Secondary Formation Research Articles

Amplified Secondary Organic Aerosol Formation Induced by Anthropogenic–Biogenic Interactions in Forests Around Megacities

AbstractThe amplification effect of anthropogenic‐biogenic interactions on secondary organic aerosol (SOA) formation remains debated, particularly regarding the impact of anthropogenic emissions on biogenic SOA (BSOA) formation in forests near megacities. This study concurrently measured typical biogenic and anthropogenic SOA tracers during day and night at the summit (1,690 m a.s.l.) and foot (200 m a.s.l.) of the Nanling mountains, a large subtropical forest adjacent to the Pearl River Delta (PRD) in southern China. Results revealed unexpectedly high concentrations of BSOA tracers (149.9 ± 70.5 ng m−3 at the summit and 109.7 ± 51.2 ng m−3 at the foot), surpassing those at most other background sites worldwide. Daytime BSOA tracer levels at the foot were consistent with nighttime levels, whereas the summit showed significantly higher concentrations at night. Nighttime correlations between O₃ and BSOA tracers at the summit suggest that high O₃ levels stimulate BSOA formation. Conversely, a negative correlation between O₃ and isoprene derived SOA (SOAI) tracers at the foot indicates that other oxidants may also influence SOAI formation. BSOA tracer concentrations rose significantly with the arrival of anthropogenic pollutants (e.g., SO₂ and NO₂), indicating that anthropogenic pollution amplifies BSOA formation by enhancing aerosol acidity (pH < 3). This amplification effect could be mitigated by the reduction of aerosol acidity due to increased NH₃ and relative humidity (RH). Our findings provide valuable insights into the interactions between anthropogenic and biogenic emissions on SOA formation and vertical distribution in forests surrounding megacities.

Effects of Titanate on Brake Wear Particle Emission Using a Brake Material Friction Test Dynamometer

We investigated the effect of lepidocrocite-type layered titanate, which is compounded in brake pads, to reduce brake particle emissions. The dust reduction effect of titanate was evaluated using a small-scale inertial brake material friction test dynamometer. The results suggested that brake particle emissions are related to the microphysical structure of the pad surface, such as the uniformity of the friction film and secondary plateau formation, and that friction materials containing titanate contribute significantly to reducing both particle mass (PM) and particle number (PN) emissions of brake particles in both non-asbestos organic (NAO) and low-steel (LS) pads. In particular, LS pads generally have a problem of having more brake particles than NAO pads, but this study found that brake particles can be significantly reduced by compounding titanate instead of tin sulfide.

CO₂ sequestration and soil improvement in enhanced rock weathering: A review from an experimental perspective

AbstractEnhanced rock weathering (ERW) is an emerging negative emission technology (NET) with significant potential for mitigating climate change and improving soil health through the accelerated chemical weathering of silicate minerals. This study adopts a critical research approach to review existing ERW experiments, focusing on the mechanisms of soil improvement and CO₂ sequestration, as well as the economic costs and environmental risks associated with its large‐scale implementation. The results demonstrate that while ERW effectively enhances soil pH and provides essential nutrients for crops, its CO₂ sequestration capacity is highly dependent on variables such as soil type, rock type, application rate, and particle size. Furthermore, the economic feasibility of ERW is challenged by high costs related to mining, grinding, and transportation, and environmental risks posed by the release of heavy metals like Ni and Cr during the weathering process. Notably, significant discrepancies exist between laboratory experiments and field applications, highlighting the need for extensive in‐situ monitoring and adjustment of ERW practices. This study underscores the importance of optimizing ERW strategies to maximize CO₂ sequestration while minimizing environmental impacts. Future research should focus on long‐term field experiments, understanding secondary mineral formation, and refining the application techniques to enhance the overall efficiency and sustainability of ERW. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Capturing Dynamic Assembly of Nanoscale Proteins During Network Formation

AbstractThe structural evolution of hierarchical structures of nanoscale biomolecules is crucial for the construction of functional networks in vivo and in vitro. Despite the ubiquity of these networks, the physical mechanisms behind their formation and self‐assembly remains poorly understood. Here, this study uses photochemically cross‐linked folded protein hydrogels as a model biopolymer network system, with a combined time‐resolved rheology and small‐angle x‐ray scattering (SAXS) approach to probe both the load‐bearing structures and network architectures respectively thereby providing a cross‐length scale understanding of the network formation. Combining SAXS, rheology, and kinetic modeling, a dual formation mechanism consisting of a primary formation phase is proposed, where monomeric folded proteins create the preliminary protein network scaffold; and a subsequent secondary formation phase, where both additional intra‐network cross‐links form and larger oligomers diffuse to join the preliminary network, leading to a denser more mechanically robust structure. Identifying this as the origin of the structural and mechanical properties of protein networks creates future opportunities to understand hierarchical biomechanics in vivo and develop functional, designed‐for‐purpose, biomaterials.

