Effects of dietary supplementation of glycerol monolaurate on laying performance, egg quality, antioxidant capacity, intestinal morphology and immune function in late-phase laying hens.

The objective of this study was to evaluate the effects of different levels of glycerol monolaurate (GML) on laying performance, egg quality, antioxidant capacity, intestinal morphology and immune function in late-phase laying hens. A total of 480 Hy-Line Variety Brown hens (age 54 wk) were randomly assigned to 5 treatments: the control group (basal diet) and 4 GML groups (basal diet supplemented with 100, 200, 300, and 400 mg/kg GML). Each treatment consisted of 8 replicates with 12 hens each and the trial lasted for 8 wk. The results showed that dietary inclusion of GML increased the ADFI in the entire experimental period and the average egg weight in wk 5 to 8 and wk 1 to 8 of the experiment (linear, P < 0.05). Dietary GML addition linearly increased albumen height, Haugh unit and yolk color, and quadratically increased eggshell thickness (P < 0.05). The serum SOD activity, T-AOC and IgG concentrations in the 200 mg/kg GML group, and GSH-Px activity in 200 and 300 mg/kg GML groups were increased, while the MDA concentration in 200 and 300 mg/kg GML groups was decreased than those in the control group (P < 0.05). The jejunal villus height and villus height: crypt depth in 300 mg/kg GML group were higher than that in the control group (P < 0.05). The mRNA expression of TLR4, IL-1ß and TNF-α in spleen and jejunum decreased with the increase of dietary GML concentration (linear, P < 0.05). In conclusion, dietary GML supplementation could improve egg quality, antioxidant capacity, intestinal morphology and immune function in late-phase laying hens, and dietary 300 mg/kg GML inclusion is suggested.

Treatment of Sinus Graft Infection After Sinus Floor Elevation: A Series of Four Case Reports.

This report of cases aims to share our treatment experiences in 4 sinus graft infection cases after sinus floor elevation and simultaneous implant placement. The preoperative and postoperative intraoral and radiographic photographs were collected and used to assess the treatment outcomes. The sinus cavity status, bone augmentation results, and implant stability were used as measurements to determine the treatment effectiveness. Four patients received partial graft removal as their surgical treatment for sinus graft infection combined with antibiotic therapy, with or without immediate secondary grafting. After early intervention, antibiotic therapy, and partial debridement of the infected sinus grafts, radiographic and clinical outcomes indicate successful resolution of the graft infection and stable bone graft levels around the implants. The keys to the successful management of the sinus graft infection were: early detection of the infection; early intervention, including partial debridement of the infected graft particles; and antibiotic therapy.

Understanding the importance of atmospheric transformation in assessing the hazards of liquid crystal monomers.

Liquid crystal monomers (LCMs), a group of synthetic chemicals released from liquid crystal devices such as televisions and smartphones, have recently been recognized as emerging contaminants due to their widespread occurrence in the environment and potential negative impacts on human health. Airborne LCMs can undergo atmospheric oxidation reactions to form various transformation products. Despite the certainty of atmospheric transformation chemistry, the knowledge about the hazard properties of transformation products remains largely unknown. Here, we perform an in silico model-based evaluation of the persistence, bioaccumulation potential, mobility, and toxicity of two representative LCMs, namely, 1-ethyl-4-(4-(4-propylcyclohexyl)phenyl)benzene and 4''-ethyl-2'-fluoro-4-propyl-1,1':4',1''-terphenyl, and their transformation products. We found that, among the investigated transformation products, 38% have overall persistence greater than the minimum of 331 days among the persistent organic pollutants regulated by the Stockholm Convention, 62% meet the bioaccumulation threshold of 1000 L kg-1 used by the United States Environmental Protection Agency, 44% are classified "mobile" according to the criterion used by the German Environmental Agency, and 58% have the potential to induce unacceptable toxic effects in aquatic organisms. Furthermore, we identified several transformation products with increased persistence, bioaccumulation potential, and mobility compared to their parent compounds. These findings not only offer insights for prioritizing LCM transformation products for future risk assessment, but also underscore the significance of considering atmospheric transformation in the evaluation of environmental risks posed by emerging contaminants, including LCMs.

