Photochemical Aging of Beijing Urban PM2.5: HONO Production

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Photochemical Aging of Beijing Urban PM2.5: HONO Production Fengxia Bao, Meng Li, Yue Zhang, Chuncheng Chen, and Jincai Zhao Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b00538 • Publication Date (Web): 01 May 2018 Downloaded from http://pubs.acs.org on May 2, 2018

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Environmental Science & Technology

Photochemical Aging of Beijing Urban PM2.5: HONO Production

Fengxia Bao a,b, Meng Li a,b , Yue Zhang a,b, Chuncheng Chen a,b,*, Jincai Zhao a,b a

Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in

Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China b

University of Chinese Academy of Sciences, Beijing, 100049, P. R. China

Corresponding Authors:

Prof. Chuncheng Chen Email: [email protected]

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ABSTRACT

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Photochemical aging represents an important transformation process of aerosol particles in the

3

atmosphere, which greatly influences the physicochemical properties and the environmental

4

impact of aerosols. In this work, we find that Beijing urban PM2.5 aerosol particles release

5

substantial HONO, a significant precursor of ·OH radicals, into the gas phase during the

6

photochemical aging process. The generation of HONO exhibits a high correlation with the

7

amount of nitrate in PM2.5. The formation rate of HONO becomes gradually decreased with the

8

irradiation time, but can be restored by introducing the acidic proton, indicative of the essential

9

role of the acidic proton in the HONO production. Other environmental factors such as relative

10

humidity, light intensity, and reaction temperature also possess important influences on HONO

11

production. The normalized photolysis rate constant for HONO (JHNO3→HONO) is in the range of

12

1.22 × 10-5 s-1 ~ 4.84 × 10-4 s-1, which is 1 ~ 3 orders of magnitudes higher than the reported

13

photolysis rate constant of gaseous HNO3. The present study implies that the photochemical

14

aging of Beijing PM2.5 is an important atmospheric HONO production source.

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Environmental Science & Technology

INTRODUCTION

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Atmospheric aerosol particles, which significantly affect the global climate, air quality and

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atmospheric chemistry, undergo complex aging processes in the atmosphere1-3. The aging of the

19

particles will change the physical and chemical properties of the particles, but also influences the

20

composition of the surrounding air by uptaking or releasing volatile species4-8. Therefore, the

21

aging process of the atmospheric particles will present great influence on their environmental

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fate and effect. Among many particle aging processes, photochemistry plays a crucial role in the

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atmosphere1, since solar radiation provides the energy to initiate many reactions that are difficult

24

to occur under the tropospheric and stratospheric conditions. In the past few decades, the

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scientific community has put large effort to study aerosol evolution in the atmosphere, but the

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level of understanding the aging processes, especially the photochemical aging process, of

27

aerosol particles is still low.

28

It is known that the oxidation of nitrogen oxides such as NO2 leads to the formation of nitric

29

acid or nitrate salt9, 10, which is consequently adsorbed on aerosol particles or deposits on other

30

environmental surfaces. It is conventionally considered that such adsorption and deposition

31

process of nitrate would remove the nitrogen oxides from the atmosphere. However, recent

32

studies found that the photolysis of HNO3/NO3- deposited on environmental surfaces can lead to

33

a rapid release of nitrogen oxides into the gas phase (renoxification)11-14. For example, the

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photolysis of nitric acid/nitrates deposited on the natural surfaces of plant leaves15,

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particulates in the marine boundary layer14 is reported to generate HONO, NO2, and/or NO. The

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irradiation of the urban grime from Toronto, Canada12, ground surfaces from Houston, Texas17

37

and urban aerosols from New York15, 18 also leads to the HONO production. In recent years, the

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PM2.5 (fine particulates with aerodynamic diameters less than 2.5 µm) pollution has been a

16

and

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serious environmental problem in cities of northern China19. Together with the high intensity of

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solar irradiation, the NOx production during the photoaging of PM2.5 may have important

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influence on the nitrogen cycling in Beijing.