SECONDARY MINERAL FORMATION IN PRODUCTIVE DEPOSITS OF THE PASHIYSKY HORIZON OF THE SOUTH TATAR ARCH (REPUBLIC OF BASHKORTOSTAN)

The article presents the results of studying the postsedimentary mineralization of productive terrigenous deposits of the Pashiysky horizon of the South Tatar arch. The authors' research was carried out on the basis of a large amount of core material from newly studied wells with the involvement of wells from the archival fund. The analytical work included the following methods: classical optical microscopy and scanning electron microscopy (SEM). Using these methods, the main types of secondary mineral formation, the form and nature of the allocation of authigenic minerals that form secondary cement were studied, and an assessment of the degree of their influence on the filtration-capacitive properties (FPP) was given. It is shown that sideritization is a fairly common phenomenon in the studied deposits, but it does not have a significant effect on the reduction of the reservoir properties of productive deposits. Detailed optical and mineralogical studies have shown that authigenic siderite in the studied rocks is presented in various forms (spherites, spherulites, oolites and granular grains) and is mostly found in silt varieties. In productive sandstones, an insignificant decrease in the reservoir properties can only be associated with expanding rims in siderite spherites. As shown by the study of the composition of these rims, they are composed mainly of ankerite, in places they contain mangano-siderite. In some samples of the Pashiysky horizon, partial replacement of siderite by iron hydroxides was observed; in isolated wells, thin layers of oolitic siderite-ferruginous rocks were encountered. It was shown that the main influence on the reduction of the filtration-capacity properties of the studied sediments is secondary silification and carbonatization. At the same time, secondary quartz is developed mainly in water-saturated sandstones and heterogeneous silt-sandstones, and, as a rule, is distributed mostly locally. Secondary silica is observed in the form of regeneration rims, xenomorphic grains and is deposited on the walls of pores and channels. A significant effect on the reduction of the porosity and permeability parameters of the productive sandstones of the Pashiysky horizon of the South Tatar arch is exerted by secondary crystalline calcite or dolomite island cement of the basal, basal-pore and poikillite type.

Decreasing the Uncertainty in the Comparison of Molecular Fingerprints of Organic Aerosols with H/D Exchange Mass Spectrometry.

High-resolution mass spectrometry (HRMS) has become an indispensable tool in the characterization of organic aerosols (OA) providing information on air quality, health assessment, climate trends, reactions, and source apportionment. Spectra-derived lists of formulas and their relative abundances are used to compare ambient OA from different sources or to monitor secondary OA formation under controlled laboratory conditions in smog chamber experiments. Various techniques are implemented to visualize common and unique features, series of precursors, and products. The disadvantage of this conventional approach is in associating elemental compositions to specific compounds, while due to several analytical limitations, the structural information remains hidden. We argue that some of the conclusions derived from this data analysis can be misleading. In this study, we applied in-ESI source H/D exchange (HDX), which facilitated enumeration of labile protons in molecules behind elemental compositions of OA. We applied this technique to compare OA from three different locations representing urban, forest, and marine environments and to examine tentative chemical information derived from Kendrick mass defect (KMD) series analysis. Significant discrepancies were found between numbers of labile protons in protogenic functional groups and the stoichiometry of chemical reactions, which are associated with KMD series. Only a portion of chemical pairs matched target stoichiometries, which highlights the existing limitations in environmental applications of conventional formula-based HRMS data interpretation strategies.

