The formation of nitro-aromatic compounds under high NOx and anthropogenic VOC conditions in urban Beijing, China

• Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both high-NO(x)and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2, VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m(-3), higher than those reported in other summertime studies (0.14-6.44 ng m(-3)). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the top two most abundant NACs, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx was found to be a more dominant source of NACs than primary biomass burning emissions. The NO2 concentration level was found to be an important factor influencing the secondary formation of NACs. A transition from low- to high-NOx regimes coincided with a shift from organic- to inorganic-dominated oxidation products. The transition thresholds were NO2 similar to 20 ppb for daytime and NO2 similar to 25 ppb for nighttime conditions. Under low-NOx conditions, NACs increased with NO2, while the NO3 concentrations and (NO3-)/NACs ratios were lower, implying organic-dominated products. Under high-NOx conditions, NAC concentrations did not further increase with NO2, while the NO3- concentrations and (NO3-)/NACs ratios showed increasing trends, signaling a shift from organic- to inorganic-dominated products. Nighttime enhancements were observed for 3M4NC and 4M5NC, while daytime enhancements were noted for 4NP, 2M4NP, and DMNP, indicating different formation pathways for these two groups of NACs. Our analysis suggested that the aqueous-phase oxidation was likely the major formation pathway of 4M5NC and 3M5NC, while photo-oxidation of toluene and benzene in the presence of NO2 could be more important for the formation of nitrophenol and its derivatives. Using the (3M4NC+4M5NC) / 4NP ratios as an indicator of the relative contribution of aqueous-phase and gas-phase oxidation pathways to NAC formation, we observed that the relative contribution of aqueous-phase pathways increased at elevated ambient RH and remained constant at RH > 30 %. We also found that the concentrations of VOC precursors (e.g., toluene and benzene) and aerosol surface area acted as important factors in promoting NAC formation, and photolysis as an important loss pathway for nitrophenols.

Ämnesord

NATURVETENSKAP  -- Geovetenskap och miljövetenskap (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences (hsv//eng)

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Meteorologi och atmosfärforskning (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Meteorology and Atmospheric Sciences (hsv//eng)

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Geokemi (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Geochemistry (hsv//eng)

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Miljövetenskap (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Environmental Sciences (hsv//eng)

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Klimatforskning (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Climate Research (hsv//eng)

NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

NATURVETENSKAP  -- Kemi -- Analytisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Analytical Chemistry (hsv//eng)

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Nyckelord

secondary organic aerosol

pure-component properties

humic-like

substances

nitrated phenols

brown carbon

light-absorption

molecular

characterization

liquid-chromatography

oh radicals

n2o5 uptake

Environmental Sciences & Ecology

Meteorology & Atmospheric Sciences

ates of america

v110

p8014

ates of america

v108

p2190

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ref (ämneskategori)

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