Potential Factors Contributing to Ozone Production in AQUAS-Kyoto Campaign in Summer 2020: Natural Source-Related Missing OH Reactivity and Heterogeneous HO2/RO2 Loss.

This study presents total OH reactivity, ancillary trace species, HO2 reactivity, and complex isoprene-derived RO2 reactivity due to ambient aerosols measured during the air quality study (AQUAS)-Kyoto campaign in September, 2020. Observations were conducted during the coronavirus disease (COVID-19) pandemic (associated with reduced anthropogenic emissions). The spatial distribution of missing OH reactivity highlights that the origin of volatile organic compounds (VOCs) may be from natural-emission areas. For the first time, the real-time loss rates of HO2 and RO2 onto ambient aerosols were measured continuously and alternately. Ozone production sensitivity was investigated considering unknown trace species and heterogeneous loss effects of XO2 (≡HO2 + RO2) radicals. Missing OH reactivity enhanced the ozone production potential by a factor of 2.5 on average. Heterogeneous loss of radicals could markedly suppress ozone production under low NO/NOx conditions with slow gas-phase reactions of radicals and change the ozone regime from VOC- to NOx-sensitive conditions. This study quantifies the relationship of missing OH reactivity and aerosol uptake of radicals with ozone production in Kyoto, a low-emission suburban area. The result has implications for future NOx-reduction policies. Further studies may benefit from the combination of chemical transport models and inverse modeling over a wide spatiotemporal range.

Relative and Absolute Sensitivity Analysis on Ozone Production in Tsukuba, a City in Japan.

The change in the ozone production rate on reducing its precursors, namely, ozone production sensitivity, is important information for developing a strategy to reduce ozone. We expanded a conventional sensitivity analysis theory by including peroxy radical loss by uptake onto particle surfaces in the aim of examining their potential impact. We also propose a new concept of absolute sensitivity that enables us to evaluate the quantitative effectiveness of precursor reduction toward mitigating ozone production over a given period and area. This study applies the theory to observations in Tsukuba, a city in Japan. The relative sensitivity analysis shows that ozone production was more sensitive to volatile organic compounds (VOCs) in the morning and evening, and it became more sensitive to NOx in the afternoon. NO depletion was a main trigger in this sensitivity regime transition. The absolute sensitivity analysis indicates that the VOC-sensitive period in the morning determines the total ozone production sensitivity in a day. While particles did not have significant impact on regime classification in Tsukuba, they have a potential to decrease the mitigating effect of VOC reduction on ozone production and to moderate the enhancement effect of NOx reduction depending upon uptake coefficients. A further study will benefit from a combination with an observation-constrained box model simulation or chemical transport modeling system, which may provide sensitivity analysis over a large spatial and temporal range.

Effect of Oxidation Process on Complex Refractive Index of Secondary Organic Aerosol Generated from Isoprene.

Oxidation of isoprene by hydroxyl radical (OH), ozone (O3), or nitrate radical (NO3) leads to the formation of secondary organic aerosol (SOA) in the atmosphere. This SOA contributes to the radiation balance by scattering and absorbing solar radiation. In this study, the effect of oxidation processes on the wavelength-dependent complex refractive index (RI) of SOA generated from isoprene was examined. Oxidation conditions did not have a large effect on magnitude and wavelength dependence of the real part of the RI. In the case of SOA generated in the presence of sulfur dioxide (SO2), significant light absorption at short visible and ultraviolet wavelengths with the imaginary part of the RI, up to 0.011 at 375 nm, was observed during oxidation with OH. However, smaller and negligible values were observed during oxidation with O3 and NO3, respectively. Moreover, in the absence of SO2, light absorption was not observed regardless of the oxidation process. There was an empirical correlation between the imaginary part of the RI and the average degree of unsaturation of organic molecules. The results obtained herein demonstrate that oxidation processes should be considered for estimating the radiative effect of isoprene-derived SOA.

The perception of air pollution and its health risk: a scoping review of measures and methods.

