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Spatial distribution of ozone formation in China derived from emissions of speciated volatile organic compounds Rongrong Wu, and Shaodong Xie Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b03634 • Publication Date (Web): 01 Feb 2017 Downloaded from http://pubs.acs.org on February 2, 2017

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Environmental Science & Technology

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Spatial distribution of ozone formation in China derived

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from emissions of speciated volatile organic compounds

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Rongrong Wu, Shaodong Xie *

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College of Environmental Sciences and Engineering, State Key Joint Laboratory of

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Environmental Simulation and Pollution Control, Peking University, Beijing, 100871, China

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* Corresponding author phone: 86-010-62755852; fax: 86-010-62755852; e-mail:

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[email protected]

1 Environment ACS Paragon Plus


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TOC/ Abstract Art

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ABSTRACT

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Ozone (O3) pollution is becoming increasingly severe in China. In addition, our limited

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understanding of the relationship between O3 and volatile organic compounds (VOCs), is an

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obstacle to improving air quality. By developing an improved source-oriented speciated VOC

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emission inventory in 2013, we estimated the ozone formation potential (OFP) and investigated

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its characteristics in China. Besides, a comparison was made between our estimates and space-

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based observations from the Ozone Monitoring Instrument (OMI) on the National Aeronautics

17

and Space Administration (NASA)’s Aura satellite. According to our estimates, m-/p-xylene,

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ethylene, formaldehyde, toluene, and propene were the five species that had the largest potential

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to form ozone, and on-road vehicles, industrial processes, biofuel combustion, and surface

20

coating were the key contributing sectors. Among different regions of China, the North China

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Plain, Yangtze River Delta and Pearl River Delta had the highest OFP values. Our results

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suggest that O3 formation is VOC-limited in major urban areas of China. Additionally,

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considering the different photochemical reactivities of various VOC species and the disparate

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energy and industry structures in the different regions of China, more efficient OFP-based and

25

localized VOC control measures should be implemented, instead of the current mass-based and

26

nationally uniform policies.



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1. Introduction

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Tropospheric ozone (O3) is a product of the photochemical oxidation of volatile organic

29

compounds (VOCs) and nitrogen oxides (NOx) in the presence of sunlight in the atmosphere.1, 2

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As an important atmospheric oxidant and greenhouse gas,3-5 O3 has adverse effects on air quality,

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climate, human health and vegetation.6-9 Therefore, studies on the spatio-temporal distribution of

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tropospheric O3 and factors that impact it have been prominent in atmospheric chemistry

33

research.

34

A dramatic increase in the emissions of O3 precursors (mainly VOCs and NOx) from

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anthropogenic sources has been observed since the Chinese Economic Reform began in 1987,

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which has led to a rise in ground-level O3 concentrations in China.9-11 Currently, high levels of

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O3 along with fine particles (PM2.5) have become one of China’s greatest environmental

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challenges.8 With the implementation of stringent control programs (e.g., Air Pollution

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Prevention and Control Action Plan and The 12th Five-Year Plan on Air Pollution Prevention

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and Control in Key Regions, including control strategies such as phasing out small sized coal-

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fired boilers and furnaces, accelerating the use of district heating and retrofitting dust removal

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apparatuses in key industries12, 13), the concentrations of PM2.5 have been reduced, but the mixing

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ratio of O3 continues to increase.14, 15 Severe O3 pollution frequently occurs in photochemically

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active seasons (e.g., summer and fall) in many regions of China, particularly in the Beijing-

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Tianjin-Hebei (BTH), Yangtze River Delta (YRD), and Pearl River Delta (PRD) regions

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(locations and boundaries of these regions are shown in Figure S1 in the Supporting

47

Information).9,

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concentration of O3 was 105 ppbv in Beijing in the third quarter of 2015, exceeding Stage II of

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China’s National Ambient Air Quality Standards (75 ppbv) and being the critical pollutant on

11, 16-18

According to the monitoring data, the maximum daily 8-hour average


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nonattainment days.19 Similar situations have been observed in the YRD and PRD regions.19

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Therefore, greater effort is needed to combat with the high levels of O3 in China.

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VOCs are crucial precursors to tropospheric O3 formation, particularly in NOx-saturated

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urban areas.8,

20-23

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particularly emissions from anthropogenic sources, could potentially help control O3 pollution in

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China. VOCs consist of thousands of compounds that significantly differ in chemical reactivity,

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with differing influences on O3 formation. Hence, VOC speciation is vital for chemical transport

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modeling of O3 formation.24 In addition, speciation is needed for regulatory purposes.

Consequently, greater knowledge of the characteristics of VOC emissions,

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In recent years, many efforts have been made to characterize the emissions and distribution

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of speciated VOCs in China,24-27 however, several issues remain unresolved. First, most of the

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source profiles used for speciation were selected from developed countries, such as the widely

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used EPA SPECIATE database.28 This could result in high uncertainties because of the

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substantial discrepancies in the profiles between China and foreign countries.29, 30 Given this

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problem, many local measurements have been conducted over the past decade on major VOC

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emission sources such as stationary fossil fuel combustion,31-33 biomass burning,34-36 vehicle

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exhaust and gasoline evaporation,30, 33, 37 industrial processes,38-40 and solvent use.29, 41 However,

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only a few of these recently obtained profiles have been used for speciation.24 Second,

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oxygenated VOCs (OVOCs), which significantly contribute to the oxidant capacity of the

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atmosphere and have a harmful effect on human health,42-44 constitute a large fraction of the

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VOC emissions from industrial solvent use, biomass burning, and diesel vehicle exhaust,24, 42, 45,

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46

but are missing in most previous studies.

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Investigations of OVOC emissions in China are still limited. Moreover, VOC emissions in

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China are increasing annually, but most of the national inventories were compiled before 2010.47



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In order to fill these gaps and provide a scientific rationale for policy making, we developed an

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improved emission inventory of speciated VOCs for the year 2013 in this study. Based on this

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inventory, the O3 formation potential (OFP) was estimated, and the characteristics of VOC-based

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O3 pollution in China were investigated.

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2. Methodology

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2.1 Estimation of total VOC emissions in 2013

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The total anthropogenic VOC emissions were calculated by Eq. (1).47 Five major source sectors

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were considered in this study, including transportation, biomass burning, stationary fossil fuel

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combustion, industrial processes and solvent utilization (in Level 1). These major sectors were

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divided into 15 sub-sectors (in Level 2), which were further divided into sources in Level 3 and

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then into classes in Level 4 according to the type of products, fuel and technology used. For

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example, industrial processes (Level 1) consisted of petroleum and related industries and other

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industrial processes in Level 2. Petroleum and related industries encompassed the following 17

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different operations in Level 3, including crude oil and natural gas extraction, petroleum refining,

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gas stations, oil product transport and storage, raw chemicals, fertilizers, pesticides, paint and ink,

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synthetic materials, chemical fibers, synthetic rubber, rubber products, reclaimed rubber,

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artificial leather and plastic manufacturing, and the impact of various products or manufacturing

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technologies were further considered in Level 4 classes. In this study, a total of 152 sources were

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considered, as shown in Table S1 in the Supporting Information (SI).47 Based on this method, the

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bulk VOC emissions were calculated. Provincial emissions in 2013 are summarized in Table S2. N

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Et = ∑ (∑ Pm,n ×VMTm,n ×EFm,n + ∑ (1-Rk )×EFs,k ×As,k ) ×10-12

(1)

p=1

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where Et is the total VOC emission (Tg); Pm,n is the vehicular population of category m, with

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emission standard n in province p (N=31, including all of the provinces, municipalities, and 6 Environment ACS Paragon Plus

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autonomous regions in mainland China); VMTm,n and EFm,n are the corresponding annual average

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mileage (km) and emission factor (g/km), respectively; Rk is the removal efficiency with

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technology k; and EFs,k and As,k are the corresponding emission factors and activity data for

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source s (except on-road vehicles), respectively.