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Nitrate anion (NO3-), ubiquitous in ambient particles, is reported to be particularly high near

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urban centers8, as NO3- is primarily formed from the anthropogenic release of NOx1. According

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to the field observations, NO3-, which is the dominant species in the water-soluble fraction of

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PM2.5 (constituting up to 25% of the total mass)20, in the atmosphere of Beijing (>10 µg·m-3) is

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significantly higher than that in the cites of New York (~ 2 µg·m-3), Hong Kong (~ 1µg·m-3),

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Shanghai (~ 7 µg·m-3), and Seoul (~ 7 µg·m-3)21.

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The large amounts of nitrate provide plenty of nitrogen sources for the photochemical

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transformation of nitrogen oxides. In addition, the suspended airborne PM2.5 can also be fully

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exposed to the incoming sunlight, and much easier to undergo photochemical reactions than

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other environmental surfaces. For now, the important renoxification during the photochemical

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aging of Beijing PM2.5 is not investigated and the influence of the environmental factors in this

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process is not clear.

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Gaseous nitrous acid (HONO) is a very important gaseous species to stimulate a series of

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further photochemical oxidation reactions of natural or industrial organic compounds by

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producing hydroxyl radicals (·OH)22-24. Recent environmental HONO observations found that

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HONO concentration in Beijing is high relative to other cities, as summarized in Table S125-27.

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However, a certain contribution of the high HONO concentration was not yet ascribed to specific

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sources. For example, field studies at urban sites of Beijing from 2014 to 2016 have shown that

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the unknown daytime HONO source rate is in the range of 1.26 ~ 3.82 ppbv·h-1 25, 26. In the

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present work, to shed light on the contribution of the photolysis of nitrate species in PM2.5

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particles to the HONO source, we examined the generation of gaseous nitrous acid (HONO)

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during the photochemical aging process of Beijing urban PM2.5 samples. The production rates for

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HONO and NO2 were measured on different PM2.5 samples and the photolysis rate constants

65

were estimated. In addition, the effects of various environmental conditions including acidity,

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relative humidity, light intensity and wavelength on the formation of HONO were also

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investigated. The contribution of photoaging of PM2.5 to the overall HONO sources was

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estimated by using the photolysis rate constants measured in the present study, and compared

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with the reported unknown source rate of HONO in Beijing. Our work provides direct evidence

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that the photochemical aging of Beijing Urban PM2.5 is an important HONO source.

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EXPERIMENTAL SECTION

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Sampling of PM2.5 particles. The ambient fine particulate matter (PM2.5) (aerodynamic particle

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size < 2.5 µm) was collected on quartz microfiber filters (Whatman, 203 mm × 254 mm) by a

74

600/AFPM1001K High Volume Sampler (see supporting information for details). Samples were

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collected on the roof of the ten-storey building of the Institute of Chemistry, CAS, Beijing

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(116°19’21.58’’E, 39°59’22.68’’N) that is a typical heavily polluted urban area. The sampled

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filters were labeled by the sampling date and stored at - 20 °C in the freezer. Fractions with given

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surface area from one randomized-chosen filter sample were used to perform the photochemical

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experiments or other analysis.

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Photochemical reaction of PM2.5. A custom-made cylindrical quartz vessel was used as the

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photochemical flow reactor. A Xenon lamp (CEAULIGHT, 300 W) was used to simulate

82

sunlight. To adjust the J value to ambient sunlight condition (solar elevation angle θ = 0o), the

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radiant output of the solar simulator was quantified by actinometry calibration28 (Supplementary

84

method section and Figure S2). During the photoreaction process, the reactor was kept at a

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constant temperature by a HX-205 water circulating bath (Beijing YKKY Technology Co., Ltd).

