In the central Arctic Ocean the formation of clouds and their properties are sensitive to the availability of cloud condensation nuclei (CCN). The vapors responsible for new particle formation (NPF), ...potentially leading to CCN, have remained unidentified since the first aerosol measurements in 1991. Here, we report that all the observed NPF events from the Arctic Ocean 2018 expedition are driven by iodic acid with little contribution from sulfuric acid. Iodic acid largely explains the growth of ultrafine particles (UFP) in most events. The iodic acid concentration increases significantly from summer towards autumn, possibly linked to the ocean freeze-up and a seasonal rise in ozone. This leads to a one order of magnitude higher UFP concentration in autumn. Measurements of cloud residuals suggest that particles smaller than 30 nm in diameter can activate as CCN. Therefore, iodine NPF has the potential to influence cloud properties over the Arctic Ocean.
Particulate matter is a component of ambient air pollution that has been linked to millions of annual premature deaths globally
. Assessments of the chronic and acute effects of particulate matter on ...human health tend to be based on mass concentration, with particle size and composition also thought to play a part
. Oxidative potential has been suggested to be one of the many possible drivers of the acute health effects of particulate matter, but the link remains uncertain
. Studies investigating the particulate-matter components that manifest an oxidative activity have yielded conflicting results
. In consequence, there is still much to be learned about the sources of particulate matter that may control the oxidative potential concentration
. Here we use field observations and air-quality modelling to quantify the major primary and secondary sources of particulate matter and of oxidative potential in Europe. We find that secondary inorganic components, crustal material and secondary biogenic organic aerosols control the mass concentration of particulate matter. By contrast, oxidative potential concentration is associated mostly with anthropogenic sources, in particular with fine-mode secondary organic aerosols largely from residential biomass burning and coarse-mode metals from vehicular non-exhaust emissions. Our results suggest that mitigation strategies aimed at reducing the mass concentrations of particulate matter alone may not reduce the oxidative potential concentration. If the oxidative potential can be linked to major health impacts, it may be more effective to control specific sources of particulate matter rather than overall particulate mass.
Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and ...trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.
Recent epidemiological evidence support the hypothesis that health effects from inhalation of air particles are governed by more than just particle mass, since specific chemical components have been ...identified as important contributors to mortality and hospitality admissions.
We studied the chemical composition and the oxidative potential (OP) of total suspended particle (TSP) samples from Milan at two sites with different traffic loads: a site in the low emission zone (LEZ) and a traffic site (TR) outside. Two a-cellular assays; dithiothreitol (OPDTT) and 2′,7' dichlorofluorescin (OPDCFH) were used to characterize the OP of the soluble fraction of particles.
TSP samples from LEZ showed significantly lower concentrations of traffic-related chemical components compared to TR. The decrease in the concentrations from TR to LEZ was maximum for EC, with a LEZ/TR ratio of 0.64 (±0.18), and a significant reduction (p < 0.01) was also observed for PAHs (LEZ/TR = 0.73 ± 0.16), elements (Mn, Cu, Zn, Cd, Pb: LEZ/TR ranged between 0.64 and 0.82), OC (LEZ/TR = 0.85 ± 0.12) and NH4+ (LEZ/TR = 0.92 ± 0.07).
OP measures, expressed as OP/m3 or OP/mg, were comparable between sites both for OPDTT and OPDCFH, thus not showing any significant impact of local traffic on OP values at sites. OPDTT and OPDCFH showed contrasting seasonal and daily trends, indicating that the two a-cellular assays gave complementary information on the OP of particles in Milan. The two OP assays resulted to be sensitive to different chemical properties of PM samples. OPDTT correlated positively only with Global Radiation (Spearman's rs = 0.38, p < 0.05), which could be considered as a proxy for high concentrations of secondary oxidizing organics, while OPDCFH was related to various PM chemical species, mainly correlated with total mass (rs = 0.65; p < 0.01), elements (e.g. Zn, rs = 0.67; As, rs = 0.65; p < 0.01) and the sum of sulfate and nitrate (rs = 0.63; p < 0.01), a proxy for secondary aerosol.