Enhanced Adsorption and Photocatalytic Activity of Vertically Oriented TiO2 Nanotube Arrays by Li Incorporation

A highly efficient, solid, and easily maneuverable adsorbent and photocatalyst, Li‐incorporated titanate nanotubes that manifest adsorption efficiency of 98.1% and photocatalytic efficiency of 99.6% in 60 min and 97.8% and 98.5%, respectively, in a shorter duration of 20 min, is synthesized by a facile two‐stage electrochemical technique. The modified nanotubes exhibit good cyclic stability of 93.7% photodegradation of malachite green dye after three continuous cycles. The adsorption data show the highest correlation for second‐order pseudo kinetics and Freundlich isotherm, suggesting multilayer chemisorption with an adsorption capacity of kF ≈ 219.51 mg1–1/nL1/ng−1. Fourier transform infrared spectroscopy (FTIR) analysis of the adsorbent before and after the adsorption corroborates the findings. X‐Ray photoelectron spectroscopy reveals the formation of a larger number of oxygen vacancies (Ti3+/Ti2+) that facilitate more carrier release for the production of reactive oxygen species during photocatalysis. X‐Ray diffraction and transmission electron microscopy analysis confirm a secondary rutile phase formation on Li doping that promotes heterogeneous multilayer adsorption. Field‐emission spectroscopic studies reveal a change in the morphology of the doped tubes with porous aggregate formation on the surface. The structural, morphological, and compositional change brought about by Li incorporation facilitates the use of titania nanotubes as an efficient adsorbent cum photocatalyst in the removal of malachite green dye.

Multiyear high-temporal-resolution measurements of submicron aerosols at 13 French urban sites: data processing and chemical composition

Abstract. This paper presents a first comprehensive analysis of long-term measurements of atmospheric aerosol components from aerosol chemical speciation monitor (ACSM) and multiwavelength Aethalometer (AE33) instruments collected between 2015 and 2021 at 13 (sub)urban sites as part of the French CARA (Chemical Characterization of Particles) program. The datasets contain the mass concentrations of major chemical species within submicron aerosols (PM1), namely organic aerosols (OAs), nitrate (NO3-), ammonium (NH4+), sulfate (SO42-), non-sea-salt chloride (Cl−), and equivalent black carbon (eBC). Rigorous quality control, technical validation, and environmental evaluation processes were applied, adhering to both guidance from the French Reference Laboratory for Air Quality Monitoring (LCSQA) and the Aerosol, Clouds, and Trace Gases Research Infrastructure (ACTRIS) standard operating procedures. Key findings include geographical differences in the aerosol chemical composition, seasonal variations, and diel patterns, which are influenced by meteorological conditions, anthropogenic activities, and proximity to emission sources. Overall, OA dominates PM1 at each site (43 %–60 % of total mass), showing distinct seasonality with higher concentrations (i) in winter, due to enhanced residential heating emissions, and (ii) in summer, due to increased photochemistry favoring secondary aerosol formation. NO3 is the second most important contributor to PM1 (15 %–30 %), peaking in late winter and early spring, especially in northern France, and playing a significant role during pollution episodes. SO4 (8 %–14 %) and eBC (5 %–11 %) complement the major fine-aerosol species, with their relative contributions strongly influenced by the origin of air masses and the stability of meteorological conditions, respectively. A comparison with the 3D chemical transport model (CTM) CHIMERE shows high correlations between simulations and measurements, albeit with an OA concentration underestimation of 46 %–76 %. Regional discrepancies in NO3 concentration levels emphasize the importance of these datasets with respect to validating air quality models and tailoring air pollution mitigation strategies. The datasets can be found at https://doi.org/10.5281/zenodo.13318298 (Chebaicheb et al., 2024).

Stable silicon isotope fractionation reflects the routing of water through a mesoscale hillslope

Concentration - isotope Ratio - Discharge (C-R-Q) relationships offer a promising means of disentangling the underlying hydrologic, geochemical, and ecological factors that produce variations in stream solute chemistry across a variety of critical zone systems. However, natural environments are both temporally and spatially complex, and prevailing interpretations of these C-R-Q patterns remain difficult to validate. Here we employ three replicate artificially constructed hillslopes at the Landscape Evolution Observatory (LEO) in Tucson, Arizona as simplified analogs to natural catchments. LEO allows us to record silicon stable isotope (δ30Si) signatures of fluid discharge under a controlled irrigation schedule in a system devoid of vegetation. This unique meso‑scale experiment enables, for the first time, evaluation of metalloid stable isotope signatures at the scale of natural hillslopes constrained to known fluid transit time distributions (TTDs) and limited to fractionation in association with secondary mineral formation. We report δ30Si in discharge samples collected over three randomized storm events of varying intensity. The data reflect consistent enrichment in the fluid phase between +1.00 and +2.07 ‰ across the three hillslopes, despite highly variable irrigation scenarios, reflecting substantial loss of SiO2 from solution due to secondary mineral precipitation. We compare results from an isotope-enabled Reactive Transport Model (RTM) and the discharge measurements from LEO to constrain the contributions of both characteristic watershed TTDs and fractionation pathways in emergent δ30Si signatures. Our study confirms and expands upon recent work in natural systems attributing intra-site variability in silicon stable isotope signatures to the routing of fluid through catchments.