Synthetic Antioxidants as Contaminants of Emerging Concern in Indoor Environments: Knowns and Unknowns.

Synthetic antioxidants, including synthetic phenolic antioxidants (SPAs), amine antioxidants (AAs), and organophosphite antioxidants (OPAs), are essential additives for preventing oxidative aging in various industrial and consumer products. Increasing attention has been paid to the environmental contamination caused by these chemicals, but our understanding of synthetic antioxidants is generally limited compared to other emerging contaminants such as plasticizers and flame retardants. Many people spend a significant portion (normally greater than 80%) of their time indoors, meaning that they experience widespread and persistent exposure to indoor contaminants. Thus, this Perspective focuses on the problem of synthetic antioxidants as indoor environmental contaminants. The wide application of antioxidants in commercial products and their demonstrated toxicity make them an important family of indoor contaminants of emerging concern. However, significant knowledge gaps still need to be bridged: novel synthetic antioxidants and their related transformation products need to be identified in indoor environments, different dust sampling strategies should be employed to evaluate human exposure to these contaminants, geographic scope and sampling scope of research on indoor contamination should be broadened, and the partition coefficients of synthetic antioxidants among different media need to be investigated.

Design Strategy of High Stability Vertically Aligned RGO@V2O5 Heterostructure Cathodes for Flexible Quasi-Solid-State Aqueous Zinc-Ion Batteries.

Among various cathodes for aqueous zinc-ion batteries (AZIBs), vanadium-based oxides have garnered significant attention in research circles owing to their exceptionally high theoretical specific capacity. However, the outstanding zinc storage capacity of vanadium pentoxide is constrained by its irreversible dissolution in an aqueous solution. Here, we propose a laser reduction of graphene oxide and construct a heterostructure of V2O5 coated with vertically aligned reduced graphene oxide (VrGO). The VrGO nanosheets effectively suppress the dissolution of V2O5 and provide channels for the efficient transport of zinc ions and electrons, so the electrochemical reaction kinetics of the electrode are improved. The AZIB based on the VrGO@V2O5 heterostructure cathode has a high specific capacity of 254.9 mAh g-1 at 0.2 A g-1 and excellent cycle stability with a capacity retention rate of 90.1% after 5000 cycles of charge and discharge. When assembled into a flexible quasi-solid-state AZIB, the capacity of the device is reduced by only 2% after 1000 bending cycles, showing good potential for wearable applications. This work provides a reliable strategy for designing flexible AZIB with high electrochemical performance and structural stability.

Wide-Potential-Window Bimetallic Hydrated Eutectic Electrolytes with High-Temperature Resistance for Zinc-Ion Hybrid Capacitors.

Aqueous zinc-ion hybrid capacitors (ZHCs) are considered ideal energy-storage devices. However, the common aqueous Zn2+ -containing electrolytes used in ZHCs often cause parasitic reactions during charging-discharging owing to free water molecules. Hydrated eutectic electrolytes (HEEs) that bind water molecules through solvation shells and hydrogen bonds can be applied at high temperatures and within a wide potential window. This study reports a novel bimetallic HEE (ZnK-HEE), consisting of zinc chloride, potassium chloride, ethylene glycol, and water, which enhances the capacity and electrochemical reaction kinetics of ZHCs. The bimetallic solvation shell in ZnK-HEE is studied by molecular dynamics and density functional theory, confirming its low step-by-step desolvation energy. A Zn//activated carbon ZHC in ZnK-HEE shows a high operating voltage of 2.1 V, along with an ultrahigh capacity of 326.9 mAh g-1 , power density of 2099.7 W kg-1 , and energy density of 343.2 Wh kg-1 at 100 °C. The reaction mechanisms of charging-discharging process are investigated by ex situ X-ray diffraction. This study reports a promising electrolyte for high-performance ZHCs, which exhibits high-temperature resistance and is operable within a wide potential window.

