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Volatile Chemical Product
Volatile Chemical Product
Volatile Chemical Product
E
Total gas-phase VOC emission factors of mobile
xposure to air pollution is the fifth ranking logical study suggests that adverse human health source fuels and VCPs are based on field (e.g.,
human health risk factor globally, follow- effects occur below current U.S. standards for near-roadway) and laboratory experiments re-
ing malnutrition, dietary risks, high blood PM2.5 and O3 (4). It is thus critical to identify and ported in the literature (Fig. 2). A key finding is
pressure, and tobacco (1). Secondary organic quantify the most important human-produced that VOC emission factors (emission amount per
aerosols (SOA), a major component of fine sources of VOC emissions to effectively mitigate unit product use) resulting from the use of many
particulate matter (PM2.5) in cities around the air pollution and improve human health. chemical products are one to two orders of mag-
world (2), form through oxidation of volatile Automotive emissions of VOCs have decreased nitude higher than from automobile exhaust. The
organic compound (VOC) precursors. Oxidation steadily from efforts to control tailpipe emissions relatively low VOC emission factor for on-road
of VOCs in the presence of nitrogen oxides in the United States (5) and Europe (6). As a result, gasoline engines today (Fig. 2) results from (i)
(NOx = NO + NO2) also contributes to tropospher- other sources of VOC emissions are likely growing combustion oxidizing most hydrocarbons in fuel
ic ozone (O3), which increases risks of mortality in relative importance (7 ). Transportation emis- to carbon dioxide, and (ii) the increasing effec-
from respiratory diseases (3). A recent epidemio- sions of NOx and VOCs have long been considered tiveness of modern three-way catalytic convert-
major contributors to formation of O3 (8) and SOA ers in reducing tailpipe VOC emissions over
1
(9–11) in urban areas, although recent studies have multiple decades (5–7). Consequently, the rela-
Cooperative Institute for Research in Environmental
Sciences, University of Colorado, Boulder, CO, USA.
suggested the importance of nonvehicular sources tive importance of VCP emissions has grown. For
2
Chemical Sciences Division, NOAA Earth System Research as major contributors (12–14). Emissions from the example, mixing ratios of acetone, a marker of
Laboratory, Boulder, CO, USA. 3Department of Mechanical use of chemical products have been difficult to coating-related VCPs in this study and in the past
Engineering, Colorado State University, Fort Collins, CO, USA. constrain in models (15 ) or from ambient mea- (16), increased in ambient air in Los Angeles from
4
Department of Civil and Environmental Engineering,
University of California, Davis, CA, USA. 5Department of
surements (16). One challenge has been the lack of 1990 to 2010 (22). This is in sharp contrast to VOCs
Chemistry and Biochemistry, University of Colorado, Boulder, available atmospheric measurements of oxygen- present in gasoline exhaust, which decreased
CO, USA. 6National Center for Atmospheric Research, ated volatile organic compounds (OVOCs) common markedly during the same period (22), except for
Boulder, CO, USA. 7Department of Chemistry, Université de in everyday household products (16 ). Here, we ethanol (23).
Montréal, Montréal, Quebec, Canada. 8Department of
Chemical and Environmental Engineering, Yale University,
focus on volatile chemical products (VCPs), includ- Although U.S. sales of VCPs are substantially
New Haven, CT, USA. 9School of Forestry and Environmental ing pesticides, coatings, printing inks, adhesives, smaller than for gasoline and diesel fuel, VOC
Studies, Yale University, New Haven, CT, USA. 10Department cleaning agents, and personal care products. These emissions from VCPs (7.6 ± 1.5 Tg) are twice as
of Civil and Environmental Engineering, Virginia Polytechnic products contain organic solvents, which lead to large as from mobile sources (3.5 ± 1.1 Tg) (Fig. 1E,
Institute and State University, Blacksburg, VA, USA.
