P. K. Quinn

National Oceanic and Atmospheric Administration, Seattle, Washington, United States

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Publications (270)811.9 Total impact

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    Chemical Reviews 04/2015; 115(10). DOI:10.1021/cr500713g · 45.66 Impact Factor
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    ABSTRACT: We present mass spectrometry measurements of black-carbon containing particles made onboard the R/V Atlantis during the CalNex 2010 study using an Aerodyne Research Inc. soot particle aerosol mass spectrometer (SP-AMS). The R/V Atlantis was deployed to characterize air masses moving offshore the California coast and to assess emissions from sources in urban ports. This work presents a first detailed analysis of the size-resolved chemical composition of refractory black carbon (rBC) and of the associated coating species (NR-PMBC). A co-located standard high resolution aerosol mass spectrometer (HR-AMS) measured the total non-refractory submicron aerosol (NR-PM1). Our results indicate that, on average, 35% of the measured NR-PM1 mass (87% of the primary and 28% of the secondary NR-PM1, as obtained from the mass-weighted average of the NR-PMBC species) was associated with rBC. The peak in the average size distribution of the rBC-containing particles measured by the SP-AMS in vacuum aerodynamic diameter (dva) varied from ~100 nm to ~450 nm dva, with most of the rBC mass below 200 dva. The NR-PMBC below 200 nm dva was primarily organic, whereas inorganics were generally found on larger rBC-containing particles. Positive matrix factorization (PMF) analyses of both SP-AMS and HR-AMS data identified organic aerosol factors that were correlated in time, but had different fragmentation patterns due to the different instruments vaporization techniques. Finally, we provide an overview of the volatility properties of NR-PMBC and report the presence of refractory oxygen species in some of the air masses encountered.
    02/2015; 120(6). DOI:10.1002/2014JD022834
  • Atmospheric Chemistry and Physics 01/2015; 15(3):3629-3666. DOI:10.5194/acpd-15-3629-2015 · 4.88 Impact Factor
  • Atmospheric Chemistry and Physics 01/2015; 15(2):2085-2118. DOI:10.5194/acpd-15-2085-2015 · 4.88 Impact Factor
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    ABSTRACT: Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site (Pasadena) in June-July 2010 during CalNex (California Research at the Nexus of Air Quality and Climate Change) and a site in an oil and gas producing region (Uintah Basin) in January-February 2013 during UBWOS 2013 (Uintah Basin Winter Ozone Studies) will be discussed. Although the VOC (volatile organic compounds) compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 +/- 1.3 in UBWOS 2013 and 2.0 +/- 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 99 %). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Compared to the original MCM model that includes only ozonolysis of unsaturated organic compounds and OH oxidation of acetylene, when we updated yields of ozonolysis of alkenes and included OH oxidation of isoprene, vinyl alcohol chemistry, reaction of formaldehyde with HO2, oxidation of aromatics, and reaction of CH3O2 with OH, the model predictions for formic acid were improved by a factor of 6.4 in UBWOS 2013 and 4.5 in CalNex, respectively. A comparison of measured and modeled HCOOH / acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 19 and 45% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be 0-6 and 0-5% in UBWOS 2013 and CalNex, respectively. We observe that air-snow exchange processes and morning fog events may also contribute to ambient formic acid concentrations during UBWOS 2013 (similar to 20% in total). In total, 53-59 in UBWOS 2013 and 50-55% in CalNex of secondary formation of formic acid remains unexplained. More work on formic acid formation pathways is needed to reduce the uncertainties in the sources and budget of formic acid and to narrow the gaps between measurements and model results.