Transcriptome analysis of human peri-implant soft tissue and periodontal gingiva: a paired design study.

OBJECTIVES: Limited information is available about the biological characterization of peri-implant soft tissue at the transcriptional level. The aim of this study was to investigate the effect of dental implant on the soft tissue in vivo by using paired samples and compare the differences between peri-implant soft tissue and periodontal gingiva at the transcriptional level. METHODS: Paired peri-implant soft tissue and periodontal gingiva tissue from 6 patients were obtained, and the pooled RNAs were analyzed by deep sequencing. Venn diagram was used to further screen out differentially expressed genes in every pair of samples. Annotation and enrichment analysis was performed. Further verification was done by quantitative real-time PCR. RESULTS: Totally 3549 differentially expressed genes (DEGs) were found between peri-implant and periodontal groups. The Venn diagram further identified 185 DEGs in every pair of samples, of which the enrichment analysis identified significant enrichment for cellular component was associated with external side of plasma membrane, for molecular function was protein binding, for biological process was immune system process, and for KEGG pathway was cytokine-cytokine receptor interaction. Among the DEGs, CST1, SPP1, AQP9, and SFRP2 were verified to be upregulated in peri-implant soft tissue. CONCLUSIONS: Peri-implant soft tissue showed altered expressions of several genes related to the cell-ECM interaction compared to periodontal gingiva. CLINICAL RELEVANCE: Compared to periodontal gingiva, altered cell-ECM interactions in peri-implant may contribute to the susceptibility of peri-implant diseases. At the transcriptional level, periodontal gingiva is generally considered the appropriate control for peri-implantitis, except regarding the cell-ECM interactions.

Obesity difference on association blood malondialdehyde level and diastolic hypertension in the elderly population: a cross-sectional analysis.

AIMS: Although increased production of malondialdehyde (MDA), an end product of lipid oxidation caused by reactive oxygen species (ROS), has been found be elevated in hypertensive population, whether MDA contributed to a changed risk of hypertension is uncertain. We aimed to investigate whether elevated blood levels of MDA contribute to increased risk of hypertension and obesity has a modified effect on the association in an older Chinese population. METHODS: Data were obtained from 2011 to 2012 of the Chinese Longitudinal Healthy Longevity Survey (CLHLS), a national cohort of older adults in China. Associations between blood MDA level and systolic and diastolic blood pressure (BP) and risk of hypertension were performed by multivariable linear regression and logistic regression analysis. RESULTS: The results of smooth curve revealed a gradual upward trend on association of blood MDA level with diastolic BP (P < 0.001), but not with systolic BP (P > 0.05). Logistic regression analysis suggested that elevated blood MDA levels were associated with increased risk of diastolic hypertension (OR = 1.079, 95% CI 1.039-1.122, P < 0.001) rather than systolic hypertension (OR = 0.978, 95% CI 0.943-1.015, P = 0.247) after adjustments of related confounding factors were made. Furthermore, we found the significant modification effect of obesity on the association between MDA level and risk of diastolic hypertension evaluated by body mass index (BMI, interaction P = 0.015) and by waist circumference (interaction P = 0.016). CONCLUSION: Our results firstly identified that increased blood MDA levels were associated with elevated risk of diastolic hypertension, rather than systolic hypertension in the non-obese old population.

Widespread formation of toxic nitrated bisphenols indoors by heterogeneous reactions with HONO.

With numerous structurally diverse indoor contaminants, indoor transformation chemistry has been largely unexplored. Here, by integrating protein affinity purification and nontargeted mass spectrometry analysis (PUCA), we identified a substantial class of previously unrecognized indoor transformation products formed through gas-surface reactions with nitrous acid (HONO). Through the PUCA, we identified a noncommercial compound, nitrated bisphenol A (BPA), from house dust extracts strongly binding to estrogen-related receptor γ. The compound was detected in 28 of 31 house dust samples with comparable concentrations (ND to 0.30 µg/g) to BPA. Via exposing gaseous HONO to surface-bound BPA, we demonstrated it likely forms via a heterogeneous indoor chemical transformation that is highly selective toward bisphenols with electron-rich aromatic rings. We used 15N-nitrite for in situ labeling and found 110 nitration products formed from indoor contaminants with distinct aromatic moieties. This study demonstrates a previously unidentified class of chemical reactions involving indoor HONO, which should be incorporated into the risk evaluation of indoor contaminants, particularly bisphenols.