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2.2 Development of the domestic source profile database

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In this study, most of the profiles used for speciation were selected from local measurements and

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domestic research. For some sources, such as ships and planes (i.e., off-road transport), of which

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the VOC emissions were relatively small and local measurements were lacking, source profiles

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were obtained from the SPECIATE v.4.4 database. The developing procedure involved the

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following steps:

106 107

(1) Source classification. To ensure consistency with the emission inventory, the source categorization of profiles was identical to those adopted in the inventory.

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(2) Searching candidate profiles. A large number of domestic profiles were selected from

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the literature and our own measurements, and were sorted according to source types. However,

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for a small proportion of VOC sources, such as ships, planes, trains, cooking, and papermaking,

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no local profiles were available. In this case, profiles from the SPECIATE database were adopted.

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The candidate profiles involved in this study are summarized in Table S3.

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(3) Determining VOC species. Because the measured VOC species from identical sources

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typically varied among different studies, we determined a unified species list for different

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profiles, which consisted of more than 130 individual species in total, as listed in Table S4.

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These species were measurable, abundant or highly reactive in the atmosphere.

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(4) Including OVOCs. As abovementioned, OVOCs are an important fraction of VOCs, but

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have often been omitted in previous studies.24, 48 In this study, we revised the profiles of missing



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OVOCs for OVOC-rich sources (including diesel vehicle exhaust, biomass burning and solvent

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use) following the method proposed by Li et al.24 The details of this method are described in the

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SI.

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(5) Constructing integrated profiles. To reduce the high uncertainties that arise from using a

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single profile, we selected as many candidate profiles as possible for each source, and weighted

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them equally. Then relative weighted percentage of a specific species was determined by

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averaging the values from all of the candidate profiles. It should be noted that although using

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integrated profiles is a useful way to reduce uncertainties, it may introduce additional

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uncertainties with the assumption that different profiles are equally weighted.24 The integrated

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profiles developed in this study are listed in Table S4.

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2.3 Calculation of speciated VOC emissions and OFP

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The speciated VOC emissions were calculated by multiplying the total emissions by the

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corresponding weight percentages, as formulated in Eq. (2):

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Etotal, j = ∑ Ei ×fi, j

(2)

i

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where Etotal,

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emissions from source i, respectively; and fi,j is the weighted percentage of species j from source

135

i.

j

and Ei are the total emissions of species j from all of the sources and VOC

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Different VOC species significantly differ in their potential to form O3, which can be

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calculated by the maximum incremental reactivity (MIR).49 The ozone formation potential (OFP)

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is a concept used to assess the maximum contribution of VOC species to O3 formation under

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optimum reaction conditions. It is widely used to determine the key species and sources of local

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O3 formation based on both emissions and reactivity.50-52 OFP can be calculated using Eq. (3):

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OFPi, j =Ei, j ×MIRj


(3)

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where OFPi,j is the OFP of species j from source i; Ei,j is the emission of species j from that

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source; and MIRj is the maximum incremental reactivity of species j.

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2.4 Spatial allocation

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Provincial emissions were distributed to grids at a resolution of 12 × 12 km using spatial

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surrogates. The surrogates used in this study were gross domestic product (GDP), second

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industry output (SIO), population, sown area (SA), and MODIS fire data (MOF). The GDP was

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used to allocate emissions from transportation and solvent use; SIO was used for industrial

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processes; population was used for stationary fossil fuel combustion; and SA and MOF were

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used for biomass burning.47 Thereafter, the gridded emissions were aggregated using Mapinfo, a

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desktop geographic information system (GIS) application used for mapping and location

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analysis.53 Finally, the gridded emissions at a resolution of 12 × 12 km were mapped by ArcGIS.

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3. Results

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3.1 Speciated emissions and OFP in China

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According to our estimates, aromatics (9.5 Tg, 32% of the total) made up the largest fraction of

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the total VOC emissions in 2013, followed by alkanes (8.4 Tg, 28%), OVOCs (5.4 Tg, 18%),

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alkenes (3.0 Tg, 10%), halocarbons (0.8 Tg, 3%), and alkynes (0.6 Tg, 2%), as shown in Table

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S5. Styrene (2.0 Tg), toluene (1.9 Tg), m-/p-xylene (1.4 Tg), benzene (1.4 Tg) and ethylene (1.2

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Tg) were the most abundant species nationwide, accounting for 26% of the total emissions. n-

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hexane (1.1 Tg, 4%), ethane (1.0 Tg, 3%), ethylbenzene (1.0 Tg, 3%), acetone (0.9 Tg, 3%), and

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formaldehyde (0.8 Tg, 3%) also significantly contributed to the total VOC emissions. The

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provincial emissions of speciated VOCs are provided in Table S6. And a comparison with

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previous studies and uncertainty analysis were made in the SI.



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The anthropogenic VOC emissions in China for the year of 2013 have the potential to form

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100.8 Tg O3. Among all of the chemical groups, aromatics were the largest contributors,

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accounting for 40% (40.5 Tg-O3) of the total OFP (see Table S5). Alkenes and OVOCs were also

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key groups, contributing to 30% and 20% of the national OFP, respectively. The relatively high

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contribution from OVOCs indicates that it is necessary to include them in the incomplete profiles

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that have been published previously.

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In terms of individual species, m/p-xylene was the species with the largest OFP, as shown in

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Table S5, and was responsible for 11% (11.3 Tg O3) of the OFP in China. Ethylene,

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formaldehyde, toluene, propene, acetaldehyde, o-xylene, styrene, 1,3-butadiene and 1,2,4-

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trimethylbenzene were other species that made a large contribution to O3 formation. Together 10

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key species accounted for 62% of the total OFP, with only about 32% of the total VOC

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emissions. From Table S5, it can be clearly seen that species with large emissions did not

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necessarily make an equally importance to OFP. For example, styrene was the individual species

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with the largest emissions (7% of the total), but its contribution to OFP was only 3%, which was

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eighth highest of all of the species investigated. In contrast, propene made up 2% of the total

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VOC emissions, ranking fifteenth in terms of emissions, while it had the fifth largest potential to

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form O3 with 7% of the total OFP. This significant discrepancy between emission-based and

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OFP-based contributions was predominantly attributed to the different chemical reactivity of

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individual species, as scaled by the MIR in this study.

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3.2 Source contributions

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3.2.1 National level

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Table 1 shows the source distribution of VOC emissions and OFP in China for 2013. Generally,

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petroleum-related industries and on-road vehicles were the two predominant sources of VOCs,


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responsible for 25% and 22% of the total emissions, respectively. Among Level 3 sources,

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passenger cars made the most significant contribution with about 16% of the total emissions,

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followed by the residential combustion of agricultural residues (1.9 Tg, 6%), coke production

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(1.5 Tg, 5%), raw chemicals manufacturing (1.5 Tg, 5%), and motorcycles (1.2 Tg, 4%) (see

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Table S8).