BACKGROUND: Although there is increasing awareness of the health risks of air pollution as a global issue, few studies have focused on the methods for assessing individuals' perceptions of these risks. This scoping review aimed to identify previous research evaluating individuals' perceptions of air pollution and its health effects, and to explore the measurement of perceptions, as a key resource for health behaviour. METHODS: The review followed the methodological framework proposed by Arksey and O'Malley. PubMed and Web of Science were searched. After initial and full-text screening, we further selected studies with standardised scales that had previously been tested for reliability and validity in assessing awareness and perceptions. RESULTS: After full-text screening, 95 studies were identified. 'Perception/awareness of air quality' was often measured, as well as 'Perception of health risk.' Only nine studies (9.5%) used validated scaled questionnaires. There was considerable variation in the scales used to measure the multiple dimensions of risk perception for air pollution. CONCLUSION: Few studies used structured scales to quantify individuals' perceptions, limiting comparisons among studies. Standardised methods for measuring health risk perception are needed.

Main findings: Among 95 studies assessing health risk perception of air pollution, only nine studies used standardised scales.Added knowledge: There was considerable variation in the scales measuring the multiple dimensions of risk perception for air pollution, which makes comparison among the studies difficult.Global health impact for policy and action: This review highlights the need for the development of globally standardised scale to measure the health risk perception of air pollution.

Molecular and cellular changes associated with the evolution of novel jaw muscles in parrots.

Vertebrates have achieved great evolutionary success due in large part to the anatomical diversification of their jaw complex, which allows them to inhabit almost every ecological niche. While many studies have focused on mechanisms that pattern the jaw skeleton, much remains to be understood about the origins of novelty and diversity in the closely associated musculature. To address this issue, we focused on parrots, which have acquired two anatomically unique jaw muscles: the ethmomandibular and the pseudomasseter. In parrot embryos, we observe distinct and highly derived expression patterns for Scx, Bmp4, Tgfß2 and Six2 in neural crest-derived mesenchyme destined to form jaw muscle connective tissues. Furthermore, immunohistochemical analysis reveals that cell proliferation is more active in the cells within the jaw muscle than in surrounding connective tissue cells. This biased and differentially regulated mode of cell proliferation in cranial musculoskeletal tissues may allow these unusual jaw muscles to extend towards their new attachment sites. We conclude that the alteration of neural crest-derived connective tissue distribution during development may underlie the spatial changes in jaw musculoskeletal architecture found only in parrots. Thus, parrots provide valuable insights into molecular and cellular mechanisms that may generate evolutionary novelties with functionally adaptive significance.

Very high particulate pollution over northwest India captured by a high-density in situ sensor network.

Exposure to particulate matter less than 2.5 µm in diameter (PM2.5) is a cause of concern in cities and major emission regions of northern India. An intensive field campaign involving the states of Punjab, Haryana and Delhi national capital region (NCR) was conducted in 2022 using 29 Compact and Useful PM2.5 Instrument with Gas sensors (CUPI-Gs). Continuous observations show that the PM2.5 in the region increased gradually from < 60 µg m-3 in 6-10 October to up to 500 µg m-3 on 5-9 November, which subsequently decreased to about 100 µg m-3 in 20-30 November. Two distinct plumes of PM2.5 over 500 µg m-3 are tracked from crop residue burning in Punjab to Delhi NCR on 2-3 November and 10-11 November with delays of 1 and 3 days, respectively. Experimental campaign demonstrates the advantages of source region observations to link agricultural waste burning and air pollution at local to regional scales.

Fluorescence detection of atmospheric nitrogen dioxide using a blue light-emitting diode as an excitation source.

We report on the development of a low-cost and compact instrument for quantifying atmospheric NO(2) concentrations by detecting NO(2) fluorescence using a commercial light-emitting diode around 435 nm as a fluorescence excitation light source. The minimum detectable limit of the NO(2) instrument developed has been estimated to be 9.8 parts per billion of volume mixing ratio (ppbv) in a 60 s integration time and with a signal-to-noise ratio of 2.

PM2.5 diminution and haze events over Delhi during the COVID-19 lockdown period: an interplay between the baseline pollution and meteorology.