A polyaniline surface-modified Prussian blue analogue cathode for flexible aqueous Zn-ion batteries.

Aqueous Zn-ion batteries have gained popularity due to their low cost and high safety, but their low energy density limits their application scenarios. Although the Prussian blue analogue (PBA) has the characteristics of high redox potential, the poor capacity and cycling performance restrict its further development. Here, we propose a modification strategy of a polyaniline (PANI) coating on zinc ferricyanide (ZnHCF). The PANI coating inhibits the dissolution of ZnHCF and enables the Zn-ion battery to present two long-flat discharge voltage platforms as well as a high capacity of 150 mA h g-1, which provides a new idea for the development of high-performance PBA battery materials. Meanwhile, owing to the spring-like structure, the battery has a high stretchability of 600% and maintains stable electrochemical properties during stretching.

The L-shaped association between superoxide dismutase levels and blood pressure in older Chinese adults: community-based, cross-sectional study.

BACKGROUND: As an antioxidant, serum superoxide dismutase (SOD) have been found to be associated with hypertension. METHODS: The data were derived from the Chinese Longitudinal Healthy Longevity Survey (CLHLS), a prospective cohort study in China. We explored the association between serum SOD and blood pressure (BP) using multivariable correction analysis in an older Chinese population. RESULTS: We observed a significantly gradual downward trend in the association between serum SOD levels and diastolic BP (DBP) in participants with lower serum SOD levels (< 58 IU/mL), while no associations were observed between serum SOD levels and DBP in participants with higher serum SOD levels (> 58 IU/mL). Similar results showed a significant gradual downward trend in associations between serum SOD levels and the risk of diastolic hypertension only at SOD < 58 IU/mL. Multiple linear regression analysis suggested that serum SOD was negatively correlated with DBP (Sß = -0.088,P < 0.001) but not with SBP (Sß = 0.013, P = 0.607). Multiple logistic regression analysis suggested that serum SOD was independently associated with the risk of diastolic hypertension (OR = 0.984, 95% CI: 0.973-0.996, P = 0.010) but not with the risk of systolic hypertension (OR = 1.001, 95% CI: 0.990-1.012,P = 0.836)) after adjusting for relevant confounding factors. Serum SOD levels (< 58 IU/mL, > 58 IU/mL) were an effect modifier of the association between serum SOD and DBP (interactionP = 0.0038) or the risk of diastolic hypertension (interaction P = 0.0050). CONCLUSIONS: Our study indicated for the first time that there was an L-shaped association between serum SOD levels and the risk of diastolic hypertension in the older Chinese population.

Inhibitory effect of roflumilast on experimental periodontitis.

BACKGROUND: Phosphodiesterase-4 (PDE4) has been identified as a valid therapeutic target in several inflammatory diseases. In this study, we assessed PDE4 in gingival tissue from patients with chronic periodontitis and evaluated the therapeutic effects of the PDE4 inhibitor, roflumilast, in an experimental rat model of periodontitis. METHODS: Gingival tissue specimens from 20 healthy subjects and 20 patients with periodontitis were collected, and the mRNA expression levels of PDE4, interleukin (IL)-1ß, and IL-6 were assessed. Ninety rats were divided randomly into three groups (30 per group): non-ligature group, ligature-induced periodontitis group (L), and ligature-induced periodontitis with roflumilast administered group (5 mg/kg/d) (L+R). Rats were euthanized on days 3, 8, and 14. Alveolar bone resorption was analyzed using microcomputed tomography. Inflammation and osteoclast number were analyzed histologically. Finally, the mRNA expression levels of PDE-4, IL-1ß, IL-6, tumor necrosis factor (TNF)-α, and nuclear factor kappa B (NF-κB) were assessed in the rat gingival tissue. RESULTS: The mRNA expression levels of PDE4, IL-1ß, and IL-6 in the gingiva were significantly higher in patients with periodontitis compared with healthy individuals (P <0.05). Alveolar bone loss, degree of inflammation, number of TRAP-positive multinucleated osteoclasts, and mRNA expression levels of IL-1ß, IL-6, TNF-α, NF-κB, and PDE4 in the L+R group were significantly lower than those in the L group (P <0.05). CONCLUSIONS: PDE4 expression was increased in the gingiva of patients with periodontitis. Roflumilast may decrease alveolar bone loss and the expression of inflammatory cytokines in rats with ligature-induced periodontitis.

