Aerosol Indirect Effects in Marine Stratocumulus: The Importance of Explicitly Predicting Cloud Droplet Activation

Bulatovic, I; Ekman, AML; Savre, J; Riipinen, I; Leck, C
2019 | Geophys Res Lett | 46 (6) (3473-3481)
Climate models generally simulate a unidirectional, positive liquid water path (LWP) response to increasing aerosol number concentration. However, satellite observations and large-eddy simulations show that the LWP may either increase or decrease with increasing aerosol concentration, influencing the overall magnitude of the aerosol indirect effect (AIE). We use large-eddy simulation to investigate the LWP response of a marine stratocumulus cloud and its dependence on different parameterizations for obtaining cloud droplet number concentration (CDNC). The simulations confirm that the LWP response is not always positiveregardless of CDNC treatment. However, the AIE simulated with the model version with prescribed CDNC is almost 3 times larger compared to the version with prognostic CDNC. The reason is that the CDNC in the prognostic scheme varies in time due to supersaturation fluctuations, collection, and other microphysical processes. A substantial spread in simulated AIE may thus arise simply due to the CDNC treatment. Plain Language Summary Our poor understanding of aerosol-cloud-radiation interactions (aerosol indirect effects) results in a major uncertainty in estimates of anthropogenic aerosol forcing. In climate models, the cloud water response to an increased aerosol number concentration may be especially uncertain as models simplify, or do not account for, processes that affect the cloud droplet number concentration and the total amount of cloud water. In this study, we employ large-eddy simulation to explore how different model descriptions for obtaining the number concentration of cloud droplets influences the cloud water response of a marine stratocumulus cloud and thus the simulated aerosol indirect effect. Our simulations show a qualitatively similar cloud water response regardless of model description: the total amount of cloud water increases first and then decreases with increasing aerosol concentration. However, the simulated aerosol indirect effect is almost 3 times as large when the number concentration of cloud droplets is prescribed compared to when it is dependent on the calculated supersaturation and other microphysical processes such as collisions between cloud droplets. Our findings show that a relatively simple difference in the treatment of the number concentration of cloud droplets in climate models may result in a significant spread in the simulated aerosol indirect effect.

Role of base strength, cluster structure and charge in sulfuric-acid-driven particle formation

Myllys, N.; Kubečka, J.; Besel, V.; Alfaouri, D.; Olenius, T.; Smith, J. N.; Passananti, M.;
2019 | Atmos. Chem. Phys. | 19 (9753-9768)

Solvent-Assisted Paper Spray Ionization Mass Spectrometry (SAPSI-MS) for the Analysis of Biomolecules and Biofluids

Riboni, N; Quaranta, A; Motwani, HV; Osterlund, N; Graslund, A; Bianchi, F; Ilag, LL
2019 | Sci Rep | 9
alzheimers-disease , ambient ionization , amyloid-beta peptide , human serum-albumin , proteins
Paper Spray Ionization (PSI) is commonly applied for the analysis of small molecules, including drugs, metabolites, and pesticides in biological fluids, due to its high versatility, simplicity, and low costs. In this study, a new setup called Solvent Assisted Paper Spray Ionization (SAPSI), able to increase data acquisition time, signal stability, and repeatability, is proposed to overcome common PSI drawbacks. The setup relies on an integrated solution to provide ionization potential and constant solvent flow to the paper tip. Specifically, the ion source was connected to the instrument fluidics along with the voltage supply systems, ensuring a close control over the ionization conditions. SAPSI was successfully applied for the analysis of different classes of biomolecules: amyloidogenic peptides, proteins, and N-glycans. The prolonged analysis time allowed real-time monitoring of processes taking places on the paper tip, such as amyloid peptides aggregation and disaggregation phenomena. The enhanced signal stability allowed to discriminate protein species characterized by different post translational modifications and adducts with electrophilic compounds, both in aqueous solutions and in biofluids, such as serum and cerebrospinal fluid, without any sample pretreatment. In the next future, application to clinical relevant modifications, could lead to the development of quick and cost-effective diagnostic tools.

