Size separation method for absorption characterization in brown carbon: Application to an aged biomass burning sample

Lorenzo, Robert A. Di; Young, Cora J.

doi:10.1002/2015gl066954

Cited by 62 publications

(103 citation statements)

References 49 publications

(121 reference statements)

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“…It should be noted that complete separation could not be achieved in this work. Other techniques, such as size-exclusion chromatography (Di Lorenzo and Young, 2016;Di Lorenzo et al, 2017), may yield better separation based on molecular weights, but may not be able to resolve compounds in the relatively low molecular weight range in the current study. Nonetheless, the first fraction can be qualitatively described as a "monomerrich" fraction, and the second fraction can be regarded as an "oligomer-rich" fraction (Figs.…”

Section: Op Of Oligomers In Nsoamentioning

confidence: 92%

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

Wang

Soong

et al. 2018

Atmos. Chem. Phys.

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Abstract. Owing to the complex nature and dynamic behaviors of secondary organic aerosol (SOA), its ability to cause oxidative stress (known as oxidative potential, or OP) and adverse health outcomes remains poorly understood. In this work, we probed the linkages between the chemical composition of SOA and its OP, and investigated impacts from various SOA evolution pathways, including atmospheric oligomerization, heterogeneous oxidation, and mixing with metal. SOA formed from photooxidation of the two most common polycyclic aromatic hydrocarbons (naphthalene and phenanthrene) were studied as model systems. OP was evaluated using the dithiothreitol (DTT) assay. The oligomerrich fraction separated by liquid chromatography dominates DTT activity in both SOA systems (52 ± 10 % for naphthalene SOA (NSOA), and 56 ± 5 % for phenanthrene SOA (PSOA)). Heterogeneous ozonolysis of NSOA was found to enhance its OP, which is consistent with the trend observed in selected individual oxidation products. DTT activities from redox-active organic compounds and metals were found to be not additive. When mixing with highly redox-active metal (Cu), OP of the mixture decreased significantly for 1,2-naphthoquinone (42 ± 7 %), 2,3-dihydroxynaphthalene (35 ± 1 %), NSOA (50 ± 6 %), and PSOA (43 ± 4 %). Evidence from proton nuclear magnetic resonance ( 1 H NMR) spectroscopy illustrates that such OP reduction upon mixing can be ascribed to metal-organic binding interactions. Our results highlight the role of aerosol chemical composition under atmospheric aging processes in determining the OP of SOA, which is needed for more accurate and explicit prediction of the toxicological impacts from particulate matter.

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Section: Op Of Oligomers In Nsoamentioning

confidence: 92%

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

Wang

Soong

et al. 2018

Atmos. Chem. Phys.

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“…The full method for the collection and extraction of BB particle samples collected during July wildfires in British Columbia is detailed in Di Lorenzo et al (2017). Briefly, PM 2.5 samples were collected at two sites approximately 100 km east of the BB location.…”

Section: Bc Fire Sample Analysismentioning

confidence: 99%

“…Laboratory investigations have shown that methylamines can be produced by marine phytoplankton degradation of quaternary amines to maintain an osmotic gradient as well as during periods of known zooplankton grazing (Gibb et al, 1999b). Based on the HYSPLIT back trajectories calculated for these samples (Di Lorenzo et al, 2017), it is possible that the BB plume particles interacted with gaseous DMA and DEA emitted from inland agricultural sources along the St. Lawrence River, coastal phytoplankton blooms, or with enhanced amine emissions in the coastal zone, which has been observed in the marine boundary layer of California (Youn et al, 2015). The high concentrations of DMA and DEA produced by marine biological activity could then partition into the BB particles and react to neutralize acids (e.g.…”

Section: Analytical Column Stabilitymentioning

confidence: 99%

“…These PM 2.5 samples were collected every 8 h while the plume was traversing each site and during collection the PM 2.5 concentration was in excess of 200 µg m −3 . The relative ages for the smoke plumes sam- pled at both sites were calculated to be 20 h old, or less, and back trajectories indicated that the plume did not travel over the open ocean before being sampled (Di Lorenzo et al, 2017). In these test samples, the method was again able to detect the presence of four different amines (iMPAH + , TMAH + , DEAH + , and TEAH + ) with loadings of Na + , NH + 4 , and K + at ratios in excess of 100 : 1 (Fig.…”

Section: Time Series Of Amines In Fresh Biomass-burning Plume Particlmentioning

confidence: 99%

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Quantitation of 11 alkylamines in atmospheric samples: separating structural isomers by ion chromatography