    Atmospheric Chemistry and Physics 01/2015; 15(4):1975-1993. DOI:10.5194/acp-15-1975-2015 · 5.51 Impact Factor
  • Atmospheric Chemistry and Physics 01/2015; 15(7):10677-10708. DOI:10.5194/acpd-15-10677-2015 · 4.88 Impact Factor
  • Atmospheric Chemistry and Physics 01/2015; 15(5):6403-6444. DOI:10.5194/acpd-15-6403-2015 · 4.88 Impact Factor
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    Bulletin of the American Meteorological Society 12/2014; 95(12):1873-1895. DOI:10.1175/BAMS-D-13-00017.1 · 11.57 Impact Factor
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    ABSTRACT: The sources and composition of atmospheric marine aerosol particles (aMA) have been investigated with a range of physical and chemical measurements from open-ocean research cruises. This study uses the characteristic functional group composition (from Fourier transform infrared, or FTIR, spectroscopy) of aMA from five ocean regions to show that: (i) The organic functional group composition of aMA that can be identified as mainly atmospheric primary marine (ocean-derived) aerosol particles (aPMA) is 65 ± 12% hydroxyl, 21 ± 9% alkane, 6 ± 6% amine, and 7 ± 8% carboxylic acid functional groups. Contributions from photochemical reactions add carboxylic acid groups (15%-25%), shipping effluent in seawater and ship emissions add additional alkane groups (up to 70%), and coastal or continental emissions mix in alkane and carboxylic acid groups. (ii) The organic composition of aPMA is nearly identical to model generated primary marine aerosol particles from bubbled seawater (gPMA, which has 55 ± 14% hydroxyl, 32 ± 14% alkane, and 13 ± 3% amine functional groups), indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. (iii) While the seawater organic functional group composition was nearly invariant across all three ocean regions studied and the ratio of organic carbon to sodium (OC/Na+) in the gPMA remained nearly constant over a broad range of chlorophyll-a concentrations, the gPMA alkane group fraction appeared to increase with chlorophyll-a concentrations (r =0.66). gPMA from productive seawater had a larger fraction of alkane functional groups (42 ± 9%) compared to gPMA from non-productive seawater (22 ± 10%), perhaps due to the presence of surfactants in productive seawater that stabilize the bubble film and lead to preferential drainage of the more soluble (lower alkane group fraction) organic components. gPMA has a hydroxyl group absorption peak location characteristic of monosaccharides and disaccharides, where the seawater OM hydroxyl group peak location is closer to that of polysaccharides. This may result from the larger saccharides preferentially remaining in the seawater during gPMA and aPMA production.
    11/2014; 119(22). DOI:10.1002/2014JD021913
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    ABSTRACT: We investigate hygroscopic growth of marine aerosols from three research cruises: TexAQS-GoMACCS 2006, ICEALOT 2008 and CalNex 2010. Particle hygroscopic growth was characterized by measuring the effect of water uptake under sub-saturated conditions on the aerosol light extinction at 532 nm. Mie theory calculations were utilized to convert the observed optical growth factors (fext(RH)) into physical growth factors (GF) at 85% RH. GF is found to be a more robust measure of aerosol hygroscopic growth than fext(RH), which can be biased by changes in aerosol dry size. Consistent with previous observations, the overall GF(85%) for submicron aerosol depended on the fraction of organics. The submicron GFOM(85%) specifically was found to range from 1.0-1.3 for all three campaigns. A robust positive linear dependence of the overall supermicron GF(85%) on the mass fraction of sea salt was observed. During TexAQS, two types of dust particles with distinct hygroscopic properties were identified in the supermicron mode; one that originated from the Sahara desert was moderately hygroscopic (GFdust(85%) = ~1.4) and the other from continental sources was nearly hydrophobic. The GF(85%) of supermicron organics was estimated through hygroscopicity closure calculations. Supermicron organics that originated from marine sources were found to be substantially more hygroscopic than those from continental sources, with the latter having a GF(85%) similar to that of the submicron organics. This study demonstrates the potential of using aerosol optical measurements to retrieve hygroscopic growth factor and underlines the importance and need for future investigations on the hygroscopic properties of marine supermicron aerosols.