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RH was adjusted in the air flow through a water bubbler, and monitored with an on-line RH

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sensor (Vaisala, HMT130). Since the formation of HONO and NO2 was not changed much in the

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range of 15% ~ 75% relative humidity, an RH of 60% was typically used. Synthesized air

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composed of ultra-high-purity nitrogen and ultra-high-purity oxygen mixed at a ratio of 26:7 was

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used as the carrier gas.

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On-line gas measurements. Gaseous products HONO and NOx released during the experiment

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were flushed out of the reactor by the carrier gas and were detected on-line by a MODEL T200

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NOx analyzer (Teledyne API). This analyzer can directly measure the concentration of NO, and

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the detection of HONO and NO2 was achieved by converting them into NO with a molybdenum

95

catalyst. For HONO measurement, a Na2CO3 denuder was employed to trap HONO selectively,

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and HONO concentrations were indirectly measured by the signal difference without and with

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the carbonate denuder29, 30 (see supporting information for details). The validity of this method

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for HONO measurement was verified by measuring concentration of NO2- ions with ion

99

chromatography (ICS-900, DIONEX), after HONO was absorbed by water (Figure S3), and by

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long-path absorption photometer (LOPAP) HONO analyzer31(Figure S4).

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Calculations of HNO3 photolysis rate constant. The average production rates (mol·s-1) of

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HONO and NO2 during a period of sample irradiation (PHONO and PNO2) were calculated by the

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following equations:

104

PHONO=

105

PNO2=

ଵ଴షవ ×ி೒

௧మ ݀‫ݐ‬ ‫ܥ ׬‬ ௏೘ ×଺଴×(௧మ ି௧భ ) ௧భ ுைேை

ଵ଴షవ ×ி೒

௧మ ‫ݐ݀ ܥ ׬‬ ௏೘ ×଺଴×(௧మ ି௧భ ) ௧భ ேைଶ

(1)

(2)

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where Fg is the flow rate of the carrier gas (L·min-1); Vm (24.5 L·mol-1) is the molar volume of

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gas at 25 oC and 1 atmosphere of pressure; t1 and t2 (min) are the starting and ending time of the

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irradiation, respectively; CHONO and CNO2 (ppbv) are the on-line measured concentrations of

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HONO and NO2.

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The normalized rate constant of HNO3 photolysis leading to HONO production (JHNO3→HONO)

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and the normalized rate constant of HNO3 photolysis leading to NO2 production (JHNO3 → NO2)

112

were calculated by the following equations15:

113 114

‫ܬ‬ୌ୒୓య →ୌ୓୒୓ =

௉ౄోొో ேొోష య

௉ొోమ

‫ܬ‬ୌ୒୓య →୒୓మ = ே

ొోష య

×

×

ଷ×ଵ଴షళ ௃౛౮౦

ଷ×ଵ଴షళ ௃౛౮౦

(3)

(4)

115

Jexp (s−1) was the photolysis rate constant of nitrate in the actinometer solution exposed to the

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experimental light source, which was determined by the method of nitrate actinometry28( detailed

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in the supporting information). The calculated photolysis rate constants JHNO3→ HONO (s−1) and

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JHNO3 → NO2 (s−1) have been normalized to tropical noontime conditions on the ground (solar

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elevation angle θ = 0°) where a photolysis rate constant is ∼3 × 10−7 s−1 for aqueous nitrate and

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∼7 × 10−7 s−1 for gaseous HNO328. NNO3- (mol) is the amount of NO3- in the PM2.5 sample

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determined in the extraction solution. In principle, the photolysis rate constants of NO3- should

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be calculated on the NNO3- that is reachable to the irradiation. However, unlike the homogeneous

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systems, the inhomogeneity of the PM2.5 filter samples makes it difficult to quantify the amount

124

of the light-reachable NO3-. Accordingly, the NNO3- was estimated on the basis of the total NO3-

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amount in the PM2.5 sample in this study which is convenient to reflect the NO3- content of the

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tested sample14, 15, 16. To detect the total NNO3-, the fraction of the sample with given surface area

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was rinsed by deionized water and then sonicated for 15 min. The amount of nitrate in the PM2.5

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was measured by an ion chromatograph. DNO3- was calculated through dividing NNO3- with the

129

geometric area of the sampled filter.