•Chemical speciation and OP of urban PM in two sites and three seasons was measured.•Concentrations of traffic-related PM chemical species at LEZ site were lower than at TR site.•The oxidative potential (OPDTT and OPDCFH) of PM was comparable at TR and LEZ.•OP methods (DTT and DCFH) differed in respect to correlation with PM composition.•OPDTT and OPDCFH can provide complementary information about the oxidative capacity of particles.
Organic gases emitted during the flaming phase of residential wood combustion are characterized individually and by functionality using proton transfer reaction time-of-flight mass spectrometry. The ...evolution of the organic gases is monitored during photochemical aging. Primary gaseous emissions are dominated by oxygenated species (e.g., acetic acid, acetaldehyde, phenol and methanol), many of which have deleterious health effects and play an important role in atmospheric processes such as secondary organic aerosol formation and ozone production. Residential wood combustion emissions differ considerably from open biomass burning in both absolute magnitude and relative composition. Ratios of acetonitrile, a potential biomass burning marker, to CO are considerably lower ( ∼ 0.09 pptv ppbv−1) than those observed in air masses influenced by open burning ( ∼ 1–2 pptv ppbv−1), which may make differentiation from background levels difficult, even in regions heavily impacted by residential wood burning. A considerable amount of formic acid forms during aging ( ∼ 200–600 mg kg−1 at an OH exposure of (4.5–5.5) × 107 molec cm−3 h), indicating residential wood combustion can be an important local source for this acid, the quantities of which are currently underestimated in models. Phthalic anhydride, a naphthalene oxidation product, is also formed in considerable quantities with aging ( ∼ 55–75 mg kg−1 at an OH exposure of (4.5–5.5) × 107 molec cm−3 h). Although total NMOG emissions vary by up to a factor of ∼ 9 between burns, SOA formation potential does not scale with total NMOG emissions and is similar in all experiments. This study is the first thorough characterization of both primary and aged organic gases from residential wood combustion and provides a benchmark for comparison of emissions generated under different burn parameters.
New particle formation in the atmosphere is an important parameter in governing the radiative forcing of atmospheric aerosols. However, detailed nucleation mechanisms remain ambiguous, as laboratory ...data have so far not been successful in explaining atmospheric nucleation. We investigated the formation of new particles in a smog chamber simulating the photochemical formation of H₂SO₄ and organic condensable species. Nucleation occurs at H₂SO₄ concentrations similar to those found in the ambient atmosphere during nucleation events. The measured particle formation rates are proportional to the product of the concentrations of H₂SO₄ and an organic molecule. This suggests that only one H₂SO₄ molecule and one organic molecule are involved in the rate-limiting step of the observed nucleation process. Parameterizing this process in a global aerosol model results in substantially better agreement with ambient observations compared to control runs.
Aerodyne aerosol mass spectrometer (AMS) and Aerodyne aerosol chemical speciation monitor (ACSM) mass spectra are widely used to quantify organic aerosol (OA) elemental composition, oxidation state, ...and major environmental sources. The OA CO2 + fragment is among the most important measurements for such analyses. Here, we show that a non-OA CO2 + signal can arise from reactions on the particle vaporizer, ion chamber, or both, induced by thermal decomposition products of inorganic salts. In our tests (eight instruments, n = 29), ammonium nitrate (NH4NO3) causes a median CO2 + interference signal of +3.4% relative to nitrate. This interference is highly variable between instruments and with measurement history (percentiles P 10–90 = +0.4 to +10.2%). Other semi-refractory nitrate salts showed 2–10 times enhanced interference compared to that of NH4NO3, while the ammonium sulfate ((NH4)2SO4) induced interference was 3–10 times lower. Propagation of the CO2 + interference to other ions during standard AMS and ACSM data analysis affects the calculated OA mass, mass spectra, molecular oxygen-to-carbon ratio (O/C), and f 44. The resulting bias may be trivial for most ambient data sets but can be significant for aerosol with higher inorganic fractions (>50%), e.g., for low ambient temperatures, or laboratory experiments. The large variation between instruments makes it imperative to regularly quantify this effect on individual AMS and ACSM systems.