Calcite Dissolution-Reprecipitation Reactions Are a Key Control on the Sr/Ca, Mg/Ca and δ88/86Sr Compositions of Himalayan River Waters

Silicate weathering on the continents is thought to play a critical part in regulating global climate on geological time scales but determination of the magnitude of silicate weathering fluxes is frustrated by the complexity of the weathering processes. Here we present analyses of stable Sr-isotopic compositions (𝛿88/86Sr) in a suite of river waters and bedloads from the Himalayas in Nepal to establish the lithological controls on 𝛿88/86Sr values and the secondary processes that impact carbonate weathering. A control on 𝛿88/86Sr values is lithology with the rivers in carbonate-dominated catchments marginally lower (∼0.07 ‰) than in silicate-dominated catchments. However, as for 87Sr/86Sr ratios, 𝛿88/86Sr values of carbonates are altered by silicate-carbonate mineral exchange during metamorphism. The major potential secondary control on 𝛿88/86Sr values in Himalayan catchments is precipitation of secondary calcite responsible for the marked elevation of Sr/Ca and Mg/Ca ratios in the waters. We re-evaluate the mechanisms for secondary calcite formation and conclude that a balanced solution and re-precipitation process, driven by the relative instability of the primary Mg-rich calcite, provides a better explanation for the elevated Sr/Ca ratios than simple precipitation from a highly over saturated solution. This solution-re-precipitation process is akin to that invoked to explain diagenesis of deep-sea sediments. The mechanism of secondary calcite formation impacts the distinction of cation inputs from carbonate and silicate minerals. The correlation between 𝛿88/86Sr water-calcite fractionations, Sr/Ca partition coefficients and precipitation rates allows the calcite re-precipitation rates to be inferred from the covariation of water 𝛿88/86Sr values and Sr/Ca ratios. These rates are very low (<10-8 mol m-2 s-1) but are consistent with those inferred from field estimates of the amount of calcite re-precipitated, the surface area of carbonate exposed to weathering and the calcite weathering flux. The low precipitation rates are also consistent with previously reported 𝛥44/40Ca isotope fractionations of ∼−0.2‰. The calcite reprecipitation rates are comparable to silicate weathering rates previously inferred from Li-isotopic compositions which is consistent with calcite re-precipitation taking place very close to equilibrium following the initial rapid saturation of the fluids by calcite.

Unveiling Key Genes and Unique Transcription Factors Involved in Secondary Cell Wall Formation in Pinus taeda

Pinus taeda is a key timber species, and extensive research has been conducted on its wood formation. However, a comprehensive investigation into the biosynthetic pathways of lignin, cellulose, and hemicellulose in P. taeda is lacking, resulting in an incomplete understanding of secondary cell wall (SCW) formation in this species. In this study, we systematically analyzed transcriptomic data from previously published sources and constructed detailed pathways for lignin, cellulose, and hemicellulose biosynthesis. We identified 188 lignin-related genes and 78 genes associated with cellulose and hemicellulose biosynthesis. An RT-qPCR highlighted 15 key lignin biosynthesis genes and 13 crucial genes for cellulose and hemicellulose biosynthesis. A STEM analysis showed that most essential enzyme-coding genes clustered into Profile 14, suggesting their significant role in SCW formation. Additionally, we identified seven NAC and six MYB transcription factors (TFs) from atypical evolutionary clades, with distinct expression patterns from those of the previously characterized NAC and MYB genes, indicating potentially unique functions in SCW formation. This research provides the first comprehensive overview of lignin, cellulose, and hemicellulose biosynthetic genes in P. taeda and underscores the importance of non-canonical NAC and MYB TFs, laying a genetic foundation for future studies on SCW regulatory mechanisms.