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Table 1. Source contributions to volatile organic compound (VOC) emissions and ozone

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formation potential (OFP) in China, 2013 Emissions Contribution OFPs Contribution -1 -1 (Gg yr ) (%) (Gg yr ) (%) Transportation 8056.4 26.9 33586.8 33.3 on-road vehicles 6472.3 21.6 26563.2 26.4 off-road transport 1584.1 5.3 7023.6 7.0 Biomass burning 3386.7 11.3 17402.6 17.3 agricultural residues open burning 921.8 3.1 5218.0 5.2 biofuel combustion 2465.0 8.2 12184.6 12.1 Stationary fossil fuel combustion 2221.6 7.4 7276.9 7.2 Industrial & commercial consumption 911.2 3.0 3142.0 3.1 power generation 222.4 0.7 900.9 0.9 heat supply 51.1 0.2 207.0 0.2 residential combustion 1036.8 3.5 3027.0 3.0 Industrial processes 11947.7 39.9 27965.4 27.7 petroleum & related industry 7512.4 25.1 19222.2 19.1 other industrial processes 4435.3 14.8 8743.1 8.7 Solvent utilization 4325.9 14.4 14555.5 14.4 pesticide use 861.3 2.9 1191.0 1.2 printing and dyeing 425.8 1.4 711.7 0.7 road paving with asphalt 581.5 1.9 1568.0 1.6 surface coating 2260.4 7.6 10806.5 10.7 other solvent use 196.9 0.7 278.3 0.3 Sectors

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On-road vehicles and petroleum-related industries were also major contributors to O3

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formation, accounting for 26% and 19% of the national OFP. In addition, biofuel combustion

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and surface coating were significant OFP contributing source sectors (with a potential to form

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12.2 and 10.8 Tg O3, respectively), accounting for 23% of the total OFP in China, as shown in



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Table 1. In particular, of the Level 3 source categories, passenger cars had the highest OFP (19.5

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Tg-O3), followed by the residential combustion of agricultural residues (9.3 Tg-O3), coke

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production (4.8 Tg-O3), motorcycles (4.3 Tg-O3), and reclaimed rubber manufacturing (4.0 Tg-

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O3). These five subsectors accounted for 42% of the OFP, with 35% of the total emissions, as

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shown in Table S6. The OFP-based contributions of some sectors (e.g., on-road vehicles, biofuel

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combustion, and surface coating) were clearly higher than their emission-based contributions,

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whereas contributions of the petroleum-related industries and other industrial processes

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displayed the opposite trend. This indicates that VOC emissions from transportation, biomass

206

burning, and surface coating had a higher potential to form O3 than emissions from industrial

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processes, which is mainly attributed to the larger fraction of photochemically active species

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from these sources.40, 41, 46, 54, 55

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The source contributions of 10 individual species with the largest OFP contributions are

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shown in Figure 1. The most photochemically active species for O3 formation, m/p-xylene (11.3

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Tg-O3), mainly originated from solvent use (45%), industrial processes (20%), transportation

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(19%), and stationary fossil fuel combustion (14%). Ethylene was primarily emitted from

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transportation (39%) and biomass burning (38%), and propene emissions were abundant in the

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sectors of transportation (38%), industrial processes (23%), and biomass burning (21%). As a

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widely used raw material and solvent,38,

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industrial processes. Transportation and solvent utilization also made a significant contribution to

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toluene, accounting for 25% and 17% of its emissions. The source distributions of o-xylene and

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1,2,4-trimethylbenzene were similar to those of toluene, both of which were mainly from

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industrial processes, transportation, and solvent utilization. Industrial processes dominated the

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emissions of styrene and 1,3-butadiene, occupying 65% and 64%, respectively. The source

40

43% of the toluene emissions were generated by


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distributions of formaldehyde and acetaldehyde were substantially different from the other

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species investigated, and were almost entirely from transportation and biomass burning. This is

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consistent with previous reports of carbonyls accounting for a large fraction of VOC emissions

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from biomass burning and vehicles (particularly heavy-duty diesel vehicles).46 Overall,

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transportation and industrial processes were the two sectors that most significantly contributed to

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the majority of the top 10 species, whereas biomass burning and transportation dominated the

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emissions of oxygenated compounds. 100

12

1.m/p-xylene 2.ethylene 3.formaldehyde 9

OFPs (Tg-O3)

Source contribution (%)

80

60

40 6

4.toluene 5.propene 6.aceteldehyde 7.o-xylene 8.styrene

20

9.1,3-butadiene 10.1,2,4-TM-benzene

0

3 1

228 229

2

biomass burning

3

4

5

fossil fuel combustion

6

7

transportation

8

9

10

industrial processes

solvent utilization

Figure 1. Source contributions of 10 individual species with the 10 largest OFP contributions

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3.2.2 Provincial level

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The source distributions for total OFP varied among the different provinces in China, as shown

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in Figure 2. Generally, transportation and industrial processes were the sectors that made the

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main contribution to OFP in most provinces, accounting for more than 40% of the total.

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However, in some provinces, such as Heilongjiang, Anhui, Yunnan, Jiangxi and Sichuan, where



235

agriculture is well developed and biomass is a commonly used fuel in rural areas, biomass

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burning played a more important role in O3 formation than industrial processes, contributing to

237

40%, 36%, 31%, 31% and 30% of the provincial OFP, respectively. In Shanghai, Guangdong,

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Chongqing, Zhejiang, Fujian, Jiangsu and Beijing, solvent use made a relatively high

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contribution (more than 20%) to the provincial OFP, which was mainly attributed to the large

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usage of solvents in these provinces.29, 41, 48, 52

241 242

Figure 2. Source contributions of ozone formation potential (OFP) in each province in China in

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2013


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In order to provide more specific information to regulators regarding which sources and

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species to target to mitigate O3 pollution efficiently in different regions, the major contributors to

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OFP in the three most densely populated, prosperous and severe polluted regions in China (the

247

NCP, YRD, and PRD) were considered in detail.

248

(1) The NCP region. The NCP region has the potential to form 25.45 Tg of O3 in 2013,

249

which accounted for 25% of the OFP nationwide with 26% of the national VOC emissions. As

250

shown in Figure 3, aromatics accounted for most (41%) of the OFP in this region, followed by

251

alkenes (30%) and OVOCs (18%). By source sector, on-road vehicles were the largest

252

contributor, accounting for 29% of the regional OFP, followed by petroleum and related

253

industrial processes, other industrial processes, biofuel combustion and surface coating.

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Specifically, passenger cars (23%), reclaimed rubber products (9%), residential combustion of

255

agricultural residues (8%), coke production (5%), and raw chemical manufacturing (4%) were

256

the major sectors contributing to the overall OFP.

257

The five species responsible for most of the OFP were m-/p-xylene, ethylene, propene,

258

formaldehyde, and toluene, accounting for 11%, 10%, 7%, 7%, and 7%, respectively, of the total

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OFPs in the region. Figure 4 shows the source distribution of these species. As the largest

260

contributor to the regional OFP, m-/p-xylene in the NCP was mainly emitted from surface

261

coating, petroleum and related industrial processes, and on-road vehicles. Biofuel combustion

262

(29%), on-road vehicles (24%), and off-road transportation (15%) were key sources for ethylene.