    07/2014; 119(13). DOI:10.1002/2013JD021213
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    ABSTRACT: We present a sensitive, compact detector that measures total reactive nitrogen (NOy), as well as NO2, NO, and O3. In all channels, NO2 is directly detected by laser diode based cavity ring-down spectroscopy (CRDS) at 405 nm. Ambient O3 is converted to NO2 in excess NO for the O3 measurement channel. Likewise, ambient NO is converted to NO2 in excess O3. Ambient NOy is thermally dissociated at ∼700° to form NO2 or NO in a heated quartz inlet. Any NO present in ambient air or formed from thermal dissociation of other reactive nitrogen compounds is converted to NO2 in excess O3 after the thermal converter. We measured thermal dissociation profiles for six of the major NOy components, and compared ambient measurements with other instruments during field campaigns in Utah and Alabama. Alabama measurements were made in a rural location with high biogenic emissions, and Utah measurements were made in the wintertime in unusual conditions that form high ozone from emissions related to oil and gas production. The NOy comparison in Alabama, to an accepted standard measurement method (a molybdenum catalytic converter/chemiluminescence instrument), agreed to within 12%, which we define as an upper limit to the accuracy of the NOy channel. The 1σ precision is <30 pptv at 1 second and <4 pptv at 1 minute time resolution for all measurement channels. The accuracy is 3% for the NO2 and O3 channels, and 5% for the NO channel. The precision and accuracy of this instrument make it a versatile alternative to standard chemiluminescence-based NOy instruments.
    Environmental Science and Technology 07/2014; 48(16). DOI:10.1021/es501896w · 5.48 Impact Factor
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    ABSTRACT: Quinn, P.K., A. Stohl, A. Baklanov, M.G. Flanner, A. Herber, K.Kupiainen, K.S. Law, J. Schmale, S. Sharma, V. Vestreng, and K. von Salzen, The Arctic, Radiative forcing by black carbon in the Arctic in “State of the Climate in 2013”, Bull. Amer. Meteor, Soc., 95 (7) S124 – 125, 2014.
    Bulletin of the American Meteorological Society 07/2014; 95(7):S124-125. · 11.57 Impact Factor
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    ABSTRACT: Ship-based measurements of gas-phase hydrochloric acid (HCl), particulate chloride (pCl-), and reactive nitrogen oxides (NOy) were made in the polluted marine boundary layer along the California coastline during spring 2010. These observations are used to assess both the rate of Cl atom production from HCl and the role of direct HCl emissions and subsequent partitioning as a source for pCl-. Observations of HCl made in coastal Southern California are broadly correlated with NOz (NOz ≡ NOy – NOx), peaking at 11 AM. The observed median HCl mixing ratio in Southern California is 1.3 ppb (interquartile range: 0.53 − 2.7 ppb), as compared to 0.19 ppb (interquartile range: 0.10 − 0.38 ppb) measured along the Sacramento River between San Francisco and Sacramento. Concurrent measurements of aerosol ion chemistry indicate that aerosol particles sampled in Northern California are heavily depleted in Cl-, corresponding to a mean pCl- deficit of 0.05 ± 0.03 (1σ) ppb for sub-10 μm aerosol particles. In comparison, aerosols measured in Southern California indicate that over 25% of particles showed an addition of Cl- to the particle population. Observations presented here suggest that primary sources of HCl, or gas-phase chlorine precursors to HCl, are likely underestimated in the California ARB emissions inventory. These results highlight the need for future field observations designed to better constrain direct reactive halogen emissions.