A fingerprint of source-specific health risk of PM2.5-bound components over a coastal industrial city

The influence of specific local land-use activities (continuously redistributing elements across environments) and environmental conditions (altering the chemical composition of airborne particulate matter) on the intrinsic health risk of PM2.5 exposure is sparsely reported. To fill this gap, we employed a novel integrated approach to address the influence of short-term changes in source-specific PM2.5 composition on the exposure-response risk, while controlling for weather conditions. We combine receptor-based source apportionment with conditional logistic regression in a space-time-stratified case-crossover design. This approach is different from previous studies as it: i) controls the impact of spatiotemporal variations in air pollution and human mobility using multilocation-specific fixed and disjointed space-time strata ii) addresses the spatial heterogeneity of personal exposure separating its variable effect from other predictors by allowing different baseline hazards for each space-time stratum; iii) aligns case/control periods with strong/regular episodes of source-specific PM-multipollutant fingerprint contributions rather than health outcomes. This enabled comprehensive examination of the association between source-specific PM2.5-bound species and cardiorespiratory disease hospitalizations. The epidemiological findings were that primary anthropogenic emissions [industrial (ORs 2.5 – 4.8)] were associated with higher 1-day moving average PM-induced risks. Natural-related sources [fresh / aged sea salt aerosol, dust, soil resuspension] and secondary sulfate formation were consistently associated with higher health risks (ORs 1.0 – 1.54) after 1 to 5-days since exposure. The results emphasize the importance of source-specific air quality management in complex areas and our research provides an adaptable universal tool to support targeted place-based policy interventions to mitigate air pollution impacts on health.

Significant Biogenic Source of Oxygenated Volatile Organic Compounds and the Impacts on Photochemistry at a Regional Background Site in South China.

Oxygenated volatile organic compounds (OVOCs) significantly modulate atmospheric chemistry, but the sources and air quality impacts of OVOCs in aged urban outflows remain to be elucidated. At a background site in South China, the ozone formation potential of six nonformaldehyde OVOCs studied was equivalent to that of 3.56 ppbv of formaldehyde, more than half of which was contributed by acetaldehyde. Source apportionment incorporating photochemical age revealed that considerable fractions (52.7%-62.6%) of the OVOCs were of biogenic origin, except for ethanol, which was primarily derived from anthropogenic emissions. The oxidation of cis-/trans-2-butene explained 71.1% of the in situ acetaldehyde formation. In contrast, α/β-pinenes and isoprene contributed 73.8% and 28.4% to acetone and methylglyoxal formation, respectively. An average of 12.4% of net in situ ozone (O3) production rate was attributed to the OVOCs studied, where the biogenic fractions accounted for 59%. The changes in the O3 production rate and hydroxyl radical (OH) concentration caused by OVOCs were mainly affected by ozone formation sensitivity. The effects of primary acetaldehyde and acetaldehyde-led O3 on secondary acetaldehyde formation were weak at this background site; however, they cannot be ignored in polluted areas. This study provides a scientific basis for mitigating O3 pollution driven by biogenic emissions and OVOCs.

Enhancing aviation safety: Multifunctional graphene nanostructured foams for lightweight fire suppression materials

Fuel tank fires and explosions are the primary causes of military and civilian aircraft losses and have been a major concern for the aviation and defense industries. Passive protection systems with explosion-suppression materials generate a protected environment within fuel tanks before ignition can occur and help prevent catastrophic failures. To minimize these concerns, open-cell reticulated polyurethane foams are extensively used in passive protection systems. However, fire- and explosion-related incidents are still taking place and need to be urgently addressed for aviation safety. This study investigates the effects of graphene nanostructured foams for redesigning the next-generation lightweight fire-retardant materials in aviation. Graphene foams have a unique open-cell morphology with three dimensional (3D) continuous and interconnected network structures and hollow features, which can be suitable for aircraft and defense applications. In this study, mechanical and thermal characterizations tests were conducted on graphene nanostructured foams for a better evaluation. Mechanical loading-unloading studies highlighted their outstanding mechanical energy-absorption capabilities against external loads. The thermogravimetric analysis revealed that the graphene foams provided excellent thermal properties against fire and high-temperature degradation. It was also confirmed that graphene foams uniquely manifested self-extinguishing characteristics during burning tests without catching fire or dripping for secondary fire formations. According to the tube explosion experiments, the graphene foams kept their appearance and strength after blast impacts and elevated explosion temperatures and shock waves. As a result, the proposed multifunctional graphene micro- and nanofoams offer significant potential for the next-generation fire- and explosion-suppression materials in various critical industries, such as aircraft, defense, space, drone, energy, and automotive.