263

For propene, on-road vehicles were the largest contributor (34%), followed by petroleum-related

264

industrial processes (13%), other industrial processes (11%), and biofuel combustion (11%).

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Transportation and biomass burning made up more than 90% of formaldehyde emissions. For



266

toluene, on-road vehicles, petroleum-related industries, other industrial processes, and surface

267

coating were the key sources, accounting for more than 80% of emissions.


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Figure 3. Characteristics of OFP in three typical regions of China in 2013 (NCP: the North China Plain; YRD: the Yangtze River

270

Delta; PRD: the Pearl River Delta). Only the contributions of the predominant groups or source sectors are listed considering space.



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Generally, m-/p-xylene, ethylene, propene, formaldehyde and toluene were the largest OFP-

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contributing species in the NCP region. Passenger cars, reclaimed rubber product manufacturing,

273

residential combustion of agricultural residues, coke production and raw chemicals

274

manufacturing were the predominant sources of OFP. To be more efficient for alleviating O3

275

pollution in this region, control strategies should be targeted toward these key species and

276

sources.

277

(2) The YRD region. The OFP in the YRD was estimated to be 17.56 Tg-O3 in 2013,

278

accounting for 17% of the national OFP, with 18% of VOC emissions. Similar to the NCP,

279

aromatics were the largest contributor to O3 formation. Alkenes and OVOCs were the two other

280

groups that made an important contribution to the regional OFP, as shown in Figure 3. By source

281

sector, petroleum-related industries, on-road vehicles, surface coating, and off-road

282

transportation were the key sources in this region.

283

The five largest contributors to O3 formation in this region were m-/p-xylene, toluene,

284

ethylene, propene, and formaldehyde. Together they accounted for 43% of the regional OFP,

285

with 21% of the VOC emissions. It is clear from Figure 4 that the source distribution of many

286

species in the YRD differed from that in the NCP. For example, surface coating was the

287

predominant source of m-/p-xylene emissions, accounting for nearly 60% of its emissions in the

288

YRD, which was much higher than in the NCP (31%). Similarly, 52% of the toluene emissions

289

were attributed to petroleum-related industries in the YRD, whereas this sector only contributed

290

20% of the toluene emissions in the NCP. Ethylene was mainly emitted from off-road

291

transportation, on-road vehicles, and biofuel combustion, whereas for propene, on-road vehicles

292

were the largest contributor, followed by petroleum industries and off-road transportation. Off-


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road transportation (40%) was the largest contributor to formaldehyde in this region, followed by

294

on-road vehicles (28%), biomass open burning (13%), and biofuel combustion (14%).



0.3% 4.1%0.7% 0.1% 0.8% 0.7% 6.8%

29.6%

15.2% 6.6%

0.7%

15.6%

-3

x10

40

0.7% 3.1% 4.7% 0.2%

toluene

0.1%

PRD

1.5% 0.6% 0.3%

11.4%

a

7.6%

4.6%

0.3% 15.6% 6.4% 0.1% 0.4% 10.2%

52.8%

m/p-xylene

Source sectors On-road vehicles Power generation Pesticide use

0.3%

5.0%

0.1% 0.9% 3.3%

0.4% 0.9% 5.1%

ethylene

19.8%

12.0% 21.3%

formaldehyde

toluene

33.0%

7.1%

6.0%

5.1% 3.9% 0.7% 3.2%

16.5%

20.3%

6.4%

3.1% 0.2%

ethylene propene

39.3%

13.0%

30.1%

0.7%

toluene

Off-road transport Heat supply Printing and dyeing

14.1%

1.8% 3.4%

formaldehyde 0.1%1.6% 0.1% 0.7%

28.7% 11.3%

20.2%

1.6% 0.4% 6.1%

0.7% 1.0% 0.5%

28.4%

5.4%

5.2% 2.5% 0.3% 0.5% 0.9% 11.3%

29.4%

19.3%

9.4%

24.4%

19.7%

m/p-xylene

0

ethylene propene

28.0%

1.7% 4.7%

19.9%

13.1% 6.5% 2.4% 0.8% 2.8%

14.4%

51.7%

80

20

11.5%

1.5% 1.0% 2.9%

57.3%

60

2.4% 1.5%

11.2%

3.5%0.6%2.1% 1.3% 0.7% 1.3%

11.0%

100

30.6% 23.8%

8.3%

5.4%

ethylene

0.3%3.5% 0.3% 0.3% 7.3% 15.2% 1.1%

YRD

0.2%

6.9% 6.9%

m/p-xylene

295

a

29.5%

4.6% 0.1% 0.3% 0.4%

34.2%

24.0%

0.6% 30.6%

1.3% 1.2% 0.5%

2.1%1.1% 4.1% 3.4% 0.7% 0.2% 3.8%

5.3%

20.4%

NCP

Page 20 of 39

56.9%

28.4%

18.9%

0.3% 1.7% 0.7% 1.6% 0.2% 0.1%

Styrene

Biomass open burning Residential combustion Asphalt pavement

33.4%

a

28.8%

1.9%0.6% 7.0% 1.4%2.3% 0.7% 1.0% 0.4% 3.9% 6.6%

ethylene

Biofuel combustion Petroleum industries Surface coating

15.1% 0.1%

45.1%

ethylene o-xylene

Industrial combustion Other industry process Other solvent use

296

Figure 4. Source contributions of the five species contributing most to OFP in typical regions of China in 2013 (NCP: the North

297

China Plain; YRD: the Yangtze River Delta; PRD: the Pearl River Delta)


Page 21 of 39


298

Overall, m-/p-xylene, toluene, ethylene, propene and formaldehyde were the five species

299

that made the largest contribution to O3 formation, and petroleum-related industrial processes,

300

on-road vehicles, surface coating, and off-road transportation were the main sources to OFP in

301

the YRD. Consequently, there should be a focus on controlling these key sources and species to

302

alleviate O3 pollution in this region.

303

(3) The PRD. The OFP in the PRD region was estimated to be 8.86 Tg-O3 in 2013, which

304

accounted for 9% of the national OFP, with 9% of VOC emissions. Similar to the NCP and YRD,

305

aromatics were the largest contributor (59%) to the OFP in this region. As shown in Figure 3, on-

306

road vehicles, petroleum-related industries, and surface coating were the three sources of VOCs

307

that made the greatest contribution to O3 formation in this region. Among the Level 3 sources,

308

building coating (10%), passenger cars (10%), motorcycles (10%), and residential LPG

309

combustion (8%) were important contributors (see Table S9). This was quite different from the

310

source distributions in the NCP and YRD regions, which was mainly attributed to the unique

311

energy and industrial structure in the PRD region.

312

The five species responsible for most of the OFP in this region were m-/p-xylene, toluene,

313

styrene, ethylene, and o-xylene. Together they accounted for 45% of the regional OFP, with 31%

314

of the VOC emissions. Surface coating was the largest contributor to m-/p-xylene, accounting for

315

53% of its emissions, as shown in Figure 4. Buildings, household appliances, enamel wires, and

316

vehicle coatings were the major contributing subsectors within the surface coating sector (see

317

Table S9). Most of the o-xylene emissions originated from surface coating (45%), while surface

318

coating, on-road vehicles, and petroleum-related industries were the major contributors to

319

toluene, responsible for 71% of its emissions. For styrene, more than 50% of its emissions came

320

from petroleum and related industrial processes in the PRD. Ethylene mostly originated from



321

biofuel combustion, on-road vehicles, and off-road transportation, which together accounted for

322

76% of its emissions.