11
Department of Environmental Science, Policy, and
substantial emissions of VOCs to the atmosphere. light green, dark green, and blue bars) because of
Management, University of California, Berkeley, CA, USA. We show that success in controlling air pollu- differences in emission factors. Emissions from
12
Department of Civil and Environmental Engineering, tion has changed the proportions of sources of mobile sources and VCPs should scale with driving
University of California, Berkeley, CA, USA. anthropogenic VOC emissions in the United States, and population, respectively, and be concentrated
*Corresponding author. Email: brian.mcdonald@noaa.gov
†Present address: California Air Resources Board, Sacramento, CA,
decreasing the relative contribution from trans- in cities. Other fossil sources that occur upstream
USA. ‡Present address: Department of Atmospheric Sciences, portation fuels and increasing the contribution of end users (i.e., oil and natural gas extraction, oil
Yonsei University, Seoul, Republic of Korea. from VCPs. We consider four key pieces of evidence refineries, and chemical manufacturing facilities)
Upstream
Natural Gas
Methane Emissions
502
9 4.8 ± 1.4
Plastic &
Rubber
+Inorganics Plastic & Products
5 Rubber Resins 47
Ethylene 55
31
Gasoline Fuel
1.5 ± 0.8
Gasoline Gasoline
(Mobile) Exhaust
381 1.7 ± 0.8
Propylene x VOC EF Diesel 0.33 ± 0.12
13 Pesticides 3 (Figure 2)
Pesticides
Coatings, Inks, 1.1 ± 0.7
Diesel C4 – C5 6 Adhesives
Fig. 1. Mass balance of organic compounds through the U.S. and (C)], organic solvents consumed domestically for chemical products
petrochemical industry in 2012, from crude oil and natural gas (D), and resulting emissions from use of volatile chemical products
production to resulting VOC emissions. (A to E) Within the chemical (E). Emissions from plastic, rubber, and other chemical products are
manufacturing sector, orange sections of boxes track hydrocarbon not considered here. All units are in Tg; boxes are sized proportionally
feedstocks (A), the fraction used for production of organic solvents [(B) among (B), (C), and (D) (17).
100 Pre-Catalyst
(g kg product)
(1965)
10
-1
1 Present Day
(2012)
0.1
Evaporated On-Road Off-Road On-Road Off-Road Pesticides Coatings, Cleaning Personal
Gasoline Gasoline Gasoline Diesel Diesel Inks, Agents Care
Fuel Exhaust Exhaust Exhaust Exhaust Adhesives
US Sales (Tg) 381 364 17 121 47 3.1 11 20 3.5
(±14) (±11) (±9) (±6) (±5) (±1.5) (±2) (±9) (±1.6)
Fig. 2. Total VOC emission factors for end uses of petrochemical (from Fig. 1D). The green symbol and dashed arrow illustrate the large
sources considered in this study, including from mobile sources and reductions in tailpipe VOC emission factors as precatalyst on-road gasoline
volatile chemical products. Shown in the bottom row are sales data of fuels vehicles were replaced by present-day vehicle fleets. Error bars reflect the 95%
for mobile sources (from Fig. 1A) and sales data of volatile chemical products confidence interval of the mean or expert judgment (17).
(µg m )
of individual VOCs measured IVOCs
-3
acetone
ethanol i-propanol
at Pasadena, CA, in 2010. In (A),
xylenes C9-C11
we input only emissions from 1 toluene
toluene
fossil fuels (mobile + upstream acetone
dichloromethane
sources) into the model and 0.1 C9-C11
evaluate against outdoor data
under “no chemistry” conditions; naphthalene Bias = -39% naphthalene Bias = +1%
2 2
0.01 i-propanol R = 0.59 R = 0.94
(B) is the same as (A) but
with the addition of VCP
emissions. (C and D) Comparison 0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000
toluene 2-butoxy-ethanol
toluene
the addition of VCP emissions C12-C13
1 C9-C11
indoors. For all panels, points below D5-siloxane
the 1:1 line indicate that the box dichloromethane
model underpredicts ambient 0.1 2-butoxy-ethanol
or indoor concentrations relative
Bias = -86% Bias = +13%
to observations. Shown at the 2 2
0.01 R = 0.71 R = 0.92
lower right of each panel is the
mean relative bias and R2 of the
0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000
model calculated in log space. Model
statistics exclude aldehydes, Indoor Obs. Indoor Obs.