Learning with few samples in deep learning for image classification, a mini-review.

Deep learning has achieved enormous success in various computer tasks. The excellent performance depends heavily on adequate training datasets, however, it is difficult to obtain abundant samples in practical applications. Few-shot learning is proposed to address the data limitation problem in the training process, which can perform rapid learning with few samples by utilizing prior knowledge. In this paper, we focus on few-shot classification to conduct a survey about the recent methods. First, we elaborate on the definition of the few-shot classification problem. Then we propose a newly organized taxonomy, discuss the application scenarios in which each method is effective, and compare the pros and cons of different methods. We classify few-shot image classification methods from four perspectives: (i) Data augmentation, which contains sample-level and task-level data augmentation. (ii) Metric-based method, which analyzes both feature embedding and metric function. (iii) Optimization method, which is compared from the aspects of self-learning and mutual learning. (iv) Model-based method, which is discussed from the perspectives of memory-based, rapid adaptation and multi-task learning. Finally, we conduct the conclusion and prospect of this paper.

Uncovering global-scale risks from commercial chemicals in air.

Commercial chemicals are used extensively across urban centres worldwide1, posing a potential exposure risk to 4.2 billion people2. Harmful chemicals are often assessed on the basis of their environmental persistence, accumulation in biological organisms and toxic properties, under international and national initiatives such as the Stockholm Convention3. However, existing regulatory frameworks rely largely upon knowledge of the properties of the parent chemicals, with minimal consideration given to the products of their transformation in the atmosphere. This is mainly due to a dearth of experimental data, as identifying transformation products in complex mixtures of airborne chemicals is an immense analytical challenge4. Here we develop a new framework-combining laboratory and field experiments, advanced techniques for screening suspect chemicals, and in silico modelling-to assess the risks of airborne chemicals, while accounting for atmospheric chemical reactions. By applying this framework to organophosphate flame retardants, as representative chemicals of emerging concern5, we find that their transformation products are globally distributed across 18 megacities, representing a previously unrecognized exposure risk for the world's urban populations. More importantly, individual transformation products can be more toxic and up to an order-of-magnitude more persistent than the parent chemicals, such that the overall risks associated with the mixture of transformation products are also higher than those of the parent flame retardants. Together our results highlight the need to consider atmospheric transformations when assessing the risks of commercial chemicals.

Evolution of Atmospheric Total Organic Carbon from Petrochemical Mixtures.

Reactive organic compounds play a central role in the formation of ozone and secondary organic aerosols. The ability to accurately predict their fate, in part, relies upon quantitative knowledge of the chemical and physical parameters associated with the total organic carbon (TOC), which includes both precursors and oxidation products that evolve in the atmosphere over short to long time scales. However, such knowledge, obtained via limited carbon closure experiments, has not been attained for complex anthropogenic emissions. Here we present the first comprehensive characterization of TOC in the atmospheric oxidation of organic vapors from light and heavy oil mixtures associated with oil sand operations. Despite the complexity of the investigated oil mixtures, we are able to achieve carbon closure (83-116%) within the uncertainties (±20%), with the degree of the closure being dependent upon the vapor composition and NOx levels. In contrast to biogenic precursors (e.g., α-pinene), the photochemical time scale required for a largely complete oxidation and evolution of chemical parameters is very long for the petrochemical vapors (i.e., ∼7-10 days vs ∼1 day), likely due to the lower initial precursor reactivity. This suggests that petrochemical emissions and their impacts are likely to extend further spatially than biogenic emissions, and retain more of their complex composition and reactivity for many days. The results of this work provide key parameters to regional models for further improving the representation of the chemical evolution of petrochemical emissions.