Wide-range emission of Er3+/Yb3+ co-doped lanthanum niobates: A study of temperature and excitation-dependent luminescence aiming at applications in Biophotonics

We have synthesized Er3+,Yb3+ co-doped lanthanum niobate samples by a sol–gel route and investigated their luminescent properties under different excitation sources aiming at applications in Biophotonics. The samples were crystalline and composed primarily of orthorhombic La3NbO7 with secondary formation of monoclinic LaNbO4. We verified NIR-to-visible upconversion with the naked eye under excitation at 980 and 1550 nm; emission in the green and red regions prevailed, respectively. X-ray excitation revealed prevalent emission in the blue region, attributed to the luminescence of NbO43− groups in the lattice, as well as Er3+ emissions in the visible range. All the samples presented high relative thermal sensitivity (above 1.32 % K−1) and repeatability above 97 % between 243 and 293 K. Based on the investigated luminescent properties, the samples prepared herein are versatile materials with a wide range of potential applications as scintillators, optical markers, energy converters for photodynamic therapy, and nanothermometers.

Gradient variations of formation mechanisms and sources of PM1 at the steep slope from western SiChuan Basin to eastern Tibetan Plateau

Vertical distributions of chemical components of particulate matter (PM) are essential for better understanding the climate, environmental and health effects. The steep slope from western SiChuan Basin (SCB) to eastern Tibetan Plateau (TP) provides a good platform for obtaining the gradient variations of PM chemical components. Daytime and nighttime PM1 (particulate matter smaller than 1 μm) samples were collected with the medium-volume sampler at six sites with elevation ranging from 500 m to 3500 m (Chengdu, Sanbacun, Wenchuan, Lixian, Maerkang and Hongyuan). The secondary inorganic ions and carbonaceous aerosols were the largest contributor to PM1 concentrations. The chemical components from the anthropogenic sources existed strong stratification with high concentrations inside the basin, while primary natural ions showed little discrepancy among the sites. The concentrations of primary inorganic ions from anthropogenic sources were much higher at nighttime than daytime, which was contrary to the diurnal cycle of secondary inorganic ions. Spatial heterogeneity of PM chemical components was large between basin and plateau sites, especially for NO3− and NH4+, large depending on season and daylight. The excess NH4+ concentrations existed in spring, summer and fall, while SO42− and NO3− cannot be completely neutralized by NH4+ in winter. The proportion of secondary formation in all sources significantly increased from about 10 % to 30 %–40 % with the increased elevation, while the contribution of motor vehicles declined from western SCB to eastern TP. This study will fill the scarce observations of PM chemical components at the sloped terrain and deepen the understanding of formation mechanism of heavy pollution inside the basin.

Dust event identification and characterization with one-year online observations in Beijing.

Dust storms have a profound impact on air quality, atmospheric chemistry, and human well-being by carrying vast amounts of particles over distances of thousands of kilometers. However, the overall characteristics of these dust events and their influence on secondary pollution in the northern China region are not yet well understood, due to a lack of long-term, comprehensive observations and objective identification techniques. Based on principal component analysis combined with high-time-resolution observations of particulate matter components, here we developed a robust method to identify dust storm events and identified 14 dust events in Beijing in 2019. We further classified these 14 events into two distinct types using Lagrangian particle dispersion models and backward trajectory analysis. The first type (Type I, 9 cases) is characterized by synoptic patterns in Mongolia, originating from the north and directly impacting the Beijing area. The second type (Type II, 5 cases) involves air masses from the north or northwest that temporarily pass through polluted regions south of Beijing before being carried back into the city. Consistently, during Type I dust events, we observed a sharp decrease in secondary inorganic aerosols (SIA) from 65 % to 7 %, as well as in the sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) (from 0.52 to 0.19, and 0.27 to 0.018 respectively). In contrast, during Type II dust events, SIA concentrations increased by 91 %, along with an increase in SOR (1.7 %), NOR (69 %), and f44/f43 (3.0 %), suggesting an enhancement of secondary aerosol formation resulting from the interaction between dust aerosols and gaseous anthropogenic pollutants. Our results demonstrate that dust events and the sub-type of dust events can be identified in an objective manner using the protocol developed in this study and the dynamics should be considered when discussing impacts of dust events on atmospheric chemistry.