Page 22 of 39

323

In general, the key species for O3 formation in the PRD region were similar to those in the

324

NCP and YRD regions. However, due to the disparate industrial structures and levels of

325

economic development in the three regions, the key species and sources contributing to O3

326

formation were regionally different. In the NCP, passenger cars, reclaimed rubber product

327

manufacturing, combustion of agricultural residues, and coke production were the major

328

contributors to O3 formation. In the YRD, due to the well-developed organic synthetic industry,

329

chemical fiber and raw chemicals manufacturing made a more significant contribution to OFP,

330

after passenger cars. In the PRD, building coating, passenger cars, motorcycles, and residential

331

LPG combustion were the key contributing sources to OFP. This suggests that regulators should

332

implement localized VOC control strategies among various regions in China.

333

3.3 Spatial distribution of OFP

334

The spatial distribution of OFP at a resolution of 12 × 12 km is shown in Figure 5a. Clearly, the

335

OFP in southern and eastern China was much higher than the OFP in the north and west of China,

336

particularly in the NCP, YRD, and PRD regions. The highest intensity was observed in Shanghai

337

(2.84 Gg-O3 km-2 yr-1). As shown in Figure 5a, cities in the NCP, YRD and PRD regions were

338

more likely to experience high levels of O3. Figure 5b shows the distribution of total tropospheric

339

column O3 at a spatial resolution of 1° × 1° in 2013, which was retrieved from Aura Ozone

340

Monitoring Instrument (OMI) observations.56 It shows that the annual average column O3 in the

341

NCP, YRD, PRD, the Sichuan Basin (SB) and central China was much higher than in other

342

regions, with an average value larger than 380 DU. This space-based measurement of O3

343

distribution is consistent with the distribution of OFP determined in our study, with a Moran’s I


Page 23 of 39


344

coefficient of 0.48, as shown in Figure S3. And the result of Monte Carlo analysis indicates that

345

the estimated OFP is significantly correlated to the tropospheric column O3 at the confidence

346

interval of 99.9%.



(a) OFP

(b) tropospheric column O3

347 348

Figure 5. Spatial distribution of (a) OFP and (b) annual average tropospheric column O3 retrieved from OMI data in China for 2013


Page 24 of 39

Page 25 of 39


349

4. Discussion

350

Ozone formation involves a series of photochemical reactions between VOCs and NOx, therefore,

351

it can be controlled by reducing either one of the precursors. However, due to its nonlinear

352

response to changes in the emissions of the two precursors, the O3 formation mechanism is far

353

more complex than expected. For example, in a NOx-saturated (known as VOC-sensitive) regime

354

region, NOx reduction would lead to an initial increase in O3 concentrations.

355

the design of control strategies for O3 should take the O3-VOC-NOx relationship into

356

consideration. However, our limited understanding of the O3-VOC-NOx sensitivity in China has

357

impeded the improvement of air quality. To determine the sensitivity of O3 production, it is

358

necessary to estimate the total VOC reactivity with OH.58 HCHO is used as a proxy for VOC

359

reactivity because it is a short-lived oxidation product of various VOCs.59 In this study, we used

360

the formaldehyde/nitrogen dioxide (HCHO/NO2) column ratio from the OMI as a space-based

361

indicator to characterize the O3-VOC-NOx sensitivity in China. This method has been widely

362

used and has been demonstrated to be consistent with our current understanding of O3 formation

363

sensitivity.58,

364

sensitive and VOC-sensitive conditions occurs when the HCHO/NO2 ratio is about 1.58, 60, 61

60-62

57, 58

Accordingly,

In addition, previous studies have shown that the transition between NOx-

365

Figure S4 shows the OMI-derived HCHO/NO2 column ratio over China in 2013,

366

specifically, that most areas in the NCP, YRD, PRD and SB tend to be NOx-saturated in January,

367

which was attributed to the abundant NOx supply in winter. 63, 64 A switch from a NOx-saturated

368

to NOx-sensitive regime occurs in most suburban and rural areas of the regions listed above

369

when summer arrives, as shown in Figure S4(b) and Figure S4(c), whereas the main urban areas

370

of these regions are still NOx-saturated. The seasonal transition of the chemical regime is

371

because when it turns into summertime, the ascent in HOx radicals makes the pathway of HOx



Page 26 of 39

372

loss dominated primarily by reaction with peroxy radicals, leading to the O3 production sensitive

373

to NOx.61 This result is consistent with modeling analyses and in-situ observations in China.8, 20-

374

23, 65

375

in the fall, with the chemical regime switching from mixed to NOx-saturated. This seasonal

376

transition is theoretically expected because of the increase in the NOx supply and decline in the

377

HOx supply during this period.61 According to our estimates, in most of the well-developed

378

regions of China, such as the NCP, YRD, PRD and SB, and particularly the major urban areas,

379

the O3 production is VOC-limited throughout the year. Therefore, an increased focus on VOC

380

emission control is recommended to reduce O3 pollution in China.

The HCHO/NO2 ratio decreases to less than 1 over most areas in eastern and central China

381

Currently, VOC emissions are not legally regulated in China. In recent years, several VOC

382

control policies have been issued, including the reducing VOC emissions during industrial

383

processes, tighter fuel quality standards and vehicular emission standards, the introduction of oil

384

and gas vapor recovery systems in gas stations, and the use of water-based or low organic-

385

content solvents to replace organic solvents.66 However, these measures were all mass-based,

386

without

387

countermeasures were much more effective than mass-based VOC strategies in mitigating O3

388

pollution.67, 68 The experience in California indicates that simple mass-based reduction measures

389

may occasionally result in an unexpectedly higher OFP.67 In this study, the top 20 species in

390

terms of emissions (see Table S5) together accounted for 60% of the total VOC emissions. From

391

a mass-based perspective, these 20 compounds should be key targets for control. The total VOC

392

emissions would be reduced by 60% if emissions of these species were completely eliminated,

393

which would lead to an OFP reduction of 62%. From an OFP-based perspective, the top 20 OFP

394

contributing species (see Table S5) should be targeted, and a reduction of 75% of the OFP, with

considering

reactivity.

Previous

studies

have


shown

that

reactivity-based

Page 27 of 39


395

a reduction of 43% of VOC emissions, would be achieved if these 20 species were fully

396

controlled. This suggests that OFP-based VOC control measures would be more efficient to

397

alleviate O3 pollution.

398

In general, our results indicate that O3 formation in China is sensitive to VOC emissions in

399

urban areas in most regions, and OFP-based VOC reduction strategies are more efficient than

400

emission-based strategies for O3 reduction. Consequently, policy makers should shift current

401

emission-based limits to reactivity-based policies. In addition, due to the disparate industrial

402

structures and economic development levels among the different regions in China, control

403

strategies should be suited to local conditions.

404

Supporting Information

405

Additional information, including four figures and seven tables, were noted in the manuscript.

406

These materials are available free of charge via the Internet at http://pubs.acs.org.

407

Author Information

408

Corresponding Authors: Shaodong Xie

409

Phone: 86-010-62755852; fax: 86-010-62755852; e-mail: [email protected]

410

Present Address: Room 402, College of Environmental Sciences and Engineering, State Key

411

Joint Laboratory of Environmental Simulation and Pollution Control, Peking University, No.5

412

Yiheyuan Road, Haidian District, Beijing, 100871, China

413

Notes: The authors declare no competing financial interest.