Liquid crystal display screens as a source for indoor volatile organic compounds.

Liquid crystal displays (LCDs) have profoundly shaped the lifestyle of humans. However, despite extensive use, their impacts on indoor air quality are unknown. Here, we perform flow cell experiments on three different LCDs, including a new computer monitor, a used laptop, and a new television, to investigate whether their screens can emit air constituents. We found that more than 30 volatile organic compounds (VOCs) were emitted from LCD screens, with a total screen area-normalized emission rate of up to (8.25 ± 0.90) × 109 molecules ⋅ s-1 ⋅ cm-2 In addition to VOCs, 10 liquid crystal monomers (LCMs), a commercial chemical widely used in LCDs, were also observed to be released from those LCD screens. The structural identification of VOCs is based on a "building block" hypothesis (i.e., the screen-emitted VOCs originate from the "building block chemicals" used in the manufacturing of liquid crystals), which are the key components of LCD screens. The identification of LCMs is based upon the detailed information of 362 currently produced LCMs. The emission rates of VOCs and LCMs increased by up to a factor of 9, with an increase of indoor air humidity from 23 to 58% due to water-organic interactions likely facilitating the diffusion rates of organics. These findings indicate that LCD screens are a potentially important source for indoor VOCs that has not been considered previously.

Long non-coding RNA and mRNA expression profiles in peri-implantitis vs periodontitis.

BACKGROUND AND OBJECTIVE: Peri-implantitis is a biofilm-mediated infectious disease that results in progressive loss of implant-supporting bone. As compared to its analogue periodontitis, peri-implantitis is generally known to be more aggressive, with comparatively rapid progression and less predictable treatment outcomes, especially when advanced. An understanding of molecular mechanisms underpinning the similarities and differences between peri-implantitis and periodontitis is essential to develop novel management strategies. This study aimed to compare long non-coding RNAs (lncRNAs) and messenger RNA (mRNA) expression profiles between peri-implantitis and periodontitis. METHODS: Inflamed soft tissue from peri-implantitis and periodontitis lesions, and healthy gingival tissue controls were analyzed by microarray. Cluster graphs, gene ontology (GO) analysis, and pathway analysis were performed. Quantitative real-time PCR was employed to verify microarray results. The expression levels of RANKL and OPG in the three tissue types were also evaluated, using qRT-PCR. Coding non-coding (CNC) network analyses were performed. RESULTS: Microarray analyses revealed 1079 lncRNAs and 1003 mRNAs as differentially expressed in peri-implantitis when compared to periodontitis. The cyclooxygenase-2 pathway was the most up-regulated biological process in peri-implantitis as compared to periodontitis, whereas hemidesmosome assembly was the most down-regulated pathway. Osteoclast differentiation was relatively up-regulated, and RANKL/OPG ratio was higher in peri-implantitis than in periodontitis. CONCLUSIONS: The study demonstrated that peri-implantitis and periodontitis exhibit significantly different lncRNA and mRNA expression profiles, suggesting that osteoclast differentiation-related pathways are comparatively more active in peri-implantitis. These data highlight potential molecular targets for periodontitis and peri-implantitis therapy development.

Experimental Study of OH-Initiated Heterogeneous Oxidation of Organophosphate Flame Retardants: Kinetics, Mechanism, and Toxicity.

