5. Crama, Y. et al.

(2016) A brand-new cheating attempt: a

case of usurped identity. 4OR-Q. J. Oper. Res. 14, 333–336
6. Biagioli, M. (2016) Watch out for cheats in citation game. (SO 2), and fine atmospheric particulate
Nature 535, 201
Special Issue: Big Questions in Chemistry Bangladesh since 2010. High annual
Science & Society
Addressing the Global
Air Pollution Crisis:
Chemistry’s Role
V. Faye McNeill*
Air pollution has reached danger-
ous levels in many locations where
environmental policies have not
kept pace with rapid development.
Poor air quality results from
anthropogenic and natural emis-
sions, and their chemical process-
ing in the atmosphere. Chemistry
is key to diagnosing pollution sour-
ces, designing efficient control
strategies, and developing pollu-
tion-reduction technologies.
Air Pollution Crisis
Over 90% of the world’s population lives
in areas where ambient air pollution
exceeds World Health Organization
(WHO) guidelines [1]. Concentrations of
harmful air pollutants, such as nitrogen
dioxide (NO2), ozone (O3), sulfur dioxide exposure was estimated to be responsi-
ble for 4.2 million premature deaths in
matter (PM2.5), are increasing in many 2015 (with 1.09 and 1.11 million deaths
of the world’s most populous countries in India and China, respectively) [1]. PM2.5
(Table 1). PM2.5 has increased particu- exposure decreases average life expec-
larly rapidly for India, Pakistan, and tancy by 1.5 years/person in India and
roughly 1.3 years/person in China, North
average PM2.5 levels are punctuated in Africa, and the Middle East [2]. Although
some locations, including capital cities PM2.5 is typically measured and reported
Delhi and Beijing, by extreme air pollution in terms of mass only, it is clear that the
events lasting several days (Figure 1). chemical composition of PM2.5 affects its
Hospital admissions spike during these health impacts. Many common aerosol
extreme events, and schools, airports, components are cytotoxic or carcino-
and businesses may shut down due to genic, such as polycyclic aromatic hydro-
the health hazard and decreased carbons and their oxidation products.
visibility. Oxygenated organics and trace metals
have been connected to oxidative stress
PM2.5 response in the lungs [3]. Toxicity of
PM2.5 refers to the mass of atmospheric organic aerosol particles increases as
aerosol particles with diameters less they undergo oxidative aging in the atmo-
than or equal to 2.5 mm. Particles sphere [4].
smaller than 2.5 mm penetrate deeply
into the lungs upon inhalation, while Sources and Chemical
larger particles are trapped in the upper Processing of Air Pollution
respiratory tract. Measurements of Air pollutants originate from a wide vari-
PM10 (mass of particles 10 mm or ety of human activities and natural pro-
smaller) and total suspended particulate cesses. The language used to discuss
matter (TSP) include PM2.5, but PM10 PM2.5 sources often gives the impression
and TSP mass are dominated by large that each particle can be traced to a
particles, so information on small par- particular polluter. However, air quality
ticles is often lost. is a complex, nonlinear response to a
combination of anthropogenic emissions
Exposure to elevated levels of PM2.5 leads and natural factors. Some processes,
to acute and chronic diseases, especially such as combustion (e.g., for energy,
respiratory and cardiovascular disease transportation, agricultural burning, wild-
and premature death. Globally, PM2.5 fires, or cooking) result in direct emission

Table 1. Four Major Air Pollutants, Their Average Annual Concentrations in Four Locations, and WHO Guideline Levels. Data are from local ground-
based monitoring stations in 2017, accessed via the OpenAQ platform, except as noted. WHO guideline levels are for the mean annual
concentration, except as noted.
Pollutant Annual average (mg/m3) WHO guideline (mg/m3)

Detroit, USA London, UK Beijing, China Delhi, India

a
NO2 16.4 38 50.0 46.6 40

O3 63.5 34.5 90.1a 36.2 100b

PM2.5 8.7 13.3 62.0 126.3 10

SO2 7.6 4.8 9.4a 16.3 20c

a
Average data for autumn 2016 to autumn 2017 [14].
b
Eight-hour mean.
c
Twenty-four-hour mean.