Delhi, a tropical Indian megacity, experiences one of the most severe air pollution in the world, linked with diverse anthropogenic and biomass burning emissions. First phase of COVID-19 lockdown in India, implemented during 25 March to 14 April 2020 resulted in a dramatic near-zeroing of various activities (e.g. traffic, industries, constructions), except the "essential services". Here, we analysed variations in the fine particulate matter (PM2.5) over the Delhi-National Capital Region. Measurements revealed large reductions (by 40-70%) in PM2.5 during the first week of lockdown (25-31 March 2020) as compared to the pre-lockdown conditions. However, O3 pollution remained high during the lockdown due to non-linear chemistry and dynamics under low aerosol loading. Notably, events of enhanced PM2.5 levels (300-400 µg m-3) were observed during night and early morning hours in the first week of April after air temperatures fell close to the dew-point (~ 15-17 °C). A haze formation mechanism is suggested through uplifting of fine particles, which is reinforced by condensation of moisture following the sunrise. The study highlights a highly complex interplay between the baseline pollution and meteorology leading to counter intuitive enhancements in pollution, besides an overall improvement in air quality during the COVID-19 lockdown in this part of the world.

Total hydroxyl radical reactivity measurements in a suburban area during AQUAS-Tsukuba campaign in 2017.

Missing hydroxyl radical (OH) reactivity from unknown/unmeasured trace species empirically accounts for 10%-30% of total OH reactivity and may cause significant uncertainty regarding estimation of photochemical ozone production. Thus, it is essential to unveil the missing OH reactivity for developing an effective ozone mitigation strategy. In this study, we conducted simultaneous observations of total OH reactivity and 54 reactive trace species in a suburban area as part of the Air QUAlity Study (AQUAS)-Tsukuba campaign for the summer of 2017 to gain in-depth insight into total OH reactivity in an area that experienced relatively high contributions of secondary pollutants. The campaign identified on average 35.3% of missing OH reactivity among total OH reactivity (12.9 s-1). In general, ozone-production potential estimation categorized ozone formation in this area as volatile organic compound (VOC)-limited conditions, and missing OH reactivity may increase ozone production potential 40% on average if considered. Our results suggest the importance of photochemical processes of both AVOCs and BVOCs for the production of missing OH reactivity and that we may underestimate the importance of reducing precursors in approach to suppressing ozone production if we ignore the contribution of their photochemical products.

Atmospheric chemistry of BrO radicals: kinetics of the reaction with C2H5O2 radicals at 233-333 K.

Cavity ring-down spectroscopy was used to study the title reaction in 50-200 Torr of O2 diluent at 233-333 K. There was no discernible effect of total pressure, and a rate constant of k(BrO + C2H5O2) = (3.8 +/- 1.7) x 10(-12) cm3 molecule(-1) s(-1) was determined at 293 K in 150 Torr total pressure of O2 diluent. The addition of 1.4 x 10(17) molecules cm(-3) of H2O vapor had no measurable impact on k(BrO + C2H5O2) at 293 K and 150 Torr. The rate constant exhibited a negative temperature dependence and was described by k(BrO + C2H5O2) = 6.5 x 10(-13) exp((505 +/- 570)/T) cm3 molecule(-1) s(-1). Results are discussed with respect to the atmospheric chemistry of BrO radicals.

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions.

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO2 and water vapour were observed. The isotope ratios of both CO2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ13C-CO2 and δ18O-CO2 increased, while δ2H-H2Ov and δ18O-H2Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO2 and H2Ov could be used as a tracer of meteorological information.

In situ measurement of CO2 and water vapour isotopic compositions at a forest site using mid-infrared laser absorption spectroscopy.