130 131

RESULTS AND DISCUSSION

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HONO production during the photochemical aging of Beijing urban PM2.5. Figure 1a shows

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a typical profile for the change in concentrations of HONO and NO2 in the reaction system

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during the photoaging of Beijing urban PM2.5 under the irradiation of simulated solar light.

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HONO was initially generated very quickly. However, when the photo-irradiation was turned

136

off, the HONO generation stopped immediately and its concentration in the reactor decayed

137

slowly. Moreover, when the sample was heated up to 60 oC in the dark, little HONO was

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observed, indicating that the formation of HONO was attributed to the photochemical reaction of

139

particles, but not to the simple thermal reaction. Compared with HONO, another common

140

atmospheric nitrogen oxide NO2 was almost undetectable during the irradiation (Figure 1a, blue

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line). This phenomenon was universally observed on other PM2.5 samples (Figure S5 and Table.

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1).

143

The average HONO production rates within the first 15 min of irradiation were further

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investigated on different PM2.5 samples. As shown in Figure 1b, HONO generation rate exhibited

145

a high correlation with DNO3- in the samples (with a R2 of 0.85), suggesting that the observed

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HONO production during the photochemical aging of Beijing PM2.5 originates from HNO3/NO3-.

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We also tried to correlate the HONO production of samples with the pollution level of the

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sampling day. As shown in Figure S6, the HONO production rate obtained in the present study

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exhibited significant positive correlation with the official-released AQI (Air Quality Index) and

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the concentrations of PM2.5 and NO2 of the sampling day of PM2.5, while the correlation is not

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very significant with the SO2 concentration. It is possible that, at high pollution level, the

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concentration of nitrate in the PM2.5 should be accordingly high and consequently a high HONO

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production rate is obtained, in agreement with Figure 1b.

154 155

Figure 1. (a) HONO and NO2 production from the PM2.5 sample (NOV16) during the

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irradiation; (b)Average HONO production rate within the first 15 min of irradiation as a function

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of DNO3-(left, red rhombuses); The photolysis rate constant JHNO3→HONO of PM2.5 surfaces as a

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function of DNO3- (RH = 60%, temperature = 25 oC)(right, blue circles).

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The HNO3 photolysis rate constants for HONO (JHNO3→HONO) and NO2 (JHNO3→NO2) production

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on different PM2.5 samples are summarized in Table 1. The observed JHNO3→HONO values were

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distributed from 1.22 × 10-5 s-1 to 4.84 × 10-4 s-1 with a mean value of 8.24 × 10−5 s-1. The JHNO3→

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HONO

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orders of magnitude, and are similar to the reported values (6.0 × 10−6 s-1 ~ 3.7 × 10−4 s−1) on

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plant leaves, metal sheets, and construction materials15. It is noted that the photolysis rate

values of PM2.5 samples are higher than that of gaseous HNO3 (about 3 × 10-7 s-1) by 1-3

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constants listed in Table 1 are the average rates in the irradiation of the first 15 min. As shown in

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Figure 2, with extended irradiation time, the HNO3 photolysis rate constants decreased gradually.

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Furthermore, in the atmosphere, the nitrogen cycle exists among HNO3 and the reactive nitrogen

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species. The more nitrogen species are formed by the photolysis of HNO3, the rapider

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transformation of the nitrogen species back to the HNO3 occurs. As a result, the amount of

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particulate nitrate can be largely maintained by the dynamical nitrogen cycling, besides other

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external nitrate sources.