Secondary Organic Aerosol Formation from the Photooxidation of Aromatic Ketone Intermediate Volatile Organic Compounds.

Oxygenated aromatics are substantial secondary organic aerosol (SOA) precursors, such as benzyl alcohol and phenolic compounds. Aromatic ketone intermediate volatile organic compounds (IVOCs), as a subclass of oxygenated aromatics, were found in anthropogenic source emissions and may contribute to SOA formation. However, the SOA yields and formation pathways of aromatic ketone IVOCs remain unknown. In this study, the photooxidations of aromatic ketone IVOCs in the absence and presence of NOx were studied in an oxidation flow reactor, and the particle- and gas-phase oxidation products were measured. The maximum SOA yields of benzophenone and 1,2-diphenylethanone are 0.24 and 0.33-0.35, respectively, relatively high among oxygenated aromatics. The SOA yields in the presence of NOx are 2-3 times higher than those in the absence of NOx in the late stage of oxidation. As the photooxidation proceeds, H/C of SOA slightly increases with O/C, and a greater amount of more-oxidized ring-retaining products exists in the particle phase in the presence of NOx. Based on gas-phase products and possible reaction pathways, functionalization of benzoic acid via the phenolic pathway is favored in the presence of NOx. Thus, our study highlights the significant SOA formation from aromatic ketone IVOCs, especially in the presence of NOx during long-time photooxidation.

Anthropogenic Extremely Low Volatility Organics (ELVOCs) Govern the Growth of Molecular Clusters Over the Southern Great Plains During the Springtime

AbstractNew particle formation (NPF) often drives cloud condensation nuclei concentrations and the processes governing nucleation of molecular clusters vary substantially in different regions. The growth of these clusters from ∼2 to >10 nm diameters is often driven by the availability of extremely low volatility organic vapors (ELVOCs). Although the pathways to ELVOC formation from the oxidation of biogenic terpenes are better understood, the mechanistic pathways for ELVOC formation from oxidation of anthropogenic organics are less well understood. We integrate measurements and detailed regional model simulations to understand the processes governing NPF and secondary organic aerosol formation at the Southern Great Plain (SGP) observatory in Oklahoma and compare these with a site within the Bankhead National Forest (BNF) in Alabama, southeast USA. During our two simulated NPF event days, nucleation rates are predicted to be at least an order of magnitude higher at SGP compared to BNF largely due to lower sulfuric acid (H2SO4) concentrations at BNF. Among the different nucleation mechanisms in WRF‐Chem, we find that the dimethylamine (DMA) + H2SO4 nucleation mechanism dominates at SGP. We find that anthropogenic ELVOCs are critical for explaining the growth of particles observed at SGP. Treating organic particles as semisolid, with strong diffusion limitations for organic vapor uptake in the particle phase, brings model predictions into closer agreement with observations. We also simulate two non‐NPF event days observed at the SGP site and show that low‐level clouds reduce photochemical activity with corresponding reductions in H2SO4 and anthropogenic ELVOC concentrations, thereby explaining the lack of NPF.

A large long standing keratinous cyst on the cheek: a case report

Epidermal inclusion cysts or keratinous cysts can be congenital or acquired. These slow-growing, chronic cysts can sometimes be neglected, unless they affect cosmesis or present the fear of turning malignant. We present a case of a keratinous cyst on a patient’s cheek, overlooked for many years, which slowly and steadily kept on growing and finally presenting as a disfiguring ovoid swelling over the patient’s cheek. Epithelial inclusion cysts have a tendency of slow but steady growth, with a rare of real risk of malignant change. Secondary infection, abscess formation, pressure effect and cosmetic effect are a few complications seen in such cases. Improper excision of these cysts leads to recurrence due to left over residual cyst tissue. This unearths the importance of timely investigation and treatment of swellings that we might at first assume to be insignificant.