Trends in Chemistry, April 2019, Vol. 1, No. 1 5

 Emissions
Figure 1. Air Pollution Origins. Air pollution results from a combination of natural and human emissions, meteorology, and multiphase atmospheric chemical
processing. PM2.5, Fine atmospheric particulate matter.
of PM2.5 into the atmosphere. However,
in many locations, including Delhi [5] and
Beijing [6], a major portion of particulate
matter is formed via chemical reactions
and physical transformations of precur-
sor gases. Aerosols formed in this way
are referred to as secondary particles.
For example, sulfate, a common particle
component, is formed via the oxidative
processing of SO2 gas in atmospheric
water (i.e., cloud droplets or hygroscopic
aerosols under humid conditions). It has
been proposed that NO2 participates in
the multiphase conversion of SO2 into
sulfate under the extremely polluted con-
ditions encountered during winter haze
events in Beijing [7,8]. If true, this would
have major environmental policy implica-
tions, suggesting that sulfate formation
could be reduced by controlling NO2
emissions (i.e., from transportation)
rather than SO2 emissions alone. How-
ever, the proposed reaction requires
basic conditions, which are thermody-
namically unfavorable in atmospheric
aerosols [9]. Another secondary particle
type is secondary organic aerosol (SOA).
Volatile organic compounds may be oxi-
dized in the atmosphere and trans-
formed into SOA material via
multiphase processes. The organic pre-
cursors to SOA may be emitted by
6 Trends in Chemistry, April 2019, Vol. 1, No. 1
Atmospheric chemical
processing
Gas phase
Meteorology
photochemistry
900
800
MulƟphase Thermo- 700
600
chemistry dynamics 500
400
300
200
100
0
11/2/2017
vegetation or from human activities,
and the oxidative capacity of the atmo-
sphere is also influenced by both natural
and anthropogenic factors. As a result,
SOA formation is only partly controllable
[10].
Air-Quality Data Needs
Availability of air-quality data varies
widely in the areas of the world most
affected by air pollution. Monitoring
networks in China and India are
expanding rapidly, and since 2015
the Central Pollution Control Board
(CPCB) of India has begun monitoring
PM2.5 (a more useful metric than PM10
or TSP for understanding health
impacts of particulate pollution). But
most African countries, and South
Asian countries besides India, do not
have monitoring networks. Data collec-
tion by government agencies may be
supplemented by monitors operated by
other entities, such as universities and
foreign diplomatic posts. Reliable
ground-based ambient air-quality data
collection for PM 2.5, O 3, and precursor
gases such as SO2 and NO2 is essential
for diagnosing the severity and tempo-
ral trends of the air-quality problem,
quantifying exposures, and testing
models. Efforts by groups like OpenAQ
Air polluƟon
PM2.5(μg/m3)
U.S. diplomaƟc post: New Delhi
11/3/2017 11/4/2017 11/5/2017 11/6/2017
(https://www.openaq.org) to aggre-
gate and archive publicly available
ground-based measurements are use-
ful to the public, scientific community,
and policymakers, and can help raise
public awareness.
Networks of low-cost air-quality sensors
have emerged as an alternative to costly
research-grade monitors. While these
sensors generally suffer from limited
accuracy, data science techniques for
merging low-cost sensor data with
remote sensing data, models, and data
from ground-based monitors have
shown promise [11]. These devices
may be of particular value in less-devel-
oped areas with sparse ground-based
monitoring, or in circumstances where
power is limited, such as following a
natural disaster. Low-cost sensor net-
works may also provide observations
with high spatial resolution, leading to
improved exposure estimates.
Remote measurements from satellites
can provide a check for ground-based
air-quality data and models. They can
also help fill gaps where ground-based
data are unavailable. The capacity to
view air pollution in near-real time from
space also offers opportunities to raise
public awareness with powerful imag-
ery. Although the spatial resolution for
satellite data is not yet on the city level,
satellite-derived trends in individual
pollutants can be useful. Trends in
SO2 and NO 2 emissions measured by
NASA’s Aura satellite’s Ozone Monitor-
ing Instrument were recently shown to
conflict with ground-level measure-
ments of these species made by the
India’s CPCB [Bhuyan, R. (2017) So,
how polluted is India’s air, really? Live-
Mint.com, Hindustan Times (http://
www.livemint.com/Politics/
J40ovl9VMuffWmLYP4zqIO/
Contradictory-data-and-fight-against-
air-pollution-in-India.html)]. Many fac-
tors may contribute to this discrep-
ancy, but it points to the value of
satellite data as a counterpoint to
with rewards potentially realized on a Acknowledgements
timescale longer than that of a political The author acknowledges the Columbia Earth Insti-
term. This makes expensive and inef- tute and the Columbia Center for Global Energy Policy
fective ‘quick fix’ solutions, such as for support. I am also grateful to Prof. Arlene Fiore and
Dr Julia Nunes for helpful discussions.
large-scale outdoor air filters, tempting
for politicians. Air pollution crosses
political boundaries with ease, with Disclaimer Statement
emissions from one city, state, or coun- The author declares no conflict of interest.
try often affecting air quality in another.
Department of Chemical Engineering, Columbia
In addition, there are often powerful University, New York, NY 10027, USA
economic interests opposing pollution
control. Worldwide opponents of envi- *Correspondence: vfm2103@columbia.edu (V.F. McNeill).
ronmental laws raise concerns over 10.1016/j.trechm.2019.01.005
detrimental impacts on economic © 2019 Elsevier Inc. All rights reserved.
growth due to higher costs. However,
air-quality improvements can have a
positive economic impact by increas- References
ing the life span of the population and 1. Cohen, A.J. et al. (2017) Estimates and 25-year trends of
the global burden of disease attributable to ambient air
reducing health care costs. Since its pollution: an analysis of data from the Global Burden of
inception in 1970, the US Clean Air Diseases Study 2015. Lancet 389, 1907–1918