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Table 1. HNO3 photolysis rate constants for HONO (JHNO3 → HONO) and NO2 (JHNO3 → NO2)

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production and the production ratio of HONO/NO2 on different PM2.5 samplesa. Date

JHNO3→HONO -5

JHNO3→NO2

Yield ratio HONO/NO2

APR24

s-1 2.13±0.22

JUL05

7.31±0.33

1.21±0.13

6.07±0.40

JUL06

12.58±0.03

2.39±0.04

5.26±0.1

AUG31

14.58±0.16

5.05±0.83

2.97±0.47

SEP02

28.22±3.30

5.32±0.78

5.31±0.16

SEP05

34.62±19.54

14.92±9.63

2.40±0.24

SEP06

8.15±1.17

3.59±1.50

2.56±1.40

OCT13

1.30±0.11

0.23±0.00

5.59±0.51

OCT18

1.50±0.32

0.59±0.25

2.65±0.58

OCT25

6.55±0.92

3.17±1.26

2.32±0.88

NOV03

1.79±0.08

0.26±0.02

6.90±0.73

NOV09

1.91±0.30

0.36±0.01

5.30±0.96

NOV16

2.54±0.57

0.67±0.31

4.90±3.67

DEC12

3.26±0.47

1.45±0.03

2.24±0.27

10

s-1 0.46±0.02 10

-5

4.59±0.31

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DEC20

1.70±0.02

0.52±0.03

3.25±0.12

Median value

8.24

3.43

3.95

Mean value

3.59

1.3

3.55

a

The average HONO and NO2 production within the first 15 min of irradiation were used,

175

and the error bars were obtained by repeating each experiment 2-4 times with different fractions

176

from the same sample.

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Figure 1b shows the change of the JHNO3→HONO as a function of DNO3- in PM2.5 samples. The

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JHNO3→HONO value decreased sharply with the increasing DNO3-. Such a decrease may be caused by

179

the screening effect of the PM2.5 particles to the light. As shown in Figure S7, there are plenty of

180

light-absorbing species within PM2.5 particles. These light-absorbing species would hinder the

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light absorption of nitrate in the inside and underside of the particle. Moreover, it is very often

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that more than single layer of PM2.5 particles were collected on the filter samples. In the multi-

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layer situation, the particles in the lower layers of the filter sample would absorb less light than

184

those on the first layer due to the screening effect. Usually, higher DNO3- goes with more PM2.5

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particles, and the screening effect becomes stronger. Therefore, the JHNO3→HONO decreases with

186

DNO3-. To verify this assumption, we correlated the content (%) of elemental carbon (one of the

187

most important light-absorbers in PM2.5) in different PM2.5 samples (Table S3) to the

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corresponding photolysis rate constants JHNO3→HONO in Table 1. An apparent negative correlation

189

was observed (Figure S8), indicating that light-absorbing species within PM2.5 particles would

190

really exert light screening effect in the photochemical HONO production. In our experiments,

191

the observed DNO3- of PM2.5 filter samples varied from 1.63 × 10-4 to 3.02 × 10-2 mol∙m-2, which

192

is 1 ~ 3 magnitude higher than the DNO3- on natural surfaces16, 32. The similar JHNO3→HONO values

193

imply that the production of HONO during the photoaging of PM2.5 is more efficient than that on

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natural surfaces. Moreover, in the real atmosphere, the screening effect between the suspended

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PM2.5 particles should be minimized because of the less density of the particles. Thus, the real

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JHNO3→HONO value in the atmosphere should be higher than that of our laboratory observations. It

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is also possible that the decrease of the JHNO3→HONO with DNO3- can be partially caused by the

198

confining effect of the solid matrix of particle, which makes the photoproducts of HNO3 inside

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the particle difficult to escape from the particle bulk or the lower layers of the sample.