We conducted continuous, high time-resolution measurements of CO2 and water vapour isotopologues ((16)O(12)C(16)O, (16)O(13)C(16)O and (18)O(12)C(16)O for CO2, and H2(18)O for water vapour) in a red pine forest at the foot of Mt. Fuji for 9 days from the end of July 2010 using in situ absorption laser spectroscopy. The δ(18)O values in water vapour were estimated using the δ(2)H-δ(18)O relationship. At a scale of several days, the temporal variations in δ(18)O-CO2 and δ(18)O-H2O are similar. The orders of the daily Keeling plots are almost identical. A possible reason for the similar behaviour of δ(18)O-CO2 and δ(18)O-H2O is considered to be that the air masses with different water vapour isotopic ratios moved into the forest, and changed the atmosphere of the forest. A significant correlation was observed between δ(18)O-CO2 and δ(13)C-CO2 values at nighttime (r(2)≈0.9) due to mixing between soil (and/or leaf) respiration and tropospheric CO2. The ratios of the discrimination coefficients (Δa/Δ) for oxygen (Δa) and carbon (Δ) isotopes during photosynthesis were estimated in the range of 0.7-1.2 from the daytime correlations between δ(18)O-CO2 and δ(13)C-CO2 values.

Development of the trigeminal motor neurons in parrots: implications for the role of nervous tissue in the evolution of jaw muscle morphology.

Vertebrates have succeeded to inhabit almost every ecological niche due in large part to the anatomical diversification of their jaw complex. As a component of the feeding apparatus, jaw muscles carry a vital role for determining the mode of feeding. Early patterning of the jaw muscles has been attributed to cranial neural crest-derived mesenchyme, however, much remains to be understood about the role of nonneural crest tissues in the evolution and diversification of jaw muscle morphology. In this study, we describe the development of trigeminal motor neurons in a parrot species with the uniquely shaped jaw muscles and compare its developmental pattern to that in the quail with the standard jaw muscles to uncover potential roles of nervous tissue in the evolution of vertebrate jaw muscles. In parrot embryogenesis, the motor axon bundles are detectable within the muscular tissue only after the basic shape of the muscular tissue has been established. This supports the view that nervous tissue does not primarily determine the spatial pattern of jaw muscles. In contrast, the trigeminal motor nucleus, which is composed of somata of neurons that innervate major jaw muscles, of parrot is more developed compared to quail, even in embryonic stage where no remarkable interspecific difference in both jaw muscle morphology and motor nerve branching pattern is recognized. Our data suggest that although nervous tissue may not have a large influence on initial patterning of jaw muscles, it may play an important role in subsequent growth and maintenance of muscular tissue and alterations in cranial nervous tissue development may underlie diversification of jaw muscle morphology.

A gas-phase kinetic study of the reaction between bromine monoxide and methylperoxy radicals at atmospheric temperatures.

The rate constant of the reaction of BrO with CH(3)O(2) was determined to be k1 = (6.2 +/- 2.5) x 10(-12) cm3 molecule(-1) s(-1) at 298 K and 100-200 Torr of O2 diluent. Quoted uncertainty was two standard deviations. No significant pressure dependence of the rate constants was observed at 100-200 Torr total pressure of N2 or O2 diluents. Temperature dependence of the rate constants was further investigated over the range 233-333 K, and an Arrhenius type expression was obtained for k1 = 4.6 x 10(-13) exp[(798 +/- 76)/T] cm3 molecule(-1) s(-1). The product branching ratios were evaluated and the atmospheric implications were discussed.

N(4S) formation following the 193.3-nm ArF laser irradiation of NO and NO2 and its application to kinetic studies of N(4S) reactions with NO and NO2.

Formation of the ground-state nitrogen atom, N((4)S), following 193.3-nm ArF laser irradiation of NO and NO(2) was detected directly by a technique of laser-induced fluorescence (LIF) spectroscopy at 120.07 nm. Tunable vacuum ultraviolet (VUV) laser radiation around 120.07 nm was generated by two-photon resonance four-wave sum frequency mixing in Hg vapor. Photoexcitation processes of NO and NO(2) giving rise to the N((4)S) formation are discussed on the basis of the Doppler profiles of the nascent N((4)S) atoms produced from the photolysis of NO and NO(2) and the photolysis laser-power dependence of the N((4)S) signal intensities. Using laser flash photolysis and vacuum ultraviolet laser-induced fluorescence detection, the kinetics of the reactions of N((4)S) with NO and NO(2) have been investigated at 295 +/- 2 K. The rate constants for the reactions of N((4)S) with NO and NO(2) were determined to be (3.8 +/- 0.2) x 10(-11) and (7.3 +/- 0.9) x 10(-12) cm(3) molecule(-1) s(-1), respectively, where the quoted uncertainties are 2sigma statistical uncertainty including estimated systematic error.