    06/2014; 119(11). DOI:10.1002/2013JD020992
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    ABSTRACT: Aerosol variations and trends over different land and ocean regions from 1980 to 2009 are analyzed with the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and observations from multiple satellite sensors and available ground-based networks. Excluding time periods with large volcanic influence, aerosol optical depth (AOD) and surface concentration over polluted land regions generally vary with anthropogenic emissions, but the magnitude of this association can be dampened by the presence of natural aerosols, especially dust. Over the 30-year period in this study, the largest reduction in aerosol levels occurs over Europe, where AOD has decreased by 40–60% on average and surface sulfate concentrations have declined by a factor of up to 3–4. In contrast, East Asia and South Asia show AOD increases, but the relatively high level of dust aerosols in Asia reduces the correlation between AOD and pollutant emission trends. Over major dust source regions, model analysis indicates that the change of dust emissions over the Sahara and Sahel has been predominantly driven by the change of near-surface wind speed, but over Central Asia it has been largely influenced by the change of the surface wetness. The decreasing dust trend in the North African dust outflow region of the tropical North Atlantic and the receptor sites of Barbados and Miami is closely associated with an increase of the sea surface temperature in the North Atlantic. This temperature increase may drive the decrease of the wind velocity over North Africa, which reduces the dust emission, and the increase of precipitation over the tropical North Atlantic, which enhances dust removal during transport. Despite significant trends over some major continental source regions, the model-calculated global annual average AOD shows little change over land and ocean in the past three decades, because opposite trends in different land regions cancel each other out in the global average, and changes over large open oceans are negligible. This highlights the necessity for regional-scale assessment of aerosols and their climate impacts, as global-scale average values can obscure important regional changes.
    ATMOSPHERIC CHEMISTRY AND PHYSICS 05/2014; DOI:10.5194/acp-14-3657-2014 · 5.30 Impact Factor
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    ABSTRACT: Physical and biogeochemical processes in seawater controlling primary marine aerosol (PMA) production and composition are poorly understood and associated with large uncertainties in estimated fluxes into the atmosphere. PMA production was investigated in the biologically-productive NE Pacific Ocean and in biologically-productive and oligotrophic regions of the NW Atlantic Ocean. Physicochemical properties of model PMA, produced by aeration of fresh seawater under controlled conditions, were quantified. Diel variability in model PMA mass and number fluxes was observed in biologically productive waters, increasing following sunrise and decreasing to pre-dawn levels overnight. Such variability was not seen in oligotrophic waters. Surfactant scavenging by aeration in the aerosol generator without replenishing the seawater in the reservoir during daytime reduced model PMA production in productive waters to nighttime levels but had no influence on production from oligotrophic waters. Results suggest bubble-plume interactions with sunlight-mediated biogenic surfactants in productive seawater significantly enhanced model PMA production.
    04/2014; 41(7). DOI:10.1002/2014GL059436
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    ABSTRACT: The Spectral Deconvolution Algorithm (SDA) and SDA+ (extended SDA) methodologies can be employed to separate the fine and coarse mode extinction coefficients from measured total aerosol extinction coefficients, but their common use is currently limited to AERONET Aerosol Optical Depth (AOD). Here we provide the verification of the SDA+ methodology on a non-AERONET aerosol product, by applying it to fine and coarse mode nephelometer and Particle Soot Absorption Photometer (PSAP) data sets collected in the marine boundary layer. Using datasets collected on research vessels by NOAA PMEL, we demonstrate that with accurate input, SDA+ is able to predict the fine and coarse mode scattering and extinction coefficient partition in global data sets representing a range of aerosol regimes. However, in low-extinction regimes commonly found in the clean marine boundary layer, SDA+ output accuracy is sensitive to instrumental calibration errors. This work was extended to the calculation of coarse and fine mode scattering coefficients with similar success. This effort not only verifies the application of the SDA+ method to in situ data, but by inference verifies the method as a whole for a host of applications, including AERONET. Study results open the door to much more extensive use of nephelometers and PSAPs, with the ability to calculate fine and coarse mode scattering and extinction coefficients in field campaigns that do not have the resources to explicitly measure these values.