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Influence of acidic protons and H2O. Another notable phenomenon for the photochemical

201

aging of PM2.5 is that the formation rate of HONO becomes gradually decreased with the

202

irradiation time. After 10 h of irradiation, HONO was hardly produced anymore (Figure 2). At

203

this point, 95% of the original NO3- was still left in the sample (Figure S9). Interestingly, when

204

HCl flow was introduced into the reaction system, the HONO production was restored. As a

205

control experiment, the photoaged PM2.5 sample without light irradiation showed no HONO

206

production in HCl flux (Figure S10). These results indicate that the acidic proton plays an

207

important role in the photochemical HONO production. One of a possible role of the proton is to

208

assist the escape of HONO by protonating the photochemically-generated nitrite, which implies

209

that the photolysis of nitrate still proceeds in the absence of protons. If this is the case, other NOx

210

such as NO2 should be formed or nitrite should be accumulated in the particles after the acidic

211

proton was depleted. However, as shown in Figure 2, when HONO production decreased with

212

the irradiation time, the formation of NO2 was scarce. In addition, after the cease of

213

photochemical HONO production, introducing gaseous HCl did not enhance the release of

214

HONO in the dark, but restored HONO production under irradiation, which excludes the

215

possibility of the accumulation of nitrite in the particles by photolysis of nitrate. More

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reasonably, the photolysis reaction is ceased in the lack of the protons. HNO3, rather than NO3-,

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is the main photoactive species for the HONO formation. Besides, even in the HCl flux, the

218

photochemical reaction underwent a rapid decrease and stopped after further 10 h of irradiation

219

(Figure 2). This decrease should not result from the depletion of HNO3, since 66% of the original

220

NO3- was still left after 10 h of irradiation in the presence of HCl (See Figure S9). It is reported

221

that HNO3 can be reduced by VOC (electron donors) emitted by the aerosol surface, leading to

222

HONO formation33. Therefore, it is possible that the decrease in the HONO production is caused

223

by consumption of reactive electron donors (eq. 5). We also note that under environmental

224

conditions, plenty of sulfuric acid, formed by the oxidation of SO2 in the atmosphere, can be

225

uptaken by PM2.5. The HCl-promotive effect implies that the sulfuric acid ubiquitous in the

226

atmosphere would similarly enhance the formation of HONO. However, the experimental

227

validation for this assumption in our laboratory is not feasible because the low-volatile H2SO4 is

228

difficult to be introduced into the reaction system in a gaseous form.

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HNO3 + 2H+ + 2e- + hv → HONO + H2O

(5)

230

HNO3 + H2O + hv → HONO + 2·OH

(6)

231

HNO3+ hv → NO2 + ·OH

(7)

232

NO2 + H2O+ hv → HONO + ·OH

(8)

233

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Figure 2. The decay of HONO and NO2 production from Beijing urban PM2.5 (NOV28) with the

235

irradiation time, and its restoration by introducing HCl flow (bubbled from 1 M HCl solution

236

with the flow rate of 500 mL/min).

237

The influence of H2O on the HONO production was evaluated at different relative humidity

238

(RH) during the photochemical aging of Beijing PM2.5 (Figure 3 and S11). At low RH (< 5%),

239

the formation of HONO was quite slow, and became rapid at intermediate RH (15%~75%).

240

However, at RH > 90%, the photolysis rate decreased. Similar effects have been reported on the

241

photolysis of nitrate adsorbed on aluminum oxide by Grassian and coworkers34, who found that

242

the photolysis was enhanced at low relative humidity (RH < 20%), but depressed at high relative

243

humidity (RH > 45%). There are several possible explanations for the effect of water vapor on

244

HONO production: (i) as shown in eq. 6, H2O molecules can directly participate in the HNO3

245

photolysis reaction probably in the form of H2O/HNO3 clusters35; (ii) as shown in eq.7 and eq.8,

246

H2O molecules may promote the secondary reaction of NO2, produced by the photolysis of

247

HNO3, to HONO, since strong humidity dependence for the heterogeneous transformation of

248

NO2 to HONO has been reported36; (iii) it is also possible that RH can affect phase state of the

249

particle and hence their physical and chemical properties. For example, the higher RH will lead

250

to the decreased viscosity of the matrix, which can accelerate the molecular motion and thus

251

promote the rate of photochemical reactions37. To further evaluate the role of the water in the

252

HONO production, the photochemical reaction was performed at RH = 0%. Under this condition,

253

both HONO and NO2 production were almost below the detection limit (Figure 3a, b). The lack

254

of NO2 production excludes the second explanation. Namely, the HONO production in the PM2.5

255

particles should be generated from the H2O/HNO3 interaction during the photochemical aging

256

rather than from the secondary reaction of photo-generated NO2 with H2O vapor.

