximately 3 min) of cold argon plasma jet treatment, and the reduction was up to 66% after approximately 15 min of treatment. CONCLUSION The results indicate that cold argon plasma jet treatment could be a suitable platform for alleviating the immunoreactivity of peanut protein. This work demonstrates an efficient, compact, and rapid platform for mitigating the allergenicity of peanuts, and shows great potential for the plasma platform as a non‐thermal technique in the food industry. © 2023 Society of Chemical Industry.

Hsu, Fu‐Chiun↗