Nitrate radical quantum yield from peroxyacetyl nitrate photolysis.

Peroxyacetyl nitrate (PAN, CH3C(O)OONO2) is a ubiquitous pollutant that is primarily destroyed by either thermal or photochemical mechanisms. We have investigated the photochemical destruction of PAN using a combination of laser pulsed photolysis and cavity ring-down spectroscopic detection of the NO3 photoproduct. We find that the nitrate radical quantum yield from the 289 nm photolysis of PAN is Phi(NO3)PAN = 0.31 +/- 0.08 (+/-2 sigma). The quantum yield is determined relative to that of dinitrogen pentoxide, which is assumed to be unity, under identical experimental conditions. The instrument design and experimental procedure are discussed as well as auxiliary experiments performed to further characterize the performance of the optical cavity and photolysis system.

Atmospheric chemistry of CH3CHF2 (HFC-152a): kinetics, mechanisms, and products of Cl atom- and OH radical-initiated oxidation in the presence and absence of NO(x).

Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(2P(3/2)) (denoted Cl) atom- and the OH radical-initiated oxidation of CH3CHF2 in 700 Torr of air or N2; diluents at 295 +/- 2 K were studied using smog chamber/FTIR techniques. Relative rate methods were used to measure k(Cl + CH3CHF2) = (2.37 +/- 0.31) x 10(-13) and k(OH + CH3CHF2) = (3.08 +/- 0.62) x 10(-14) cm3 molecule(-1) s(-1). Reaction with Cl atoms gives CH3CF2 radicals in a yield of 99.2 +/- 0.1% and CH2CHF2 radicals in a yield of 0.8 +/- 0.1%. Reaction with OH radicals gives CH3CF2 radicals in a yield >75% and CH2CHF2 radicals in a yield <25%. Absolute rate data for the Cl reaction were measured using quantum-state selective LIF detection of Cl(2P(j)) atoms under pseudo-first-order conditions. The rate constant k(Cl + CH3CHF2) was determined to be (2.54 +/- 0.25) x 10(-13) cm3 molecule(-1) s(-1) by the LIF technique, in good agreement with the relative rate results. The removal rate of spin-orbit excited-state Cl(2P(1/2)) (denoted Cl) in collisions with CH3CHF2 was determined to be k(Cl + CH3CHF2) = (2.21 +/- 0.22) x 10(-10) cm3 molecule(-1) s(-1). The atmospheric photooxidation products were examined in the presence and absence of NO(x). In the absence of NO(x)(), the Cl atom-initiated oxidation of CH3CHF2 in air leads to formation of COF2 in a molar yield of 97 +/- 5%. In the presence of NO(x), the observed oxidation products include COF2 and CH3COF. As [NO] increases, the yield of COF2 decreases while the yield of CH3COF increases, reflecting a competition for CH3CF2O radicals. The simplest explanation for the observed dependence of the CH3COF yield on [NO(x)] is that the atmospheric degradation of CH3CF2H proceeds via OH radical attack to give CH3CF2 radicals which add O2 to give CH3CF2O2 radicals. Reaction of CH3CF2O2 radicals with NO gives a substantial fraction of chemically activated alkoxy radicals, [CH3CF2O]. In 1 atm of air, approximately 30% of the alkoxy radicals produced in the CH3CF2O2 + NO reaction possess sufficient internal excitation to undergo "prompt" (rate >10(10) s(-1)) decomposition to give CH3 radicals and COF2. The remaining approximately 70% become thermalized, CH3CF2O, and undergo decomposition more slowly at a rate of approximately 2 x 10(3) s(-1). At high concentrations (>50 mTorr), NO(x) is an efficient scavenger for CH3CF2O radicals leading to the formation of CH3COF and FNO.