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The evolution of organic aerosol (OA) and brown carbon (BrC) in wildfire plumes, including the relative contributions of primary versus secondary sources, has been uncertain in part because of limited knowledge of the precursor emissions and the chemical environment of smoke plumes. We made airborne measurements of a suite of reactive trace gases, particle composition, and optical properties in fresh western US wildfire smoke in July through August 2018. We use these observations to quantify primary versus secondary sources of biomass-burning OA (BBPOA versus BBSOA) and BrC in wildfire plumes. When a daytime wildfire plume dilutes by a factor of 5 to 10, we estimate that up to one-third of the primary OA has evaporated and subsequently reacted to form BBSOA with near unit yield. The reactions of measured BBSOA precursors contribute only 13 ± 3% of the total BBSOA source, with evaporated BBPOA comprising the rest. We find that oxidation of phenolic compounds contributes the majority of BBSOA from emitted vapors. The corresponding particulate nitrophenolic compounds are estimated to explain 29 ± 15% of average BrC light absorption at 405 nm (BrC Abs405) measured in the first few hours of plume evolution, despite accounting for just 4 ± 2% of average OA mass. These measurements provide quantitative constraints on the role of dilution-driven evaporation of OA and subsequent radical-driven oxidation on the fate of biomass-burning OA and BrC in daytime wildfire plumes and point to the need to understand how processing of nighttime emissions differs.

Sulfate ( SO 4 2 − ) and nitrate ( NO 3 − ) account for half of the fine particulate matter mass over the eastern United States. Their wintertime concentrations have changed little in the past decade despite considerable precursor emissions reductions. The reasons for this have remained unclear because detailed observations to constrain the wintertime gas–particle chemical system have been lacking. We use extensive airborne observations over the eastern United States from the 2015 Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) campaign; ground-based observations; and the GEOS-Chem chemical transport model to determine the controls on winter SO 4 2 − and NO 3 − . GEOS-Chem reproduces observed SO 4 2 − − NO 3 − − NH 4 + particulate concentrations (2.45 μg sm-3) and composition ( SO 4 2 − : 47%; NO 3 − : 32%; NH 4 + : 21%) during WINTER. Only 18% of SO₂ emissions were regionally oxidized to SO 4 2 − during WINTER, limited by low [H₂O₂] and [OH]. Relatively acidic fine particulates (pH∼1.3) allow 45% of nitrate to partition to the particle phase. Using GEOS-Chem, we examine the impact of the 58% decrease in winter SO₂ emissions from 2007 to 2015 and find that the H₂O₂ limitation on SO₂ oxidation weakened, which increased the fraction of SO₂ emissions oxidizing to SO 4 2 − . Simultaneously, NOx emissions decreased by 35%, but the modeled NO 3 − particle fraction increased as fine particle acidity decreased. These feedbacks resulted in a 40% decrease of modeled [ SO 4 2 − ] and no change in [ NO 3 − ], as observed. Wintertime [ SO 4 2 − and [ NO 3 − ] are expected to change slowly between 2015 and 2023, unless SO₂ and NOx emissions decrease faster in the future than in the recent past.

Decades of air quality improvements have substantially reduced the motor vehicle emissions of volatile organic compounds (VOCs). Today, volatile chemical products (VCPs) are responsible for half of the petrochemical VOCs emitted in major urban areas. We show that VCP emissions are ubiquitous in US and European cities and scale with population density. We report significant VCP emissions for New York City (NYC), including a monoterpene flux of 14.7 to 24.4 kg · d−1 · km−2 from fragranced VCPs and other anthropogenic sources, which is comparable to that of a summertime forest. Photochemical modeling of an extreme heat event, with ozone well in excess of US standards, illustrates the significant impact of VCPs on air quality. In the most populated regions of NYC, ozone was sensitive to anthropogenic VOCs (AVOCs), even in the presence of biogenic sources. Within this VOC-sensitive regime, AVOCs contributed upwards of ∼20 ppb to maximum 8-h average ozone. VCPs accounted for more than 50% of this total AVOC contribution. Emissions from fragranced VCPs, including personal care and cleaning products, account for at least 50% of the ozone attributed to VCPs. We show that model simulations of ozone depend foremost on the magnitude of VCP emissions and that the addition of oxygenated VCP chemistry impacts simulations of key atmospheric oxidation products. NYC is a case study for developed megacities, and the impacts of VCPs on local ozone are likely similar for other major urban regions across North America or Europe.