Visualizing reaction and diffusion in xanthan gum aerosol particles exposed to ozone

Alpert, PA; Arroyo, PC; Dou, J; Krieger, UK; Steimer, SS; Forster, JD; Ditas, F; Pohlker, C; Rossignol, S; Passananti, M; Perrier, S; George, C; Shiraiwa, M; Berkemeier, T; Watts, B; Ammann, M
2019 | Phys Chem Chem Phys | 21 (37) (20613-20627)
atmospheric aerosols , cloud surface-chemistry , fe(ii) oxidation , heterogeneous oh oxidation , multiphase chemical-kinetics , phase state , relative-humidity , secondary organic aerosol , shikimic acid ozonolysis , spectromicroscopy , temperature-dependence
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Atmospheric aerosol particles with a high viscosity may become inhomogeneously mixed during chemical processing. Models have predicted gradients in condensed phase reactant concentration throughout particles as the result of diffusion and chemical reaction limitations, termed chemical gradients. However, these have never been directly observed for atmospherically relevant particle diameters. We investigated the reaction between ozone and aerosol particles composed of xanthan gum and FeCl2 and observed the in situ chemical reaction that oxidized Fe2+ to Fe3+ using X-ray spectromicroscopy. Iron oxidation state of particles as small as 0.2 µm in diameter were imaged over time with a spatial resolution of tens of nanometers. We found that the loss off Fe2+ accelerated with increasing ozone concentration and relative humidity, RH. Concentric 2-D column integrated profiles of the Fe2+ fraction, ɑ, out of the total iron were derived and demonstrated that particle surfaces became oxidized while particle cores remained unreacted at RH = 0-20%. At higher RH, chemical gradients evolved over time, extended deeper from the particle surface, and Fe2+ became more homogeneously distributed. We used the kinetic multi-layer model for aerosol surface and bulk chemistry (KM-SUB) to simulate ozone reaction constrained with our observations and inferred key parameters as a function of RH including Henry's Law constant for ozone, HO3, and diffusion coefficients for ozone and iron, DO3 and DFe, respectively. We found that HO3 is higher in our xanthan gum/FeCl2 particles than for water and increases when RH decreased from about 80% to dry conditions. This coincided with a decrease in both DO3 and DFe. In order to reproduce observed chemical gradients, our model predicted that ozone could not be present further than a few nanometers from a particle surface indicating near surface reactions were driving changes in iron oxidation state. However, the observed chemical gradients in ɑ observed over hundreds of nanometers must have been the result of iron transport from the particle interior to the surface where ozone oxidation occurred. In the context of our results, we examine the applicability of the reacto-diffusive framework and discuss diffusion limitations for other reactive gas-aerosol systems of atmospheric importance.

Longitudinal analysis reveals early-pregnancy associations between perfluoroalkyl sulfonates and thyroid hormone status in a Canadian prospective birth cohort

Reardon, AJF; Moez, EK; Dinu, I; Goruk, S; Field, CJ; Kinniburgh, DW; MacDonald, AM; Martin, JW
2019 | Environ Int | 129 (389-399)
child-development , free-thyroxine , longitudinal study design , neuropsychological development , perfluorinated acid isomers , perfluoroalkyl acids , perfluoroalkyl carboxylates , perfluoroalkyl sulfonates , perfluorooctane sulfonate , peroxidase antibodies , polyfluoroalkyl substances , pregnancy , serum concentrations , sprague-dawley rats , subclinical hypothyroidism , thyroid hormones
Serum perfluoroalkyl acids (PFAAs) have been linked to disruption of maternal thyroid hormone homeostasis, but results have varied between studies which we hypothesized was due to timing of the thyroid hormone measurements, variability in PFAA isomer patterns, or presence of other stressors. In a longitudinal study design, we investigated the time-dependency of associations between PFAA isomers and thyroid hormones during pregnancy and post-partum while considering thyroid peroxidase antibody (TPOAb) status and mercury (Hg) co-exposure. In participants of a prospective Canadian birth cohort (n = 494), free thyroxine (FT4), free triiodothyronine (FT3), thyroid stimulating hormone (TSH) and TPOAb were quantified in maternal plasma collected in each trimester and 3-months postpartum, and 25 PFAAs (15 linear and 10 branched) and Hg were quantified in samples collected during the second trimester. Perfluorohexane sulfonate (PFHxS) and total branched isomers of perfluorooctane sulfonate (PFOS) were positively associated with TSH in mixed-effect models, with strongest associations early in gestation. Throughout pregnancy and post-partum, PFHxS was inversely associated with FT4, consistent with elevated TSH, while Hg was inversely associated with FT3. In TPOAb-positive women, negative associations were found between PFUnA and FT4, and 1m-PFOS and TSH, supporting previous studies that thyroid disorder could increase susceptibility to PFAA-mediated hormone dysregulation. Hg did not confound associations but was a significant interaction term, revealing further positive associations between PFOS isomers (Sigma 3m + 4m-PFOS) and TSH. Higher perfluoroalkyl sulfonate exposures were associated with higher TSH and/or lower FT4, strongly suggestive that PFHxS and branched PFOS isomers are risk factors for subclinical maternal hypothyroidism. Isomer-specific analysis is important in future studies, as crude measures of 'totalPFOS' masked the associations of branched isomers. A concerning result was for PFHxS which had consistent negative associations with FT4 at all time points and a positive association with TSH in early pregnancy when fetal development is most sensitive to disruption.

