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.

Personal Exposure to Fine Particles (PM2.5) in Northwest Africa: Case of the Urban City of Bamako in Mali.

Personal exposure to particulate matter (PM) from anthropogenic activities is a major concern in African countries, including Mali. However, knowledge of particulates is scant. This study was undertaken to characterize personal exposure to PM2.5 microns or less in diameter (PM2.5) in the city of Bamako in Mali. The exposure to PM2.5, through daily activities was observed from September 2020 to February 2021. Participants wore palm-sized optical PM2.5 sensors on their chest during their daily activities. The exposure levels in four different groups of residents were investigated in relation to their daily activities. The variation in PM2.5 concentration was measured during different activities in different microenvironments, and the main sources of exposure were identified. The highest average 10 min concentrations were observed at home and in bedrooms, while the participants were using specific products typically used in Africa, Asia, and South America that included insecticides (IST; 999 µg/m3) and incense (ICS; 145 µg/m3), followed by traffic (216 µg/m3) and cooking (150 µg/m3). The lowest average 10 min concentrations were also observed in the same microenvironment lacking IST or ICS (≤14 µg/m3). With no use of specific products, office workers and students were the least exposed, and drivers and cooks were the most exposed. The concentrations are up to 7.5 and 3 times higher than the World Health Organization's yearly and daily recommended exposure levels, respectively, indicating the need to promptly elaborate and apply effective mitigation strategies to improve air quality and protect public health. This study highlights the importance of indoor air pollution sources related to culture and confirms previous studies on urban outdoor air pollution sources, especially in developing countries. The findings could be applied to cities other than Bamako, as similar practices and lifestyles are common in different cultures.

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.

Transport of perfluoroalkyl substances (PFAS) from an arctic glacier to downstream locations: implications for sources.

Perfluoroalkyl substances (PFAS) have been globally detected in various environmental matrices, yet their fate and transport to the Arctic is still unclear, especially for the European Arctic. In this study, concentrations of 17 PFAS were quantified in two ice cores (n=26), surface snow (n=9) and surface water samples (n=14) collected along a spatial gradient in Svalbard, Norway. Concentrations of selected ions (Na(+), SO4(2-), etc.) were also determined for tracing the origins and sources of PFAS. Perfluorobutanoate (PFBA), perfluorooctanoate (PFOA) and perfluorononanoate (PFNA) were the dominant compounds found in ice core samples. Taking PFOA, PFNA and perfluorooctane-sulfonate (PFOS) as examples, higher concentrations were detected in the middle layers of the ice cores representing the period of 1997-2000. Lower concentrations of C8-C12 perfluorocarboxylates (PFCAs) were detected in comparison with concentrations measured previously in an ice core from the Canadian Arctic, indicating that contamination levels in the European Arctic are lower. Average PFAS concentrations were found to be lower in surface snow and melted glacier water samples, while increased concentrations were observed in river water downstream near the coastal area. Perfluorohexanesulfonate (PFHxS) was detected in the downstream locations, but not in the glacier, suggesting existence of local sources of this compound. Long-range atmospheric transport of PFAS was the major deposition pathway for the glaciers, while local sources (e.g., skiing activities) were identified in the downstream locations.

Field survey of trans-boundary air pollution with high time resolution at coastal sites on the Sea of Japan during winter in Japan.

An intensive field survey, with 6-h measurement intervals, of concentrations of chemical species in particulate matter and gaseous compounds was carried out at coastal sites on the Sea of Japan during winter. The concentration variation of SO(2)(g) and HNO(3)(g) were well correlated, whereas the NH(3)(g) concentration variation had no correlation with those of SO(2)(g) and HNO(3)(g). The NH(4) (+) (p)/non-sea-salt- (nss-)SO(4) (2 -)(p) ratio in particulate matter was mainly affected by the location of the sampling site. One or more concentration peaks of nss-Ca(2 +) for survey period were observed. Backward trajectories analyses for the highest nss-Ca(2 +) concentration peaks showed some inconsistency in pathways. We consider that insufficient mixing of the atmosphere and/or insufficient time for the transported air pollutants to react with those discharged locally are the most likely explanations for the discrepancies between the measured products [HNO(3)][NH(3)] and the calculated values.