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Production and Measurement of Organic Particulate Matter in a Flow Tube Reactor

Organic particulate matter (PM) is increasingly recognized as important to the Earth's climate system as well as public health in urban regions, and the ...

Harvard University

The complex refractive indices of three different types of secondary organic material (SOM) were obtained for 220 to 1200 nm using a variable angle spectroscopic ellipsometer. Aerosol particles were produced in a flow tube reactor by ozonolysis of volatile organic compounds, including the monoterpenes α-pinene and limonene and the aromatic catechol (benzene-1,2-diol). Optically reflective thin films of SOM were grown by electrostatic precipitation of the aerosol particles onto silicon substrates. The ellipsometry analysis showed that both the real and imaginary components of the refractive indices decreased with increasing wavelength. The real part n(λ) could be parametrized by the three-term form of Cauchy's equation, as follows: n(λ) = B + C/λ(2) + D/λ(4) where λ is the wavelength and B, C, and D are fitting parameters. The real refractive indices of the three SOMs ranged from 1.53 to 1.58, 1.49-1.52, and 1.48-1.50 at 310, 550, and 1000 nm, respectively. The catechol-derived SOM absorbed light in the ultraviolet (UV) range. By comparison, the UV absorption of the monoterpene-derived SOMs was negligible. On the basis of the measured refractive indices, optical properties were modeled for a typical atmospheric particle population. The results suggest that the wavelength dependence of the refractive indices can vary the Angstrom exponent by up to 0.1 across the range 310 to 550 nm. The modeled single-scattering albedo can likewise vary from 0.97 to 0.85 at 310 nm (UV-B). Variability in the optical properties of different types of SOMs can imply important differences in the relative effects of atmospheric particles on tropospheric photochemistry, as well as possible inaccuracies in some satellite-retrieved properties such as optical depth and mode diameter. 

Complex refractive indices of thin films of secondary organic materials by spectroscopic ellipsometry from 220 to 1200 nm.

The reactivity of secondary organic material (SOM) of variable viscosity, ranging from nonliquid to liquid physical states, was studied. The SOM, produced in aerosol form from terpenoid and aromatic precursor species, was reacted with ammonia at variable relative humidity (RH). The ammonium-to-organic mass ratio (MNH4+/MOrg) increased monotonically from <5% RH to a limiting value at a threshold RH, implicating a transition from particle reactivity limited by diffusion at low RH to one limited by other factors at higher RH. For the studied size distributions and reaction times, the transition corresponded to a diffusivity above 10-17.5 ± 0.5 m2 s-1. The threshold RH values for the transition were <5% RH for isoprene-derived SOM, 35-45% RH for SOM derived from α-pinene, toluene, m-xylene, and 1,3,5-trimethylbenzene, and >90% for β-caryophyllene-derived SOM. The transition RH for reactivity differed in all cases from the transition RH of a nonliquid to a liquid state. For instance, for α-pinene-derived SOM the transition for chemical reactivity of 35-45% RH can be compared to the nonliquid to liquid transition of 65-90% RH. These differences imply that chemical transport models of atmospheric chemistry should not use the SOM liquid to nonliquid phase transition as one-to-one surrogates of SOM reactivity.

Chemical Reactivity and Liquid/Nonliquid States of Secondary Organic Material.

Rapid buildup of greenhouse gases is expected to increase the Earth surface mean temperature, with unclear effects on temperature variability. This adds urgency to better understand the direct effects of the changing climate on human health. However, the effects of prolonged exposures to temperatures, which are important for understanding the public health burden, are unclear. Here we demonstrate that long-term survival was significantly associated with both seasonal mean values and standard deviations (SDs) of temperature among the Medicare population (aged 65+) in New England, and break that down into long-term contrasts between ZIP codes and annual anomalies. A rise in summer mean temperature of 1 °C was associated with 1.0% higher death rate whereas an increase in winter mean temperature corresponded to 0.6% lower mortality. Increases in temperature SDs for both summer and winter were harmful. The increased mortality in warmer summers was entirely due to anomalies, while it was long term average differences in summer SD across ZIP codes that drove the increased risk. For future climate scenarios, seasonal mean temperatures may in part account for the public health burden, but excess public health risk of climate change may also stem from changes of within season temperature variability.

Impacts of Temperature and its Variability on Mortality in New England.

Accurate estimates of spatio-temporal resolved near-surface air temperature (Ta) are crucial for environmental epidemiological studies. However, values of Ta are conventionally obtained from weather stations, which have limited spatial coverage. Satellite surface temperature (Ts) measurements offer the possibility of local exposure estimates across large domains. The Southeastern United States has different climatic conditions, more small water bodies and wetlands, and greater humidity in contrast to other regions, which add to the challenge of modeling air temperature. In this study, we incorporated satellite Ts to estimate high resolution (1km×1km) daily Ta across the southeastern USA for 2000-2014. We calibrated Ts-Ta measurements using mixed linear models, land use, and separate slopes for each day. A high out-of-sample cross-validated R(2) of 0.952 indicated excellent model performance. When satellite Ts were unavailable, linear regression on nearby monitors and spatio-temporal smoothing was used to estimate Ta. The daily Ta estimations were compared to the NASA's Modern-Era Retrospective Analysis for Research and Applications (MERRA) model. A good agreement with an R(2) of 0.969 and a mean squared prediction error (RMSPE) of 1.376°C was achieved. Our results demonstrate that Ta can be reliably predicted using this Ts-based prediction model, even in a large geographical area with topography and weather patterns varying considerably. 

Estimating daily air temperature across the Southeastern United States using high-resolution satellite data: A statistical modeling study.