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O₃), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O₃ and methane (CH₄) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O₃. The observed BrO concentrations increase strongly with altitude (∼3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Bry), or model overestimated Brywet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Brysource from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O₃ needs to be considered when estimating past and future ozone radiative effects.

Aircraft measurements, laboratory photolysis experiments and modelling calculations reveal a mechanism for the recycling of nitric acid into nitrogen oxides; this enables observations to be reconciled with model studies, and suggests that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Rapid NO x recycling in marine air Nitrogen oxides play a central role in tropospheric chemistry, but current understanding of the processes responsible for their formation and removal from the atmosphere is insufficient to reconcile model studies with observations. This paper presents aircraft measurements, laboratory photolysis experiments and modelling calculations that reveal a mechanism for the rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. The authors suggest that this process could be an important tropospheric nitrogen oxide source in remote oceanic regions with implications for tropospheric oxidant and secondary atmospheric aerosol formation. Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere 1 . Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides 1 . However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed 2 , 3 . A ‘renoxification’ process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies 2 , 3 , 4 , but the mechanisms responsible for this process remain uncertain 5 , 6 , 7 , 8 , 9 . Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism 10 , 11 suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth’s surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.

External cycling regenerating nitrogen oxides (NO x  ≡ NO + NO 2 ) from their oxidative reservoir, NO z , is proposed to reshape the temporal–spatial distribution of NO x and consequently hydroxyl radical (OH), the most important oxidant in the atmosphere. Here we verify the in situ external cycling of NO x in various environments with nitrous acid (HONO) as an intermediate based on synthesized field evidence collected onboard aircraft platform at daytime. External cycling helps to reconcile stubborn underestimation on observed ratios of HONO/NO 2 and NO 2 /NO z by current chemical model schemes and rationalize atypical diurnal concentration profiles of HONO and NO 2 lacking noontime valleys specially observed in low-NO x atmospheres. Perturbation on the budget of HONO and NO x by external cycling is also found to increase as NO x concentration decreases. Consequently, model underestimation of OH observations by up to 41% in low NO x atmospheres is attributed to the omission of external cycling in models. External cycling regenerates nitrogen oxides from the NO x oxidative reservoir, NO z . Aircraft observations reveal NO x external cycling compensates for NO x aging, sustaining NO x distribution and production of OH radicals far from NO x emission sources

The protective and preservative role of apple skin in maintaining the integrity of the fruit is well-known, with its mechanical behaviour playing a pivotal role in determining fruit storage capacity. This study employs a combination of experimental and numerical methodologies, specifically utilising the digital image correlation (DIC) technique. A specially devised inverse strategy is applied to evaluate the mechanical behaviour of apple skin under uniaxial tensile loading. Three apple cultivars were tested in this work: Malus domestica Starking Delicious, Malus pumila Rennet, and Malus domestica Golden Delicious. Stress–strain curves were reconstructed, revealing distinct variations in the mechanical responses among these cultivars. Yeoh’s hyperelastic model was fitted to the experimental data to identify the coefficients capable of reproducing the non-linear deformation. The results suggest that apple skin varies significantly in composition and structure among the tested cultivars, as evidenced by differences in elastic properties and non-linear behaviour. These differences can significantly affect how fruit is handled, stored, and transported. Thus, the insights resulting from this research enable the development of mathematical models based on the mechanical behaviour of apple tissue, constituting important data for improvements in the economics of the agri-food industry.