sparse ground-based measurements.
In addition to long-term data collection,
short-term intensive measurement
campaigns with advanced instrumenta-
tion for detailed chemical analysis can
provide deeper insight into the underly-
ing sources and chemistry of PM2.5.
High-resolution time-of-flight aerosol
mass spectrometry measurements in
four cities across China during winter
2013 revealed the relative contributions
of coal burning, mineral dust, transpor-
tation, and secondary sources of PM2.5
[6]. Recent measurements in Delhi and
Act has led to well-documented 2. Apte, J.S. et al. (2018) Ambient PM2.5 reduces global and
regional life expectancy. Environ. Sci. Technol. Lett. 5,
improvements in air quality. During that 546–551
same time period, the US also experi- 3. Verma, V. et al. (2015) Organic aerosols associated with
the generation of reactive oxygen species (ROS) by water-
enced substantial growth in the econ- soluble PM2.5. Environ. Sci. Technol. 49, 4646–4656
omy (GDP) and vehicle miles traveled 4. Chowdhury, P.H. et al. (2018) Exposure of lung epithelial
[13]. cells to photochemically aged secondary organic aerosol
shows increased toxic effects. Environ. Sci. Technol. Lett
5, 424–430
The political challenges of air-quality 5. Gani, S. et al. (2018) Submicron aerosol composition in
the world’s most polluted megacity: the Delhi Aerosol
policy development and implementa- Supersite campaign. Atmos. Chem. Phys. Discuss. Pub-
tion, coupled with the communication lished online November 15, 2018. DOI: 10.5194/acp-
2018-1066
divide between technical specialists
6. Huang, R.-J. et al. (2014) High secondary aerosol contri-
and policy makers, can result in science bution to particulate pollution during haze events in China.
being sidelined during the planning and Nature 514, 218–222
7. Cheng, Y. et al. (2016) Reactive nitrogen chemistry in
decision-making process. However, aerosol water as a source of sulfate during haze events
science, and chemistry in particular, is in China. Sci. Adv. 2, e1601530

outside Kathmandu reveal signatures in
the aerosol chemical composition that
are common to both locations but not
observed elsewhere [5,12]. High partic-
ulate chloride levels are observed in the
early morning hours, which may be
linked to waste burning or industrial
sources.
Policy Challenge
Clearing the air requires a combination
of political will and technical insight.
Controlling pollution sources often
requires politically unpopular actions,
essential for understanding the sources
and formation pathways of PM2.5. With-
out this understanding, it is impossible
to design effective and economically
efficient air pollution control strategies
for the protection of public health.
Chemistry and chemical engineering
are also key to technological develop-
ments such as pollution control tech-
nology, renewable energy, and
advanced battery technology, that will
enable societies to address their envi-
ronmental quality and climate goals
simultaneously with continued eco-
nomic growth and development.
8. Wang, G. et al. (2016) Persistent sulfate formation from
London fog to Chinese haze. Proc. Natl. Acad. Sci. U. S. A
113, 13630–13635
9. Guo, H. et al. (2017) High levels of ammonia do not raise
fine particle pH sufficiently to yield nitrogen oxide-domi-
nated sulfate production. Sci. Rep. 7, 12109
10. Carlton, A.G. et al. (2010) To what extent can biogenic
SOA be controlled? Environ. Sci. Technol. 44, 3376–3380
11. Zimmerman, N. (2018) A machine learning calibration
model using random forests to improve sensor perfor-
mance for lower-cost air quality monitoring. Atmos. Meas.
Tech. 11, 291–313
12. Jayarathne, T. et al. (2018) Nepal Ambient Monitoring and
Source Testing Experiment (NAMaSTE): emissions of par-
ticulate matter from wood- and dung-fueled cooking fires,
garbage and crop residue burning, brick kilns, and other
sources. Atmos. Chem. Phys. 18, 2259–2286
13. US EPA Office of Air and Radiation (2011) The Benefits and
Costs of the Clean Air Act from 1990 to 2020, Final Report,
Revision A, April 2011, US Environmental Protection
Agency