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Figure 3. Cumulative HONO production (red columns) or NO2 production (blue columns) after

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50 min irradiation of Beijing urban PM2.5 as a function of the relative humidity (Temperature =

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25 oC).

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The unique properties of PM2.5 surfaces. In order to evaluate the effect of different

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heterogeneous surfaces on HONO production, the HONO and NO2 production were detected

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during photolysis of HNO3 loaded on different substrate surfaces (Figure 4). The HNO3 loaded

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on quartz microfiber filters and pyrex glass was nearly inert and no HONO or NO2 was detected

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in our reaction system, in agreement with the reported low photolysis rate of HNO3 (JHNO3→HONO

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= 2.4 × 10−7 s-1) on quartz glass surfaces38. On the surface of TiO2 and Al2O3, significant NO2

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production was observed under irradiation, while the production of HONO was still negligible.

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The HONO/NO2 production ratios for Al2O3 and TiO2 were much less than 1 (Table S2). By

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contrast, PM2.5 surface showed high activity for the heterogeneous HONO production (more than

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an order of magnitude over TiO2 and Al2O3), but quite low yield for NO2. The HONO/NO2

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production ratio for PM2.5 (JUL07) was much larger than 1 (Table S2), which is very distinctive

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from other heterogeneous interfacial reactions on traditional metal oxide nano-/micro-particles.

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Figure 4. Cumulative (a) HONO (NHONO) and (b) NO2 production (NNO2) divided by the amount

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of NO3- (NNO3-) absorbed on different supports as the function of irradiation time.

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The unique photochemical properties of urban PM2.5 to the selective HONO generation may

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originate from its complicated composition (component analysis of Beijing urban PM2.5 samples

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is detailed in Table S3). Beijing urban PM2.5 contains various organic acid and other organic

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species21, 39, which can act as both the proton and electron donors. In addition, the inorganic

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acids (H2SO3, H2SO4 and HNO3, mostly from the chemical transformation of SOx and NOx) in

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Beijing urban PM2.5 samples also play very important roles in the photochemical aging process

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by both providing acidic protons and active reaction environments.

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Influences of Environmental factors on the HONO generation. In the atmosphere, the

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heterogeneous chemical reactions on atmospheric PM surfaces are significantly affected by

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environmental factors (i.e. temperature, light wavelength and intensity). The influences of the

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typical environmental factors on the HONO formation were further investigated. As shown in

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Figure S12a, no HONO generation was observed under dark conditions. With the increase of

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light intensity, the HONO production rate was gradually increased. Furthermore, the wavelength

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of incident light also affected directly the HONO production (Figure S12b). When the PM2.5

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sample was illuminated by using visible light with wavelength λ > 400 nm, the average HONO

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production rate within 0.5 h irradiation was 2.13 × 10-12 mol·s-1, decreasing 63.1% compared to

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that of the full spectrum illuminated sample with the value of 5.78 × 10-12 mol·s-1 under identical

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light intensity. These results imply that HONO generation reaction on urban PM2.5 samples is

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mainly initiated by UV light ( λ < 400 nm).

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Temperature is another environmental factor that possesses important influence on the HONO

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production during the photochemical aging of PM2.5. As shown in Figure 5, under identical light

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intensity and RH (60%), the HONO production rate increased with the temperature increasing

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from 5 ~ 40 oC.

300 301

Figure 5. Cumulative HONO production from the PM2.5 sample (NOV16) as a function of the

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irradiation time (t) at different temperature.