414

Acknowledgements

415

This work received funding from the National Natural Science Foundation as part of the key

416

project entitled The development and validation of emission inventories of anthropogenic volatile

417

organic compounds in the Beijing-Tianjin-Hebei region, China (No. 91544106), and the



418

Environmental Protection Ministry of China as part of the program named The research of

419

emission reduction and regulatory system of volatile organic compounds (VOCs) in key sectors

420

(No. 20130973).


Page 28 of 39

Page 29 of 39


421

References

422

(1) Stevenson, D.; Young, P.; Naik, V.; Lamarque, J.-F.; Shindell, D. T.; Voulgarakis, A.; Skeie,

423

R.; Dalsoren, S. B.; Myhre, G.; Berntsen, T. Tropospheric ozone changes, radiative forcing and

424

attribution to emissions in the Atmospheric Chemistry and Climate Model Intercomparison

425

Project (ACCMIP). Atmos. Chem. Phys. 2013, 13, (6), 3063-3085.

426

(2) Thompson, A. M.; Balashov, N. V.; Witte, J.; Coetzee, J.; Thouret, V.; Posny, F. Tropospheric

427

ozone increases over the southern Africa region: bellwether for rapid growth in Southern

428

Hemisphere pollution? Atmos. Chem. Phys. 2014, 14, (18), 9855-9869.

429

(3) Monks, P. S.; Archibald, A.; Colette, A.; Cooper, O.; Coyle, M.; Derwent, R.; Fowler, D.;

430

Granier, C.; Law, K. S.; Mills, G. Tropospheric ozone and its precursors from the urban to the

431

global scale from air quality to short-lived climate forcer. Atmos. Chem. Phys. 2015, 15, (15),

432

8889-8973.

433

(4) Xu, W.; Lin, W.; Xu, X.; Tang, J.; Huang, J.; Wu, H.; Zhang, X. Long-term trends of surface

434

ozone and its influencing factors at the Mt Waliguan GAW station, China–Part 1: Overall trends

435

and characteristics. Atmos. Chem. Phys. 2016, 16, (10), 6191-6205.

436

(5) Young, P.; Archibald, A.; Bowman, K.; Lamarque, J.-F.; Naik, V.; Stevenson, D.; Tilmes, S.;

437

Voulgarakis, A.; Wild, O.; Bergmann, D. Pre-industrial to end 21st century projections of

438

tropospheric ozone from the Atmospheric Chemistry and Climate Model Intercomparison Project

439

(ACCMIP). Atmos. Chem. Phys. 2013, 13, (4), 2063-2090.

440

(6) Allen, R. J.; Sherwood, S. C.; Norris, J. R.; Zender, C. S. Recent Northern Hemisphere

441

tropical expansion primarily driven by black carbon and tropospheric ozone. Nature 2012, 485,

442

(7398), 350-354.

443

(7) Cooper, O.; Parrish, D.; Stohl, A.; Trainer, M.; Nédélec, P.; Thouret, V.; Cammas, J.-P.;



Page 30 of 39

444

Oltmans, S.; Johnson, B.; Tarasick, D. Increasing springtime ozone mixing ratios in the free

445

troposphere over western North America. Nature 2010, 463, (7279), 344-348.

446

(8) Ding, A.; Fu, C.; Yang, X.; Sun, J.; Zheng, L.; Xie, Y.; Herrmann, E.; Nie, W.; PetÃĪjÃĪ, T.;

447

Kerminen, V.-M. Ozone and fine particle in the western Yangtze River Delta: an overview of 1 yr

448

data at the SORPES station. Atmos. Chem. Phys. 2013, 13, (11), 5813-5830.

449

(9) Ding, A. J.; Wang, T.; Thouret, V.; Cammas, J. P.; Nédélec, P. Tropospheric ozone

450

climatology over Beijing: analysis of aircraft data from the MOZAIC program. Atmos. Chem.

451

Phys. 2008, 8, (1), 1-13.

452

(10) Richter, A.; Burrows, J. P.; Nüß, H.; Granier, C.; Niemeier, U. Increase in tropospheric

453

nitrogen dioxide over China observed from space. Nature 2005, 437, (7055), 129-132.

454

(11) Wang, T.; Wei, X.; Ding, A.; Poon, S. C.; Lam, K.; Li, Y.; Chan, L.; Anson, M. Increasing

455

surface ozone concentrations in the background atmosphere of Southern China, 1994-2007.

456

Atmos. Chem. Phys. 2009, 9, (2), 6217-6227.

457

(12) Air Pollution Prevention And Control Action Plan; China’s State Council (translated by

458

Clean Air Alliance of Chian): Beijing, 2013; http://www.cleanairchina.org/product/6349.html

459

(accessed on 26 June 2016).

460

(13) The 12th Five-Plan on Air Pollution Prevention And Control in Key Regions; Ministry of

461

Environmental

462

http://www.zhb.gov.cn/gkml/hbb/bwj/201212/W020121205566730379412.pdf (accessed on 19

463

January 2017).

464

(14) China Environmental State Bulletin; Ministry of Environmental Protection of the People’s

465

Republic

466

http://jcs.mep.gov.cn/hjzl/zkgb/2014zkgb/201506/t20150608_303142.shtml (accessed on 1 July

Protection

of

of

the

People’s

Republic

China:


of

China:

Beijing,

Beijing,

2012;

2014;

Page 31 of 39


467

2016).

468

(15) China Environmental State Bulletin; Ministry of Environmental Protection of the People’s

469

Republic

470

http://www.zhb.gov.cn/gkml/hbb/qt/201606/W020160602411685220884.pdf (accessed on 1 July

471

2016)

472

(16) Cheung, V. T.; Wang, T. Observational study of ozone pollution at a rural site in the Yangtze

473

Delta of China. Atmos. Environ. 2001, 35, (29), 4947-4958.

474

(17) Wang, T.; Ding, A.; Gao, J.; Wu, W. S. Strong ozone production in urban plumes from

475

Beijing, China. Geophys. Res. Lett. 2006, 33, (21), 320-337.

476

(18) Xu, X.; Lin, W.; Wang, T.; Yan, P.; Tang, J.; Meng, Z.; Wang, Y. Long-term trend of surface

477

ozone at a regional background station in eastern China 1991–2006: enhanced variability. Atmos.

478

Chem. Phys. 2008, 8, (10), 2595-2607.

479

(19) The Air Quality Report for the 74 Cities in The Third Quarter of 2015; China National

480

Environmental

481

http://www.zhb.gov.cn/hjzl/dqhj/cskqzlzkyb/201605/P020160526417794112082.pdf

482

on 1 July 2016).

483

(20) Chen, P.; Quan, J.; Zhang, Q.; Tie, X.; Gao, Y.; Li, X.; Huang, M. Measurements of vertical

484

and horizontal distributions of ozone over Beijing from 2007 to 2010. Atmos. Environ. 2013, 74,

485

37-44.

486

(21) Shao, M.; Lu, S.; Liu, Y.; Xie, X.; Chang, C.; Huang, S.; Chen, Z. Volatile organic

487

compounds measured in summer in Beijing and their role in ground‐level ozone formation. J.

488

Geophys. Res.: Atmos. 2009, 114, (7), 1291-1298.