Trends in Chemistry, April 2019, Vol. 1, No. 1 7

14. Chen, L. et al. (2018) Assessing air-quality in Beijing-Tian-
jin-Hebei region: the method and mixed tales of PM2.5 and
O3. Atmos. Environ. 193, 290–301
Special Issue: Big Questions in Chemistry
From Thermochemical to
Electrochemical Synthesis
The need to decouple industrial pro-
cesses from fossil fuel-derived energy
sources only grows more urgent with
the rapid increase in global energy
chemical processes. Currently, only a
small fraction of chemical manufacturing
is electrochemical in nature, with most of
the volume centered in chloro-alkali and
aluminum production. Although organic
electrosynthetic processes are signifi-

Science & Society demand and multiple global initiatives to

mitigate climate change. Chemical
Organic manufacturing, already responsible for
26% of the world energy demand [1], is
Electrosynthesis for highly energy intensive, requiring large
Sustainable Chemical amounts of fossil fuel-supplied heat to
drive thermochemical processes. How-
Manufacturing ever, electrochemical processes have
emerged as a promising platform for
Daniela E. Blanco1 and
the integration of renewable energy sour-
Miguel A. Modestino1,*
ces in the chemical industry. Electro-
chemical processes can directly
Renewable-electricity-powered
interconvert clean electricity into chemical
electrosynthetic processes for the energy, resulting in a vast reduction of the
production of high-value organic CO2 emissions that emanate from current
chemicals can contribute to the thermochemical processes. Additionally,
reduction of the chemical indus- electrochemical manufacturing of organic
try’s carbon footprint. This Science molecules represents an undeniable
& Society article discusses current opportunity for improved efficiency and
challenges and opportunities for access to untapped reaction pathways
the deployment of these pro- with potential for new industrial chemical
cesses, including pathways to transformations.
enhance reactant solubility, elec-
Electrochemical processes hold signifi-
trolyte stability, and the dynamic
cant promise in the chemical industry,
operation of electrochemical
especially since redox reactions consti-
reactors. tute a large fraction of the highest-volume
cantly smaller in volume, their implemen-
tation could result in sustainability
improvements for the production of more
than 75% of chemical products [85_TD$IF][2,3]). The
deployment of such processes repre-
sents a clear opportunity to support the
development of an emission-free chemi-
cal industry. Currently, however, three
major challenges must be addressed to
realize organic electrosynthetic pro-
cesses at scale: (i) the limited electro-
chemical stability of aqueous
electrolytes; (ii) the low solubility of reac-
tants in these electrolytes; and (iii) the
presence of multiple reaction pathways
that lead to undesired by-products.
Challenges with Electrosynthetic
Chemical Manufacturing
Widening the electrochemical stability
window of the electrolyte is a challenge
long acknowledged by the scientific
community, since inexpensive aqueous
electrolytes are limited in stability by the
onset potentials of the water reduction
and oxidation reactions (Box 1). One
promising alternative is the use of ionic

Box 1. Key Challenges of Organic Electrosynthesis

Limited Stability of Electrolytes
Scalable electrochemical processes rely on inexpensive aqueous electrolytes. These electrolytes have a limited electrochemical stability window dictated by the
onset potential of the water oxidation or reduction reaction: the hydrogen evolution reaction (HER) in the cathode and the oxygen evolution reaction (OER) in the
anode. If the desired transformation requires reductive potentials below or oxidative potentials above those of water, the organic reaction will face competition from
the HER and the OER, respectively, lowering the energy conversion efficiency.

Low Reactant Solubility

Most organic species suffer from low solubility in aqueous electrolytes. Under steady-state operation, the diffusion rate of reactants from the bulk electrolyte to the
electrode needs to match their consumption rate at reactive sites. Low concentrations of organic reactants in the bulk electrolyte lead to slow diffusion rates, resulting
in limitations on the maximum attainable production rate. Furthermore, high electrochemical reaction rates lower the local concentration of organic species in the
near-electrode region. This change in reactant local concentration affects reaction selectivity and the distribution of various electrosynthetic products.

Selectivity Over Reaction Pathways

Organic electrosynthesis is often characterized by the presence of several reaction pathways, leading to desired products or undesired by-products. The operation of
electrosynthetic reactors with fluctuating renewable sources can impose varying reaction potentials, which trigger strong variations in reaction pathways, affecting
selectivity and production rates.

8 Trends in Chemistry, April 2019, Vol. 1, No. 1