et al. 2017

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Amines are important drivers in particle formation and growth, which have implications for Earth's climate. In this work, we developed an ion chromatographic (IC) method using sample cation-exchange preconcentration for separating and quantifying the nine most abundant atmospheric alkylamines (monomethylamine (MMAH + ), dimethylamine (DMAH + ), trimethylamine (TMAH + ), monoethylamine (MEAH + ), diethylamine (DEAH + ), triethylamine (TEAH + ), monopropylamine (MPAH + ), isomonopropylamine (iMPAH + ), and monobutylamine (MBAH + )) and two alkyl diamines (1, 4-diaminobutane (DABH + ) and 1, 5-diaminopentane (DAPH + )). Further, the developed method separates the suite of amines from five common atmospheric inorganic cations (Na + , NH + 4 , K + , Mg 2+ , Ca 2+ ). All 16 cations are greater than 95 % baseline resolved and elute in a runtime of 35 min. This paper describes the first successful separation of DEAH + and TMAH + by IC and achieves separation between three sets of structural isomers, providing specificity not possible by mass spectrometry. The method detection limits for the alkylamines are in the picogram per injection range and the method precision (±1σ ) analyzed over 3 months was within 16 % for all the cations. The performance of the IC method for atmospheric application was tested with biomass-burning (BB) particle extracts collected from two forest fire plumes in Canada. In extracts of a size-resolved BB sample from an aged plume, we detected and quantified MMAH + , DMAH + , TMAH + , MEAH + , DEAH + , and TEAH + in the presence of Na + , NH + 4 , and K + at molar ratios of amine to inorganic cation ranging from 1 : 2 to 1 : 1000. Quantities of DEAH + and DMAH + of 0.2-200 and 3-1200 ng m −3 , respectively, were present in the extracts and an unprecedented amine-to-ammonium molar ratio greater than 1 was observed in particles with diameters spanning 56-180 nm. Extracts of respirable fine-mode particles (PM 2.5 ) from a summer forest fire in British Columbia in 2015 were found to contain iMPAH + , TMAH + , DEAH + and TEAH + at molar ratios of 1 : 300 with the dominant cations. The amine-to-ammonium ratio in a time series of samples never exceeded 0.15 during the sampling of the plume. These results and an amine standard addition demonstrate the robustness and sensitivity of the developed method when applied to the complex matrix of BB particle samples. The detection of multiple alkylamines in the analyzed BB samples indicates that this speciation and quantitation approach can be used to constrain BB emission estimates and the biogeochemical cycling of these reduced nitrogen species.

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“…It remains unclear whether BrC is comprised of low concentrations of strongly absorbing chromophores or a large number of weakly absorbing chromophores in a complex organic matrix. To date, several classes of compounds have been identified as BrC in biomass burning organic aerosols (BBOA), such as nitroaromatic compounds (Desyaterik et al, 2013;Zhang et al, 2013;Mohr et al, 2013;Lin et al, 2016), humic-like substances (HULIS; Dinar et al, 2008;Hoffer et al, 2006;Fan et al, 2016;Wang et al, 2017), and other high-molecular-weight substances (i.e., compounds > 400 Da; Di Lorenzo and Young, 2016;Di Lorenzo et al, 2017;Wong et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Atmospheric evolution of molecular-weight-separated brown carbon from biomass burning

et al. 2019

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Abstract. Biomass burning is a major source of atmospheric brown carbon (BrC), and through its absorption of UV/VIS radiation, it can play an important role in the planetary radiative balance and atmospheric photochemistry. The considerable uncertainty of BrC impacts is associated with its poorly constrained sources, transformations, and atmospheric lifetime. Here we report laboratory experiments that examined changes in the optical properties of the water-soluble (WS) BrC fraction of laboratory-generated biomass burning particles from hardwood pyrolysis. Effects of direct UVB photolysis and OH oxidation in the aqueous phase on molecular-weight-separated BrC were studied. Results indicated that the majority of low-molecular-weight (MW) BrC (<400 Da) was rapidly photobleached by both direct photolysis and OH oxidation on an atmospheric timescale of approximately 1 h. High MW BrC (≥400 Da) underwent initial photoenhancement up to ∼15 h, followed by slow photobleaching over ∼10 h. The laboratory experiments were supported by observations from ambient BrC samples that were collected during the fire seasons in Greece. These samples, containing freshly emitted to aged biomass burning aerosol, were analyzed for both water- and methanol-soluble BrC. Consistent with the laboratory experiments, high-MW BrC dominated the total light absorption at 365 nm for both methanol and water-soluble fractions of ambient samples with atmospheric transport times of 1 to 68 h. These ambient observations indicate that overall, biomass burning BrC across all molecular weights has an atmospheric lifetime of 15 to 28 h, consistent with estimates from previous field studies – although the BrC associated with the high-MW fraction remains relatively stable and is responsible for light absorption properties of BrC throughout most of its atmospheric lifetime. For ambient samples of aged (>10 h) biomass burning emissions, poor linear correlations were found between light absorptivity and levoglucosan, consistent with other studies suggesting a short atmospheric lifetime for levoglucosan. However, a much stronger correlation between light absorptivity and total hydrous sugars was observed, suggesting that they may serve as more robust tracers for aged biomass burning emissions. Overall, the results from this study suggest that robust model estimates of BrC radiative impacts require consideration of the atmospheric aging of BrC and the stability of high-MW BrC.

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Size separation method for absorption characterization in brown carbon: Application to an aged biomass burning sample

Cited by 62 publications

References 49 publications

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

Quantitation of 11 alkylamines in atmospheric samples: separating structural isomers by ion chromatography

Atmospheric evolution of molecular-weight-separated brown carbon from biomass burning

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