Climate change may affect human health, particularly for elderly individuals who are vulnerable to temperature changes. While many studies have investigated the acute effects of heat, only a few have dealt with the chronic ones. We have examined the effects of seasonal temperatures on survival of the elderly in the Southeastern USA, where a large fraction of subpopulation resides. We found that both seasonal mean temperature and its standard deviation (SD) affected long-term survival among the 13 million Medicare beneficiaries (aged 65+) in this region during 2000-2013. A 1 °C increase in summer mean temperature corresponded to an increase of 2.5% in death rate. Whereas, 1 °C increase in winter mean temperature was associated with a decrease of 1.5%. Increases in seasonal temperature SD also influence mortality. We decomposed seasonal mean temperature and its temperature SD into long-term geographic contrasts between ZIP codes and annual anomalies within ZIP code. Effect modifications by different subgroups were also examined to find out whether certain individuals are more vulnerable. Our findings will be critical to future efforts assessing health risks related to the future climate change.

Chronic effects of temperature on mortality in the Southeastern USA using satellite-based exposure metrics.

The energy flows in Earth's natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representative of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic compared with biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate  for the biogenic case is at least 10 times greater than that of the anthropogenic case. These differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PM in Earth's atmosphere.

Lability of secondary organic particulate matter.

Little is known about what factors modify the effect of long-term exposure to PM2.5 on mortality, in part because in most previous studies certain groups such as rural residents and individuals with lower socioeconomic status (SES) are under-represented.

Long-term Exposure to PM2.5 and Mortality Among Older Adults in the Southeastern US.

The formation of atmospheric cloud droplets due to secondary organic aerosol (SOA) particles is important for quantifying the Earth's radiative balance under future, possibly warmer, climates, yet is only poorly understood. While cloud activation may be parametrized using the surface tension depression that coincides with surfactant partitioning to the gas-droplet interface, the extent to which cloud activation is influenced by both the chemical structure and reactivity of the individual molecules comprising this surfactant pool is largely unknown. We report herein considerable differences in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from α-pinene and β-caryophyllene, the most abundant of the monoterpenes and sesquiterpenes, respectively, that are emitted over the planet's vast forest ecosystems. Oxidation products derived from β-caryophyllene were found to exhibit significantly higher surface activity than those prepared from α-pinene, with the critical supersaturation required for cloud droplet activation reduced by 50% for β-caryophyllene aldehyde at 1 mM. These considerable reductions in the critical supersaturation were found to coincide with free energies of adsorption that exceed ∼25 kJ/mol, or just one hydrogen bond equivalent, depending on the ammonium sulfate and oxidation product concentration in the solution. Additional experiments showed that aldehyde-containing oxidation products exist in equilibrium with hydrated forms in aqueous solution, which may modulate their bulk solubility and surface activity. Equilibration time scales on the order of 10 to 10 s calculated for micrometer-sized aerosol particles indicate instantaneous surface tension depression in the activation processes leading to cloud formation in the atmosphere. Our findings highlight the underlying importance of molecular structure and reactivity when considering cloud condensation activity in the presence of SOA particles.

Cloud Activation Potentials for Atmospheric α-Pinene and β-Caryophyllene Ozonolysis Products.

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet-visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index  across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The  value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance.

Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter.

The uptake of medium-sized levoglucosan and 2,4-dinitrophenol to organic particles produced by α-pinene ozonolysis and to ammonium sulfate particles was studied from 10% to >95% relative humidity (RH). For aqueous sulfate particles, the water-normalized gas-particle partitioning coefficient of levoglucosan decreased from (1.0 ± 0.1) × 10 to (0.2 ± 0.1) × 10 (ng μg)/(ng m) from 40% to >95% RH, suggestive of a salting-in mechanism between levoglucosan and ionic ammonium sulfate solutions. For the organic particles, the levoglucosan partitioning coefficient increased from 10% to 40% RH and became invariant at (2.0 ± 0.4) × 10 (ng μg)/(ng m) above 40% RH. A kinetic limitation on uptake below 40% RH was implied, compared to a thermodynamic regime above 40% RH. The estimated diffusivity was 10 m s at 40% RH. By comparison, the uptake of 2,4-dinitrophenol onto the organic particles was below detection limit, implying an upper limit on the partitioning coefficient of 6.8 × 10 (ng μg)/(ng m) at 80% RH. The results highlight that the molecular uptake of gases onto particles can be regulated by both kinetic and thermodynamic factors, either of which can limit the uptake of medium-sized organic molecules by atmospherically relevant particles.

Influence of Particle Physical State on the Uptake of Medium-Sized Organic Molecules.

Hygroscopic growth and cloud condensation nuclei activation are key processes for accurately modeling the climate impacts of organic particulate matter. Nevertheless, the microphysical mechanisms of these processes remain unresolved. Here we report complex thermodynamic behaviors, including humidity-dependent hygroscopicity, diameter-dependent cloud condensation nuclei activity, and liquid-liquid phase separation in the laboratory for biogenically derived secondary organic material representative of similar atmospheric organic particulate matter. These behaviors can be explained by the non-ideal mixing of water with hydrophobic and hydrophilic organic components. The non-ideality-driven liquid-liquid phase separation further enhances water uptake and induces lowered surface tension at high relative humidity, which result in a lower barrier to cloud condensation nuclei activation. By comparison, secondary organic material representing anthropogenic sources does not exhibit complex thermodynamic behavior. The combined results highlight the importance of detailed thermodynamic representations of the hygroscopicity and cloud condensation nuclei activity in models of the Earth's climate system.

Pengfei Liu

School of Engineering and Applied Sciences

Harvard University

Production and Measurement of Organic Particulate Matter in a Flow Tube Reactor

Pengfei Liu

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}School of Engineering and Applied Sciences

Harvard University

Production and Measurement of Organic Particulate Matter in a Flow Tube Reactor

School of Engineering and Applied Sciences