489

(22) Tang, G.; Wang, Y.; Li, X.; Ji, D.; Hsu, S.; Gao, X. Spatial-temporal variations in surface

of

China:

Monitoring

Beijing,

Center:


Beijing,

2015;

2015; (accessed


Page 32 of 39

490

ozone in Northern China as observed during 2009–2010 and possible implications for future air

491

quality control strategies. Atmos. Chem. Phys. 2012, 12, (5), 2757-2776.

492

(23) Tang, X.; Wang, Z.; Zhu, J.; Gbaguidi, A. E.; Wu, Q.; Li, J.; Zhu, T. Sensitivity of ozone to

493

precursor emissions in urban Beijing with a Monte Carlo scheme. Atmos. Environ. 2010, 44,

494

(31), 3833-3842.

495

(24) Li, M.; Zhang, Q.; Streets, D. G.; He, K. B.; Cheng, Y. F.; Emmons, L. K.; Huo, H.; Kang,

496

S. C.; Lu, Z.; Shao, M.; Su, H.; Yu, X.; Zhang, Y. Mapping Asian anthropogenic emissions of

497

non-methane volatile organic compounds to multiple chemical mechanisms. Atmos. Chem. Phys.

498

2014, 14, (11), 5617-5638.

499

(25) Bo, Y.; Cai, H.; Xie, S. Spatial and temporal variation of historical anthropogenic NMVOCs

500

emission inventories in China. Atmos. Chem. Phys. 2008, 8, (23), 7297-7316.

501

(26) Wei, W.; Wang, S.; Chatani, S.; Klimont, Z.; Cofala, J.; Hao, J. Emission and speciation of

502

non-methane volatile organic compounds from anthropogenic sources in China. Atmos. Environ.

503

2008, 42, (20), 4976-4988.

504

(27) Wei, W.; Wang, S.; Hao, J.; Cheng, S. Trends of chemical speciation profiles of

505

anthropogenic volatile organic compounds emissions in China, 2005–2020. Front. Environ. Sci.

506

Eng. 2012, 8, (1), 27-41.

507

(28) SPECIATE Version 4.4; U.S. Environmental Protection Agency: Washington, DC, February

508

2014; https://www.epa.gov/air-emissions-modeling/speciate-version-45-through-32 (accessed on

509

19 January 2017).

510

(29) Wang, H. L.; Qiao, Y. Z.; Chen, C. H.; Lu, J.; Dai, H. X.; Qiao, L. P.; Lou, S. R.; Huang, C.;

511

Li, L.; Jing, S. G.; Wu, J. P. Source Profiles and Chemical Reactivity of Volatile Organic

512

Compounds from Solvent Use in Shanghai, China. Aerosol Air Qual. Res. 2014, 14, (1), 301-


Page 33 of 39


513

310.

514

(30) Zhang, Y.; Wang, X.; Zhang, Z.; Lü, S.; Shao, M.; Lee, F. S. C.; Yu, J. Species profiles and

515

normalized reactivity of volatile organic compounds from gasoline evaporation in China. Atmos.

516

Environ. 2013, 79, 110-118.

517

(31) Liu, Y.; Shao, M.; Fu, L.; Lu, S.; Zeng, L.; Tang, D. Source profiles of volatile organic

518

compounds (VOCs) measured in China: Part I. Atmos. Environ. 2008, 42, (25), 6247-6260.

519

(32) Tsai, S. M.; Zhang, J.; Smith, K. R.; Ma, Y.; Rasmussen, R.; Khalil, M. Characterization of

520

non-methane hydrocarbons emitted from various cookstoves used in China. Environ. Sci.

521

Technol. 2003, 37, (13), 2869-2877.

522

(33) Wang, J.; Jin, L.; Gao, J.; Shi, J.; Zhao, Y.; Liu, S.; Jin, T.; Bai, Z.; Wu, C.-Y. Investigation

523

of speciated VOC in gasoline vehicular exhaust under ECE and EUDC test cycles. Sci. Total

524

Environ. 2013, 445-446, 110-116.

525

(34) Li, X.; Wang, S.; Duan, L.; Hao, J. Characterization of non-methane hydrocarbons emitted

526

from open burning of wheat straw and corn stover in China. Environ. Res. Lett. 2009, 4, (4),

527

044015.

528

(35) Wang, H.; Lou, S.; Huang, C.; Qiao, L.; Tang, X.; Chen, C.; Zeng, L.; Wang, Q.; Zhou, M.;

529

Lu, S.; Yu, X. Source Profiles of Volatile Organic Compounds from Biomass Burning in Yangtze

530

River Delta, China. Aerosol Air Qual. Res. 2014, 14, (3), 818-828.

531

(36) Wang, S.; Wei, W.; Du, L.; Li, G.; Hao, J. Characteristics of gaseous pollutants from

532

biofuel-stoves in rural China. Atmos. Environ. 2009, 43, (27), 4148-4154.

533

(37) Tsai, J.-H.; Huang, P.-H.; Chiang, H.-L. Characteristics of volatile organic compounds from

534

motorcycle exhaust emission during real-world driving. Atmos. Environ. 2014, 99, 215-226.

535

(38) Hsu, Y.-C.; Chen, S.-K.; Tsai, J.-H.; Chiang, H.-L. Determination of volatile organic profiles



Page 34 of 39

536

and photochemical potentials from chemical manufacture process vents. J. Air Waste Manage.

537

Assoc. 2007, 57, (6), 698-704.

538

(39) Tsai, J. H.; Lin, K. H.; Chen, C. Y.; Lai, N.; Ma, S. Y.; Chiang, H. L. Volatile organic

539

compound constituents from an integrated iron and steel facility. J. Hazard. Mater. 2008, 157, (2-

540

3), 569-78.

541

(40) Zheng, J.; Yu, Y.; Mo, Z.; Zhang, Z.; Wang, X.; Yin, S.; Peng, K.; Yang, Y.; Feng, X.; Cai,

542

H. Industrial sector-based volatile organic compound (VOC) source profiles measured in

543

manufacturing facilities in the Pearl River Delta, China. Sci. Total Environ. 2013, 456-457, 127-

544

136.

545

(41) Yuan, B.; Shao, M.; Lu, S.; Wang, B. Source profiles of volatile organic compounds

546

associated with solvent use in Beijing, China. Atmos. Environ. 2010, 44, (15), 1919-1926.

547

(42) Louie, P. K. K.; Ho, J. W. K.; Tsang, R. C. W.; Blake, D. R.; Lau, A. K. H.; Yu, J. Z.; Yuan,

548

Z.; Wang, X.; Shao, M.; Zhong, L. VOCs and OVOCs distribution and control policy

549

implications in Pearl River Delta region, China. Atmos. Environ. 2013, 76, 125-135.

550

(43) Ballesteros, R.; Hernández, J.; Guillén-Flores, J. Carbonyls speciation in a typical European

551

automotive diesel engine using bioethanol/butanol–diesel blends. Fuel 2012, 95, 136-145.

552

(44) Doyle, M.; Sexton, K. G.; Jeffries, H.; Jaspers, I. Atmospheric photochemical

553

transformations enhance 1, 3-butadiene-induced inflammatory responses in human epithelial

554

cells: The role of ozone and other photochemical degradation products. Chem. Biol. Interact.

555

2007, 166, (1), 163-169.

556

(45) Ou, J.; Feng, X.; Liu, Y.; Gao, Z.; Yang, Y.; Zhang, Z.; Wang, X.; Zheng, J. Source

557

characteristics of VOCs emissions from vehicular exhaust in the Pearl River Delta region (in

558

Chinese). Acta Sci. Circum. 2014, 34, (4), 826.