The environmental risks and health impacts associated with particulate organophosphate flame retardants (OPFRs), which are ubiquitous in the global atmosphere, have not been adequately assessed due to the lack of data on the reaction kinetics, products, and toxicity associated with their atmospheric transformations. Here, the importance of such transformations for OPFRs are explored by investigating the reaction kinetics, degradation chemical mechanisms, and toxicological evolution of two OPFRs (2-ethylhexyl diphenyl phosphate (EHDP) and diphenyl phosphate (DPhP)) coated on (NH4)2SO4 particles upon heterogeneous OH oxidation. The derived reaction rate constants for the heterogeneous loss of EHDP and DPhP are (1.12 ± 0.22) × 10-12 and (2.33 ± 0.14) × 10-12 cm3 molecules-1 s-1, respectively. Using recently developed real-time particle chemical composition measurements, particulate products from heterogeneous photooxidation and the associated degradation mechanisms for particulate OPFRs are reported for the first time. Subsequent cytotoxicity analysis of the unreacted and oxidized OPFR particles indicated that the overall particle cytotoxicity was reduced by up to 94% with heterogeneous photooxidation, likely due to a significantly lower cytotoxicity associated with the oxidized OPFR products relative to the parent OPFRs. The present work not only provides guidance for future field sampling for the detection of transformation products of OPFRs, but also strongly supports the ongoing risk assessment of these emerging chemicals and most critically, their products.

Understanding the Impact of High-NOx Conditions on the Formation of Secondary Organic Aerosol in the Photooxidation of Oil Sand-Related Precursors.

Oil sands (OS) are an important type of heavy oil deposit, for which operations in Alberta, Canada, were recently found to be a large source of secondary organic aerosol (SOA). However, SOA formation from the OS mining, processing, and subsequent tailings, especially in the presence of NOx, remains unclear. Here, photooxidation experiments for OS-related precursors under high-NOx conditions were performed using an oxidation flow reactor, in which ∼95% of peroxy radicals (RO2) react with NO. The SOA yields under high-NOx conditions were found to be lower than yields under low-NOx conditions for all precursors, which is likely due to the higher volatilities of the products from the RO2 + NO pathway compared with RO2 + HO2. The SOA yields under high-NOx conditions show a strong dependence on pre-existing surface area (not observed in previous low-NOx experiments), again attributed to the higher product volatilities. Comparing the mass spectra of SOA formed from different precursors, we conclude that the fraction of m/z > 80 (F80) can be used as a parameter to separate different types of SOA in the region. In addition, particle-phase organic nitrate was found to be an important component (9-23%) of OS SOA formed under high-NOx conditions. These results have implications for better understanding the atmospheric processing of OS emissions.

Understanding the Impact of Relative Humidity and Coexisting Soluble Iron on the OH-Initiated Heterogeneous Oxidation of Organophosphate Flame Retardants.

The current uncertainties in the reactivity and atmospheric persistence of particle-associated chemicals present a challenge for the prediction of long-range transport and deposition of emerging chemicals such as organophosphate flame retardants, which are ubiquitous in the global environment. Here, the OH-initiated heterogeneous oxidation kinetics of organophosphate flame retardants (OPFRs) coated on inert (NH4)2SO4 and redox-active FeSO4 particles were systematically determined as a function of relative humidity (RH). The derived reaction rate constants for the heterogeneous loss of tricresyl phosphate (TCP; kTCP) and tris(2-butoxyethyl) phosphate (TBEP; kTBEP) were in the range of (2.69-3.57) × 10-12 and (3.06-5.55) × 10-12 cm3 molecules-1 s-1, respectively, depending on the RH and coexisting Fe(II) content. The kTCP (coated on (NH4)2SO4) was relatively constant over the investigated RH range while kTBEP was enhanced by up to 19% with increasing RH. For both OPFRs, the presence of Fe(II) enhanced their k by up to 53% over inert (NH4)2SO4. These enhancement effects (RH and Fe(II)) were attributed to fundamental changes in the organic phase state (higher RH lowered particle viscosity) and Fenton-type chemistry which resulted in the formation of reactive oxygen species, respectively. Such findings serve to emphasize the importance of ambient RH, the phase state of particle-bound organics in general, and the presence of coexisting metallic species for an accurate description of the degradation kinetics and aging of particulate OPFRs in models used to evaluate their atmospheric persistence.