(µg m -3 ) (µg m -3 )
which appear to be from other
emission sources. Alkanes non-oxy IVOCs Cycloalkanes Aromatics PAHs
Alkenes Monoterpenes Alcohols/Ketones/Esters Aldehydes Halocarbons
represent substantial VOC emissions (Fig. 1E, gray VOCs are similar across industrialized countries resents indoor air of buildings located within the
bar). Note that methane emissions are not shown (29), (ii) VOCs emitted from use of VCPs (e.g., basin (fig. S4).
in these estimates. Upstream processes are un- acetone) are found in ambient air on both con- California has an extensive regulatory report-
certain, and more research is needed to better con- tinents (30, 31), and (iii) indoor levels of VOCs ing program for consumer products (34), includ-
strain their emissions of VOCs (24–27). from chemical products are similar (32, 33). As ing residential and commercial uses, which we
In the United States, current inventories con- discussed below, our emissions inventory is well used to speciate emissions. These speciation pro-
sistently underestimate total VOC emissions from constrained by a comprehensive set of ambient files provided us with target compounds to char-
VCPs by factors of 2 to 3 nationally (table S5) and and indoor measurements, and is more extensive acterize in both outdoor and indoor environments.
regionally (table S6). Nationally, mobile-source in terms of chemical speciation than measure- We also accounted for industrial emissions from
emissions are overestimated by ~40%. The main ments used in prior source apportionment studies. VCPs (e.g., degreasing, adhesives, and coatings).
effect of our analysis is to shift the relative con- Previous studies typically relied on ambient VOC The reporting data are in agreement with a U.S.
tribution of VOC emissions from petrochemical measurements mainly of compounds found in database of chemicals (35) used as key constitu-
sources, away from mobile sources and toward fossil fuels, while not including many species ents in chemical products (table S7). The VOC
VCPs (fig. S2). At national and urban scales, we found in chemical products (16). This may ex- speciation profiles of VCPs (table S8) are distin-
attribute 15 to 42% of petrochemical VOCs to plain why prior source apportionment studies guishable from those of fossil fuels (table S9), al-
mobile sources and 39 to 62% of petrochemical have underestimated the influence of VCP emis- though there is some overlap in species present.
VOCs to VCPs. The rest is from upstream sources sions as sources of urban VOCs. The outdoor box model predictions were eval-
associated with oil and natural gas production uated against summertime ambient VOC mea-
and distribution. Chemical fingerprint of VCPs found in surements made in Pasadena during 2010 (30)
European inventories also show half of VOC ambient and indoor air (table S10). In ambient air, we found that fossil
emissions from VCPs (15, 28). This is in contrast If chemical products are an important source of fuel VOCs [from mobile sources and from local
to source apportionment studies of ambient mea- urban air pollution, then their chemical fingerprint oil and natural gas production and distribution
surements in Europe, which suggest that emissions (fig. S3) should be consistent with ambient and (36)] can only account for 61% of the mass of fresh-
from traffic are the largest source, with chemical indoor air quality measurements. To test our hy- ly emitted VOCs measured, and 59% of their
product emissions substantially overestimated pothesis, we used Los Angeles as a case study and variability (Fig. 3A). The model could be under-
(28). However, we expect VCPs to be an important modeled emissions from petrochemical sources estimating emissions as a result of biases in
source of urban VOC emissions in both European in a two-compartment box model, where one box emission inventories, chemistry, and/or trans-
and U.S. cities, because (i) transportation-related represents ambient air and a second box rep- port. However, to account for the effects of
Volatile Chemical
Products 4%
Consumer Gasoline Consumer Gasoline Consumer Gasoline
VCPs Exhaust VCPs Exhaust VCPs Exhaust
Natural Gasoline
Gas Fuel 19(7)% 18(7)%
27(10)%
38(9)% Gasoline
46(11)% 42(9)% 8(5)% Fuel
41% 47% 13(6)% Gasoline
Fuel
10(5)% 11(5)%
Diesel Gasoline Diesel
14(4)% Exhaust Fuel Exhaust
15(5)% 19(8)%
8% 9(4)% Diesel Upstream
Upstream Exhaust Emissions
Diesel Industrial Emissions Industrial Upstream Industrial
Fuel VCPs VCPs Emissions VCPs
Product Use = 37 Tg VOC Emissions = 350 ± 50 Gg VOC Reactivity = 8.8 ± 1.9 s-1 SOA Potential = 11.5 ± 2.7 Gg
Fig. 4. Contributors to ambient air pollution in Los Angeles. (A to D) Distribution of (A) petrochemical product use, (B) VOC emissions, (C) VOC
reactivity with OH, and (D) SOA formation potential across petrochemical sources only. Contributions from nonfossil sources are not shown.