New particle formation has been estimated to produce around half of cloud‐forming particles in the present‐day atmosphere, via gas‐to‐particle conversion. Here we assess the importance of new ...particle formation (NPF) for both the present‐day and the preindustrial atmospheres. We use a global aerosol model with parametrizations of NPF from previously published CLOUD chamber experiments involving sulfuric acid, ammonia, organic molecules, and ions. We find that NPF produces around 67% of cloud condensation nuclei at 0.2% supersaturation (CCN0.2%) at the level of low clouds in the preindustrial atmosphere (estimated uncertainty range 45–84%) and 54% in the present day (estimated uncertainty range 38–66%). Concerning causes, we find that the importance of biogenic volatile organic compounds (BVOCs) in NPF and CCN formation is greater than previously thought. Removing BVOCs and hence all secondary organic aerosol from our model reduces low‐cloud‐level CCN concentrations at 0.2% supersaturation by 26% in the present‐day atmosphere and 41% in the preindustrial. Around three quarters of this reduction is due to the tiny fraction of the oxidation products of BVOCs that have sufficiently low volatility to be involved in NPF and early growth. Furthermore, we estimate that 40% of preindustrial CCN0.2% are formed via ion‐induced NPF, compared with 27% in the present day, although we caution that the ion‐induced fraction of NPF involving BVOCs is poorly measured at present. Our model suggests that the effect of changes in cosmic ray intensity on CCN is small and unlikely to be comparable to the effect of large variations in natural primary aerosol emissions.
Plain Language Summary
New particle formation in the atmosphere is the process by which gas molecules collide and stick together to form atmospheric aerosol particles. Aerosols act as seeds for cloud droplets, so the concentration of aerosols in the atmosphere affects the properties of clouds. It is important to understand how aerosols affect clouds because they reflect a lot of incoming solar radiation away from Earth's surface, so changes in cloud properties can affect the climate. Before the Industrial Revolution, aerosol concentrations were significantly lower than they are today. In this article, we show using global model simulations that new particle formation was a more important mechanism for aerosol production than it is now. We also study the importance of gases emitted by vegetation, and of atmospheric ions made by radon gas or cosmic rays, in preindustrial aerosol formation. We find that the contribution of ions and vegetation to new particle formation was also greater in the preindustrial period than it is today. However, the effect on particle formation of variations in ion concentration due to changes in the intensity of cosmic rays reaching Earth was small.
Key Points
New particle formation produces over half of CCN in the present‐day and preindustrial atmospheres
BVOCs are more important to CCN formation than previously thought
Our current ion‐induced nucleation rates imply only small changes of CCN over the solar cycle
The reversible partitioning of glyoxal was studied in simulation chamber experiments for the first time by time-resolved measurements of gas-phase and particle-phase concentrations in ...sulfate-containing aerosols. Two complementary methods for the measurement of glyoxal particle-phase concentrations are compared: (1) an offline method utilizing filter sampling of chamber aerosols followed by HPLC-MS/MS analysis and (2) positive matrix factorization (PMF) analysis of aerosol mass spectrometer (AMS) data. Ammonium sulfate (AS) and internally mixed ammonium sulfate/fulvic acid (AS/FA) seed aerosols both show an exponential increase of effective Henry’s law coefficients (K H,eff) with AS concentration (c AS, in mol kg–1 aerosol liquid water, m = molality) and sulfate ionic strength, I(SO4 2–) (m). A modified Setschenow plot confirmed that “salting-in” of glyoxal is responsible for the increased partitioning. The salting constant for glyoxal in AS is K S CHOCHO = (−0.24 ± 0.02) m –1, and found to be independent of the presence of FA. The reversible glyoxal uptake can be described by two distinct reservoirs for monomers and higher molecular weight species filling up at characteristic time constants. These time constants are τ1 ≈ 102 s and τ2 ≈ 104 s at c AS < 12 m, and about 1–2 orders of magnitude slower at higher c AS, suggesting that glyoxal uptake is kinetically limited at high salt concentrations.
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