This study aimed to evaluate the potential of lactic acid bacteria (LAB) in developing alginate-based gel formulations to inhibit Staphylococcus aureus. Initially, the antagonistic actions of three lactic acid bacteria (LAB) (Lacticaseibacillus rhamnosus ATCC 10863, Lactiplantibacillus plantarum ATCC 14917, Limosilactobacillus fermentum ATCC 23271) were evaluated against S. aureus ATCC 25923. All tested LAB inhibited S. aureus, but the highest activity was observed for L. plantarum ATCC 14917 (p < 0.05). The antimicrobial effects of L. plantarum ATCC 14917 cell suspensions, sonicate cells extract, and cell-free supernatants (pH 5 or 7) were analyzed using a broth-based assay. The cell suspensions inhibited S. aureus at concentrations ≥ 10%, and these effects were confirmed by a time-kill assay. Alginate-based gels were formulated with cell suspensions, sonicate cells extract, and cell-free supernatant (pH 5). These formulations inhibited S. aureus growth. Based on the results, the alginate gel with cell suspensions at 10% was selected for further characterization. L. plantarum ATCC 14917 survived in the alginate-based gel, especially when stored at 5 °C. At this temperature, the L. plantarum-containing alginate gel was stable, and it was in compliance with microbiological standards. These findings suggest it can be a promising agent for the topical treatment of infections induced by S. aureus.

Brown carbon (BrC) consists of particulate organic species that preferentially absorb light at visible and ultraviolet wavelengths. Ambient studies show that as a component of aerosol particles, BrC affects photochemical reaction rates and regional to global climate. Some organic chromophores are especially toxic, linking BrC to adverse health effects. The lack of direct measurements of BrC has limited our understanding of its prevalence, sources, evolution, and impacts. We describe the first direct, online measurements of water-soluble BrC on research aircraft by three separate instruments. Each instrument measured light absorption over a broad wavelength range using a liquid waveguide capillary cell (LWCC) and grating spectrometer, with particles collected into water by a particle-into-liquid sampler (CSU PILS-LWCC and NOAA PILS-LWCC) or a mist chamber (MC-LWCC). The instruments were deployed on the NSF C-130 aircraft during WE-CAN 2018 as well as the NASA DC-8 and the NOAA Twin Otter aircraft during FIREX-AQ 2019, where they sampled fresh and moderately aged wildfire plumes. Here, we describe the instruments, calibrations, data analysis and corrections for baseline drift and hysteresis. Detection limits (3σ) at 365 nm were 1.53 Mm−1 (MC-LWCC; 2.5 min sampling time), 0.89 Mm−1 (CSU PILS-LWCC; 30 s sampling time), and 0.03 Mm−1 (NOAA PILS-LWCC; 30 s sampling time). Measurement uncertainties were 28 % (MC-LWCC), 12 % (CSU PILS-LWCC), and 11 % (NOAA PILS-LWCC). The MC-LWCC system agreed well with offline measurements from filter samples, with a slope of 0.91 and R2=0.89. Overall, these instruments provide soluble BrC measurements with specificity and geographical coverage that is unavailable by other methods, but their sensitivity and time resolution can be challenging for aircraft studies where large and rapid changes in BrC concentrations may be encountered.

This study reports the numerical and experimental characterization of a standard immobilization system currently being used to treat simple oblique bone fractures of femoral diaphyses. The procedure focuses on the assessment of the mechanical behavior of a bone stabilized with a dynamic compression plate (DCP) in a neutralization function, associated to a lag screw, fastened with surgical screws. The non-linear behavior of cortical bone tissue was revealed through four-point bending tests, from which damage initiation and propagation occurred. Since screw loosening was visible during the loading process, damage parameters were measured experimentally in independent pull-out tests. A realistic numerical model of the DCP-femur setup was constructed, combining the evaluated damage parameters and contact pairs. A mixed-mode (I+II) trapezoidal damage law was employed to mimic the mechanical behavior of both the screw–bone interface and bone fractures. The numerical model replicated the global behavior observed experimentally, which was visible by the initial stiffness and the ability to preview the first loading peak, and bone crack satisfactorily.