Uncertainties in source apportionment were determined by Monte Carlo analysis.
chemistry, we used a technique that extrapolates injected consumer VCP emissions into our indoor 1.6 s−1). The emissions from use of VCPs contribute
measured concentrations to fresh emission condi- box model, accounting for typical air exchange an additional 4.8 ± 3.4 s−1, bringing the summed
emissions from VCPs, which contribute ~70% in transportation emissions of ~8% per year (7, 22). 30. A. Borbon et al., J. Geophys. Res. Atmos. 118, 2041–2057
of the SOA formation potential. Consumer uses of VCPs likely remain key sources (2013).
31. B. Langford et al., Atmos. Chem. Phys. 10, 627–645 (2010).
Straight, branched, and cyclic alkanes account of human exposure to air toxics relative to fossil 32. J. M. Logue, T. E. McKone, M. H. Sherman, B. C. Singer, Indoor
for 42 ± 4% of the SOA formation potential from fuels, especially because people spend most of Air 21, 92–109 (2011).
VCPs, followed by OVOCs (29 ± 12%), alkenes their time indoors (62). 33. C. J. Weschler, Atmos. Environ. 43, 153–169 (2009).
and terpenes (17 ± 5%), and aromatics (12 ± 3%). Traditional approaches to mitigating air pol- 34. California Air Resources Board, “The California Consumer
Products Regulation” (2015).
We find SOA distributed over a wide spectrum of lution emphasize transportation and industrial 35. U.S. Environmental Protection Agency, “Chemical Data Access
species, and not dominated by any individual sources (63). However, chemical products are an Tool (CDAT)” (2016).
compound (table S8). The use of petroleum dis- emerging source of urban VOCs (22), including 36. J. Peischl et al., J. Geophys. Res. Atmos. 118, 4974–4990
tillates is a major source of heavier alkanes and SOA precursors (7), because VOC emissions from (2013).
37. S. W. Kim et al., J. Geophys. Res. Atmos. 121, 1340–1360
cycloalkanes (C5 to C15) as well as aromatics VCPs are not declining as fast as those from trans- (2016).
(e.g., toluene and xylenes). Fragrances are major portation. New paradigms leveraging research 38. R. Hossaini et al., Nat. Commun. 8, 15962 (2017).
contributors, most prominently of limonene, tools from the indoor and outdoor air quality 39. F. Klein et al., Environ. Sci. Technol. 50, 1243–1250 (2016).
a-pinene, b-pinene, and 3-carene (57 ). Relatively communities could strengthen efforts to reduce 40. X. M. Wu, M. G. Apte, R. Maddalena, D. H. Bennett, Environ. Sci.
Technol. 45, 9075–9083 (2011).
few experiments to date have characterized aerosol human exposure to O3, PM2.5, and air toxics. As 41. A. Lee et al., J. Geophys. Res. Atmos. 111, D17305 (2006).
formation from primary emissions of oxygenated the composition of chemical products has evolved 42. W. Li et al., Atmos. Environ. 178, 109–117 (2018).
IVOCs (42), especially those with six or more car- to remove chlorofluorocarbons to address strato- 43. Y. Wu, M. V. Johnston, Environ. Sci. Technol. 51, 4445–4451
bon atoms, and whose emissions are potentially spheric O3, shifted from solvent- to water-borne (2017).
44. N. L. Ng et al., Atmos. Chem. Phys. 7, 3909–3922 (2007).
important. formulations to mitigate tropospheric O3, and 45. A. A. Presto, M. A. Miracolo, N. M. Donahue, A. L. Robinson,
In the United States, O3 regulations do not ad- phased out toxic components (33), VCPs have Environ. Sci. Technol. 44, 2029–2034 (2010).
dress lower-volatility compounds (vapor pressure begun to contribute significantly to SOA forma- 46. I. B. Pollack et al., J. Geophys. Res. Atmos. 117, D00V05
<0.1 mm Hg at 20°C) (21), yet these can evaporate tion outdoors. Given that global mortality from (2012).
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