Page 35 of 39


559

(46) Dong, D.; Shao, M.; Li, Y.; Lu, S.; Wang, Y.; Ji, Z.; Tang, D. Carbonyl emissions from

560

heavy-duty diesel vehicle exhaust in China and the contribution to ozone formation potential. J.

561

Environ. Sci. 2014, 26, (1), 122-128.

562

(47) Wu, R.; Bo, Y.; Li, J.; Li, L.; Li, Y.; Xie, S. Method to establish the emission inventory of

563

anthropogenic volatile organic compounds in China and its application in the period 2008–2012.

564

Atmos. Environ. 2016, 127, 244-254.

565

(48) Ou, J.; Zheng, J.; Li, R.; Huang, X.; Zhong, Z.; Zhong, L.; Lin, H. Speciated OVOC and

566

VOC emission inventories and their implications for reactivity-based ozone control strategy in

567

the Pearl River Delta region, China. Sci. Total Environ. 2015, 530-531, 393-402.

568

(49) Carter, W. P. L. Development of an improved chemical speciation database for processing

569

emissions of volatile organic compounds for air quality models, 2013. report available at

570

http://www.engr.ucr.edu/~carter/emitdb/ (accessed on 29 July 2016).

571

(50) Duan, J.; Tan, J.; Yang, L.; Wu, S.; Hao, J. Concentration, sources and ozone formation

572

potential of volatile organic compounds (VOCs) during ozone episode in Beijing. Atmos. Res.

573

2008, 88, (1), 25-35.

574

(51) Suthawaree, J.; Tajima, Y.; Khunchornyakong, A.; Kato, S.; Sharp, A.; Kajii, Y.

575

Identification of volatile organic compounds in suburban Bangkok, Thailand and their potential

576

for ozone formation. Atmos. Res. 2012, 104, 245-254.

577

(52) Zheng, J.; Shao, M.; Che, W.; Zhang, L.; Zhong, L.; Zhang, Y.; Streets, D. Speciated VOC

578

emission inventory and spatial patterns of ozone formation potential in the Pearl River Delta,

579

China. Environ. Sci. Technol. 2009, 43, (22), 8580-6.

580

(53) MapInfo Professional, http://www.pitneybowes.com/us/location-intelligence/geographic-

581

information-systems/mapinfo-pro.html (accessed on 30 Oct., 2016)



Page 36 of 39

582

(54) Wang, Q.; Geng, C.; Lu, S.; Chen, W.; Shao, M. Emission factors of gaseous carbonaceous

583

species from residential combustion of coal and crop residue briquettes. Front. Environ. Sci. Eng.

584

2012, 7, (1), 66-76.

585

(55) Wang, M.; Shao, M.; Chen, W.; Lu, S.; Liu, Y.; Yuan, B.; Zhang, Q.; Zhang, Q.; Chang, C.

586

C.; Wang, B.; Zeng, L.; Hu, M.; Yang, Y.; Li, Y. Trends of non-methane hydrocarbons (NMHC)

587

emissions in Beijing during 2002–2013. Atmos. Chem. Phys. 2015, 15, (3), 1489-1502.

588

(56) Aura OMI/MLS tropospheric ozone data from NASA Goddard Space Flight Center

589

Website; http://acdb-ext.gsfc.nasa.gov/Data_services/cloud_slice/ (accessed on 8 Novermber

590

2016).

591

(57) Ou, J.; Yuan, Z.; Zheng, J.; Huang, Z.; Shao, M.; Li, Z.; Huang, X.; Guo, H.; Louie, P. K.K.

592

Ambient ozone control in a photochemically active region: short-term despiking or long-term

593

attainment? Environ. Sci. Technol. 2016, 50, 5720-5728.

594

(58) Duncan, B.; Yoshida, Y.; Olson, J.; Sillman, S.; Martin, R.; Lamsal, L.; Hu, Y.; Pickering,

595

K.; Retscher, C.; Allen, D.; Crawford, J. Applocation of OMI observaitons to a space-based

596

indicator of NOx and VOC controls on surface ozone formation. Atmos. Environ. 2010, 44, 2213-

597

2223.

598

(59) Sillman, S. The use of NOy, H2O2, and HNO3 as indicators for ozone-NOx-hydrocarbon

599

sensitivity in urban locations. J. Geophys. Res. 1995, 100, 14175-14188.

600

(60) Choi, Y.; Kim, H.; Tong, D.; Lee, P., Summertime weekly cycles of observed and modeled

601

NOx and O3 concentrations as a function of satellite-derived ozone production sensitivity and

602

land use types over the Continental United States. Atmos. Chem. Phys. 2012, 12, (14), 6291-

603

6307.

604

(61) Martin, R. V.; Fiore, A. M.; Van Donkelaar, A., Space-based diagnosis of surface ozone


Page 37 of 39


605

sensitivity to anthropogenic emissions. Geophys. Res. Lett. 2004, 31, (6), 337-357.

606

(62) Millet, D.; Jacob, D.; Turquety, S.; Hudman, R.; Wu, S.; Fried, A.; Walega, J.; Heikes, B.;

607

Blake, D.; Singh, H.; Anderson, B.; Clarke, A. Formaldehyde distribution over North America:

608

implications for satellite retrivals of formaldehyde columns and isoprene emissions. J. Geophys.

609

Res. 2006, 111, (D24), 4057-4065.

610

(63) Wang, S.; Xing, J.; Chatani, S.; Hao, J.; Klimont, Z.; Cofala, J.; Amann, M., Verification of

611

anthropogenic emissions of China by satellite and ground observations. Atmos. Environ. 2011,

612

45, (35), 6347-6358.

613

(64) Zou, Y.; Deng, X. J.; Zhu, D.; Gong, D. C.; Wang, H.; Li, F.; Tan, H. B.; Deng, T.; Mai, B.

614

R.; Liu, X. T.; Wang, B. G., Characteristics of 1 year of observational data of VOCs, NOx and O3

615

at a suburban site in Guangzhou, China. Atmos. Chem. Phys. 2015, 15, (12), 6625-6636.

616

(65) Nie, T.; Li, X.; Wang, X.; Shao, M.; Zhang, Y. Characteristics of the spatial distributions of

617

ozone-precursor sensitivity regimes in summer over Beijing (in Chinese). Acta Scientiarum

618

Naturalium Universitatis Pekinensis. 2014, 50, (3), 557-564.

619

(66) Control Policies of Volatile Organic Compounds (VOCs); Ministry of Environmental

620

Protection of the Pepople’s Republic of China: Beijing, 2013; Report available at

621

http://kjs.mep.gov.cn/hjbhbz/bzwb/wrfzjszc/201306/t20130603_253125.htm

622

Novermber 2016).

623

(67) Avery, R. J. Reactivity-based VOC control for solvent products: More efficient ozone

624

reduction strategies. Environ. Sci. Technol. 2006, 40, (16), 4845-4850.

625

(68) Derwent, R. G.; Jenkin, M. E.; Passant, N. R.; Pilling, M. J. Photochemical ozone creation

626

potentials (POCPs) for different emission sources of organic compounds under European

627

conditions estimated with a Master Chemical Mechanism. Atmos. Environ. 2007, 41, (12), 2570-


(accessed

on

7


628

2579.


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