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Environmental implication. Nitrous acid (HONO) is a very important gaseous species to

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stimulate a series of further photochemical oxidation reactions of natural or industrial organic

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compounds by producing hydroxyl radicals (·OH)22, 23, which has considerable impacts on the

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local atmospheric oxidation capacity. The present study reveals that the photochemical aging

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process of PM2.5 can be accompanied by the HONO release. It is reported that the nitrate in

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Beijing is significantly relative higher than that in other cities21. Together with the heavy PM2.5

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pollution in Beijing, the photochemical formation of nitrogen oxides should play a more

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important role in the nitrogen cycle in Beijing. The contribution of photoaging of PM2.5 to the

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overall HONO sources under environmental conditions can be estimated by using the photolysis

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rate constants measured in the present study and the concentration of nitrate (CNO3-) in the

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atmospheric particles. Since the difference in response bandwidth of the nitrate actinometer is

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not significant between latitude of 0 and 40° N28, the photolysis rate constants in Table 1 was

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directly used for the estimation in Beijing (39°59’22.68’’N). According to the field

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measurements at urban sites of Beijing in 2015 and 2016, CNO3- in the atmosphere of Beijing is

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around 6.64 µg·m-3 (2.62 ppbv) 26. Using this CNO3- value and our observed JHNO3→HONO (1.22 ×

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10-5 s-1 ~ 4.84 × 10-4 s-1), the noontime HONO source rate from heterogeneous photolysis of

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HNO3 is estimated to be in the range of 0.12 ~ 4.57 ppbv·h-1, with the mean value of 0.78

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ppbv·h-1, which is comparable to the reported daytime unknown HONO source rate in Beijing

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(1.85 ppbv·h-1 in the severe haze period and 1.26 ppbv·h-1 in the clean period25, or 1.30 ~ 3.82

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ppbv·h-1 26). These comparisons imply that the photochemical aging of Beijing urban PM2.5 is a

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significant HONO production source. The present study suggests that the inclusion of the photo-

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induced HONO production on PM2.5 could explain the presence of unexpected high daytime

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HONO concentrations in both urban and rural areas, and improve the accuracy of the model

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simulations based on field measurements in London, Huston and Michigan17, 24, 40-42.

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Our results also show that the HONO production from PM2.5 is affected by specific

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environmental conditions. For example, the acid can greatly accelerate the HONO release. The

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atmosphere of southern China often has high air acidity based on model simulation studies43-45,

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and should greatly enhance the HONO production of PM2.5. Moreover, it is demonstrated that the

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high light intensity during daytime promotes the HONO production of PM2.5, indicating the

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PM2.5 as a HONO source mainly contributes to the daytime HONO production. The large

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amount of HONO production in the atmosphere can cause a series of further photochemical

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oxidation reactions of natural or industrial organic compounds by producing hydroxyl radicals

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(·OH), which further induce the formation of oxidative products such as ozone, peroxy acetyl

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nitrate (PAN), and a large amount of secondary environmental pollutants. All these oxidative

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products can react with various organic compounds and stimulate the production of secondary

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organic aerosols (SOA), causing severe air pollution problems.

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ACKNOWLEDGMENT

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This work was supported by NSFC (Nos. 21590811, 21525729, 21521062, 21777168), the

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“Strategic Priority Research Program” (No. XDA09030200), the “Key Research Program of

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Frontier Sciences” (No. QYZDY-SSW-SLH028) of the Chinese Academy of Sciences, and the

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“CAS Interdisciplinary Innovation Team Program”. The authors are grateful to Prof. Pingqing Fu

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from Institute of Atmospheric Physics (CAS) and Prof. Maofa Ge from Institute of Chemistry

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(CAS) for their helpful discussion and their supports in PM2.5 samples.

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ASSOCIATED CONTENT

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Supporting Information.

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Supplementary methods; Tables of HONO measurements in Beijing and other cities, and

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components of PM2.5 samples; Figures showing calibration results and other supplementary

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materials. The Supporting Information is available free of charge on the ACS Publications

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website http://pubs.acs.org.

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