Improving environmental risk assessments of chemicals: Steps towards evidence-based ecotoxicology.

Martin Olwenn; Adams; Beasley; Belanger; Breton; Brock; Buonsante; Galay Burgos; Green; Guiney; Hall; Hanson M; Harris; Henry; Huggett; Junghans; Laskowski; Maack; Moermond; Panter; Pease; Poulsen; Roberts; Christina Rudén; Schlekat; Schoeters; Solomon; Staveley; Stubblefield; Sumpter; Warne; Wentsel; Wheeler; Wolff; Yamazaki; Zahner; Marlene Ågerstrand;
2019 | Environ Int | 128 (210-2017)

Letter to the Editor: Optimism for Nontarget Analysis in Environmental Chemistry

Samanipour, S; Martin, JW; Lamoree, MH; Reid, MJ; Thomas, KV
2019 | Environ. Sci. Technol. | 53 (10) (5529-5530)

Biomass burning and urban emission impacts in the Andes Cordillera region based on in situ measurements from the Chacaltaya observatory, Bolivia (5240 m a.s.l.)

Chauvigne, A; Aliaga, D; Sellegri, K; Montoux, N; Krejci, R; Mocnik, G; Moreno, I; Muler, T; Pandolfi, M; Velarde, F; Weinhold, K; Ginot, P; Wiedensohler, A; Andrade, M; Laj, P
2019 | Atmos. Chem. Phys. | 19 (23) (14805-14824)
absorption-coefficient , aerosol optical-properties , aethalometer , amazon basin , black carbon , free troposphere , high-altitude station , light-absorption , saharan dust , transport
This study documents and analyses a 4-year continuous record of aerosol optical properties measured at the Global Atmosphere Watch (GAW) station of Chacaltaya (CHC; 5240 m a.s.l.), in Bolivia. Records of particle light scattering and particle light absorption coefficients are used to investigate how the high Andean Cordillera is affected by both long-range transport and by the fast-growing agglomeration of La Paz-El Alto, located approximately 20 km away and 1.5 km below the sampling site. The extended multiyear record allows us to study the properties of aerosol particles for different air mass types, during wet and dry seasons, also covering periods when the site was affected by biomass burning in the Bolivian lowlands and the Amazon Basin. The absorption, scattering, and extinction coefficients (median annual values of 0.74, 12.14, and 12.96 Mm(-1) respectively) show a clear seasonal variation with low values during the wet season (0.57, 7.94, and 8.68 Mm(-1) respectively) and higher values during the dry season (0.80, 11.23, and 14.51 Mm(-1) respectively). The record is driven by variability at both seasonal and diurnal scales. At a diurnal scale, all records of intensive and extensive aerosol properties show a pronounced variation (daytime maximum, night-time minimum), as a result of the dynamic and convective effects. The particle light absorption, scattering, and extinction coefficients are on average 1.94, 1.49, and 1.55 times higher respectively in the turbulent thermally driven conditions than the more stable conditions, due to more efficient transport from the boundary layer. Retrieved intensive optical properties are significantly different from one season to the other, reflecting the changing aerosol emission sources of aerosol at a larger scale. Using the wavelength dependence of aerosol particle optical properties, we discriminated between contributions from natural (mainly mineral dust) and anthropogenic (mainly biomass burning and urban transport or industries) emissions according to seasons and local circulation. The main sources influencing measurements at CHC are from the urban area of La Paz-El Alto in the Altiplano and from regional biomass burning in the Amazon Basin. Results show a 28 % to 80 % increase in the extinction coefficients during the biomass burning season with respect to the dry season, which is observed in both tropospheric dynamic conditions. From this analysis, long-term observations at CHC provide the first direct evidence of the impact of biomass burning emissions of the Amazon Basin and urban emissions from the La Paz area on atmospheric optical properties at a remote site all the way to the free troposphere.