    Atmospheric Measurement Techniques 03/2014; 7(10):2545-2584. DOI:10.5194/amtd-7-2545-2014 · 3.21 Impact Factor
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    ABSTRACT: Breaking waves on the ocean surface generate air bubbles that scavenge organic matter from the surrounding sea water. When injected into the atmosphere, these bubbles burst, yielding sea spray aerosols enriched in organic matter, relative to the sea water. Downwind of plankton blooms, the organic carbon content of sea spray aerosol is weakly correlated with satellite-derived measurements of chlorophyll a levels, a measure of phytoplankton biomass. This correlation has been used in large-scale models to calculate the organic enrichment in sea spray aerosol. Here, we assess the relationship between the organic carbon content of sea water and freshly emitted sea spray aerosol in the presence and absence of plankton blooms in the North Atlantic Ocean and the coastal waters of California. The organic carbon content of freshly emitted sea spray aerosol was similar in all regions sampled, despite significant differences in seawater chlorophyll a levels. The proportion of freshly emitted aerosols that served as cloud condensation nuclei at a given supersaturation was also similar across sampling sites. The large reservoir of organic carbon in surface sea water remained relatively constant across the regions sampled, and independent of variations in chlorophyll a concentrations. We suggest that this reservoir is responsible for the organic carbon enrichment of freshly emitted sea spray aerosol, overwhelming any influence of local biological activity as measured by chlorophyll a levels.
    Nature Geoscience 02/2014; 7(3). DOI:10.1038/ngeo2092 · 11.67 Impact Factor
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    ABSTRACT: Emissions factors (EFs) for gas and sub-micron particle-phase species were measured in intercepted plumes as a function of vessel speed from an underway research vessel, the NOAA ship Miller Freeman, operating a medium-speed diesel engine on low-sulfur marine gas oil (fuel sulfur content ~0.1% by weight). The low-sulfur fuel in use conforms to the MARPOL fuel sulfur limit within emission control areas set to take effect in 2015 and to California-specific limits set to take effect in 2014. For many of the particle-phase species, EFs were determined using multiple measurement methodologies, allowing for an assessment of how well EFs from different techniques agree. The total sub-micron PM (PM1) was dominated by particulate black carbon (BC) and particulate organic matter (POM), with an average POM / BC ratio of 1.3. Consideration of the POM / BC ratios observed here with literature studies suggests that laboratory and in-stack measurement methods may overestimate primary POM EFs relative to those observed in emitted plumes. Comparison of four different methods for black carbon measurement indicates that careful attention must be paid to instrument limitations and biases when assessing EFBC. Particulate sulfate (SO42-) EFs were extremely small and the particles emitted by Miller Freeman were inefficient as cloud condensation nuclei (CCN), even at high super saturations, consistent with the use of very low-sulfur fuel and the overall small emitted particle sizes. All measurement methodologies consistently demonstrate that the measured EFs (fuel mass basis) for PM1 mass, BC and POM decreased as the ship slowed. Particle number EFs were approximately constant across the speed change, with a shift towards smaller particles being emitted at slower speeds. Emissions factors for gas-phase CO and formaldehyde (HCHO) both increased as the vessel slowed, while EFs for NOx decreased and SO2 EFs were approximately constant.
    Atmospheric Chemistry and Physics 01/2014; 14(3). DOI:10.5194/acp-14-1337-2014 · 4.88 Impact Factor
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    ABSTRACT: Black carbon (BC) mass emission factors (EFBC; g BC(kg fuel)
    Atmospheric Chemistry and Physics 01/2014; 14(4). DOI:10.5194/acp-14-1881-2014 · 4.88 Impact Factor
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    ABSTRACT: Copyright 2014 American Association for Aerosol Research
    Aerosol Science and Technology 01/2014; 48(3). DOI:10.1080/02786826.2013.879979 · 3.16 Impact Factor

Publication Stats

9k Citations
811.90 Total Impact Points

Institutions

  • 1997–2015
    • National Oceanic and Atmospheric Administration
      • • Pacific Marine Environmental Laboratory
      • • Chemical Science Division
      Seattle, Washington, United States
  • 1996–2015
    • NOAA Fisheries
      Silver Spring, Maryland, United States
  • 2008
    • University of Helsinki
      • Department of Physical Sciences
      Helsinki, Uusimaa, Finland
  • 1029–2007
    • University of Washington Seattle
      • • Joint Institute for the Study of the Atmosphere and Ocean
      • • Department of Atmospheric Sciences
      • • Department of Chemistry
      Seattle, Washington, United States
  • 2004
    • National Institute of Water and Atmospheric Research
      Wellington, Wellington, New Zealand