Neurodevelopmental and Metabolomic Responses from Prenatal Coexposure to Perfluorooctanesulfonate (PFOS) and Methylmercury (MeHg) in Sprague-Dawley Rats

Reardon, AJF; Karathra, J; Ribbenstedt, A; Benskin, JP; MacDonald, AM; Kinniburgh, DW; Hamilton, TJ; Fouad, K; Martin, JW
2019 | Chem. Res. Toxicol. | 32 (8) (1656-1669)
adult-blood donors , attention deficit/hyperactivity disorder , developmental exposure , fish consumption , lactational exposure , locomotor-activity , perfluorinated compounds , perfluoroalkyl acids , persistent organic pollutants , polychlorinated biphenyls
Methylmercury (MeHg) and perfluoro-octanesulfonate (PFOS) are major contaminants of human blood that are both common in dietary fish, thereby raising questions about their combined impact on human development. Here, pregnant Sprague-Dawley rats ingested a daily dose, from gestational day 1 through to weaning, of either 1 mg/kg bw PFOS (PFOS-only), 1 mg/kg MeHg (MeHg-only), a mixture of 0.1 mg/kg PFOS and 1 mg/kg MeHg (Low-Mix), or of 1 mg/kg of PFOS and 1 mg/kg MeHg (High-Mix). Newborns were monitored for physical milestones and reflexive developmental responses, and in juveniles the spontaneous activity, anxiety, memory, and cognition were assessed. Targeted metabolomics of 199 analytes was applied to sectioned brain regions of juvenile offspring. Newborns in the High-Mix group had decreased weight gain as well as delayed reflexes and innate behavioral responses compared to controls and individual chemical groups indicating a toxicological interaction on early development. In juveniles, cumulative mixture effects increased in a dose-dependent manner in tests of anxiety-like behavior. However, other developmental test results suggested antagonism, as PFOS-only and MeHg-only juveniles had increased hyperactivity and thigmotaxic behavior, respectively, but fewer effects in Low-Mix and High-Mix groups. Consistent with these behavioral observations, a pattern of antagonism was also observed in neurochemicals measured in rat cortex, as PFOS-only and MeHg-only juveniles had altered concentrations of metabolites (e.g., lipids, amino acids, and biogenic amines), while no changes were evident in the combined exposures. The cortical metabolites altered in PFOS-only and MeHg-only exposed groups are involved in inhibitory and excitatory neurotransmission. These proof-of-principle findings at relatively high doses indicate the potential for toxicological interaction between PFOS and MeHg, with developmental-stage specific effects. Future mixture studies at lower doses are warranted, and prospective human birth cohorts should consider possible confounding effects from PFOS and mercury exposure on neurodevelopment.

Influence of Biogenic Organics on the Chemical Composition of Arctic Aerosols

Choi, JH; Jang, E; Yoon, YJ; Park, JY; Kim, TW; Becagli, S; Caiazzo, L; Cappelletti, D; Krejci, R; Eleftheria, K; Park, KT; Jang, KS
2019 | Global Biogeochem Cycles | 33 (10) (1238-1250)
air mass back trajectory , arctic organic aerosols , biological exposure , carbon , climate , ft-icr ms , identification , mass spectrometry , matter dom , molecular characterization , ny-alesund , phytoplankton , station , transport history
We use an ultrahigh-resolution 15-T Fourier transform ion cyclotron resonance mass spectrometer to elucidate the compositional changes in Arctic organic aerosols collected at Ny-angstrom lesund, Svalbard, in May 2015. The Fourier transform ion cyclotron resonance mass spectrometer analysis of airborne organic matter provided information on the molecular compositions of aerosol particles collected during the Arctic spring period. The air mass transport history, combined with satellite-derived geographical information and chlorophyll concentration data, revealed that the molecular compositions of organic aerosols drastically differed depending on the origin of the potential source region. The protein and lignin compound populations contributed more than 70% of the total intensity of assigned molecules when the air masses mainly passed over the ocean region. Interestingly, the intensity of microbe-derived organics (protein and carbohydrate compounds) was positively correlated with the air mass exposure to phytoplankton biomass proxied as chlorophyll. Furthermore, the intensities of lignin and unsaturated hydrocarbon compounds, typically derived from terrestrial vegetation, increased with an increase in the advection time of the air mass over the ocean domain. These results suggest that the accumulation of dissolved biogenic organics in the Arctic Ocean possibly derived from both phytoplankton and terrestrial vegetation could significantly influence the chemical properties of Arctic organic aerosols during a productive spring period. The interpretation of molecular changes in organic aerosols using an ultrahigh-resolution mass spectrometer could provide deep insight for understanding organic aerosols in the atmosphere over the Arctic and the relationship of organic aerosols with biogeochemical processes in terms of aerosol formation and environmental changes.

Influence of Hydrodynamic Processes on the Fate of Sedimentary Organic Matter on Continental Margins

Bao R., van der Voort T., Zhao M., Guo X., Montluçon D., McIntyre C., Eglinton T.,
2018 | Global Biogeochem Cycles
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Organic Carbon Aging During Across-Shelf Transport

Bao R., Uchida M., Zhao M., Haghipour N., Montlucon D., McNichol A., Wacker L.,, Hayes J. M., Eglinton T.
2018 | Geophys Res Lett
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