Analysis of natural organic matter via fourier transform ion cyclotron resonance mass spectrometry: an overview of recent non‐petroleum applications

Among the different techniques for mass analysis, ultra‐high‐resolution Fourier transform ion cyclotron resonance (FTICR) is the method of choice for highly complex samples, as it offers unrivaled mass accuracy and resolving power, combined with a high degree of flexibility in hybrid instruments as well as for ion activation techniques. FTICR instruments are readily embraced by the biological and biomedical research communities and applied over a wide range of applications for the analysis of biomolecules such as carbohydrates, lipids, nucleic acids, and proteins. In the field of natural organic matter (NOM) analysis, petroleum‐related studies currently dominate FTICR‐MS applications. Recently, however, there is a growing interest in developing high‐performance MS methods for the characterization of NOM samples from natural aquatic and terrestrial environments. Here, we present an overview of FTICR‐MS techniques for complex, non‐petroleum NOM samples, including data analysis and novel tandem mass spectrometry (MS/MS) methods for structural classifications. © 2020 The Authors. Mass Spectrometry Reviews published by John Wiley & Sons Ltd.Peer Reviewe

Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate change variability in the North Pacific Rim

Monoterpene and isoprene secondary organic aerosol (SOA) tracers are reported for the first time in an Alaskan ice core to better understand the biological source strength before and after the industrial revolution in the Northern Hemisphere. We found significantly high concentrations of monoterpene- and isoprene-SOA tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylerythritol) in the ice core, which show historical trends with good correlation to each other since 1660s. They show positive correlations with sugar compounds (e.g., mannitol, fructose, glucose, inositol and sucrose), and anti-correlations with alpha-dicarbonyls (glyoxal and methylglyoxal) and fatty acids (e.g., C-18:1) in the same ice core. These results suggest similar sources and transport pathways for monoterpene- and isoprene-SOA tracers. In addition, we found that concentrations of C-5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) in the ice core have increased after the Great Pacific Climate Shift (late 1970s). They show positive correlations with a-dicarbonyls and fatty acids (e.g., C-18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the marine boundary layer are recorded in the ice core from Alaska. Photochemical oxidation process for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations and retreat of sea ice in the Northern Hemisphere. (C) 2015 Elsevier Ltd. All rights reserved

Historical trends of biogenic SOA tracers in an ice core from Kamchatka Peninsula

Biogenic secondary organic aerosol (SOA) is ubiquitous in the Earth’s atmosphere, influencing climate and air quality. However, the historical trend of biogenic SOA is not well known. Here, we report for the first time the major isoprene- and monoterpene-derived SOA tracers preserved in an ice core from the Kamchatka Peninsula. Significant variations are recorded during the past 300 years with lower concentrations in the early-to-middle 19th century and higher concentrations in the preindustrial period and the present day. We discovered that isoprene SOA tracers were more abundant in the preindustrial period than the present day, while monoterpene SOA tracers stay almost unchanged. The causes of the observed variability are complex, depending on atmospheric circulation, changes in emissions, and other factors such as tropospheric oxidative capacity. Our data presents an unprecedented opportunity to shed light on the formation, evolution, and fate of atmospheric aerosols and to constrain the uncertainties associated with modeling their atmospheric concentrations

NAQPMS-PDAF v2.0: A Novel Hybrid Nonlinear Data Assimilation System for Improved Simulation of PM2.5 Chemical Components

PM2.5, a complex mixture with diverse chemical components, exerts significant impacts on the environment, human health, and climate change. However, precisely describing spatiotemporal variations of PM2.5 chemical components remains a difficulty. In our earlier work, we developed an aerosol extinction coefficient data assimilation (DA) system (NAQPMS-PDAF v1.0) that is suboptimal for chemical components. This paper introduces a novel hybrid nonlinear chemical DA system (NAQPMS-PDAF v2.0) to accurately interpret key chemical components (SO42-, NO3-, NH4+, OC, and EC). NAQPMS-PDAF v2.0 improves upon v1.0 by effectively handing and balancing stability and nonlinearity in chemical DA, which is achieved by incorporating the non-Gaussian-distribution ensemble perturbation and hybrid Localized Kalman-Nonlinear Ensemble Transform Filter with an adaptive forgetting factor for the first time. The dependence tests demonstrate that NAQPMS-PDAF v2.0 provides excellent DA results with a minimal ensemble size of 10, surpassing previous reports and v1.0. A one-month DA experiment shows that the analysis field generated by NAQPMS-PDAF v2.0 is in good agreement with observations, especially reducing the underestimation of NH4+ and NO3- and the overestimation of SO42-, OC, and EC. In particular, the CORR values for NO3-, OC, and EC are above 0.96, and R2 values are above 0.93. NAQPMS-PDAF v2.0 also demonstrates superior spatiotemporal interpretation, with most DA sites showing improvements of over 50 %–200 % in CORR and over 50 %–90 % in RMSE for the five chemical components. Compared to the poor performance in global reanalysis dataset (CORR: 0.42–0.55, RMSE: 4.51–12.27 µg/m3) and NAQPMS-PDAF v1.0 (CORR: 0.35–0.98, RMSE: 2.46–15.50 µg/m3), NAQPMS-PDAF v2.0 has the highest CORR of 0.86–0.99 and the lowest RMSE of 0.14–3.18 µg/m3. The uncertainties in ensemble DA are also examined, further highlighting the potential of NAQPMS-PDAF v2.0 for advancing aerosol chemical component studies

Sources of organic matter and paleo-environmental implications inferred from carbon isotope compositions of lacustrine sediments at Inexpressible Island, Ross Sea, Antarctica

The carbon isotopic composition of organic matter (δ13Corg) was determined in two sediment cores (IIL1 and IIL9) recovered from Inexpressible Island, Ross Sea, Antarctica, and analyzed to identify the sources of that organic matter. The δ13Corg values of sediments of IIL9 were found to vary between −14.6‰ and −11.6‰, with a mean of −13.4‰ (n=48). These values were significantly higher than those of IIL1 sediments which varied between −23.2‰ and −20.4‰, with a mean of −21.8‰ (n=55). The variation in δ13Corg values in these two sediment cores indicate different sources of organic matter. The relatively high δ13Corg values in IIL9 are in accordance with a source from algae, while the low δ13Corg values in IIL1 evince significant influence from penguin guano with algae as the secondary source. Compared with the reference data from other high-latitude lake sediments and plants, the δ13Corg values in IIL9 were extremely high, a result likely related to intense competition for CO2 assimilation among algal species during the growing season in this relatively shallow pond. These results indicate that sedimentary δ13Corg is a reliable proxy for paleo-primary productivity in ponds at Inexpressible Island

Micrometeorological flux measurements of aerosol and gases above Beijing

Air pollution is estimated to cause 1.6 million premature deaths in China every year and in the winter 2016/17 Beijing had to issue health alerts and put in place ad hoc limitations on industrial and vehicular activity. Much of this pollution is attributed to emissions from industrial processes and in particular coal combustion. By contrast, the diffuse pollutant sources within the city are less well understood. This includes, e.g., emissions from the Beijing traffic fleet, the sewage system, food preparation, solid fuel combustion in the streets and small industrial processes. Within the framework of a major UK-Chinese collaboration to study air pollution and its impact on human health in Beijing, we therefore measured fluxes of a large range of pollutants from a height of 102 m on the 325 m meteorological tower at the Institute of Atmospheric Physics. Several instruments were mounted at 102 m: fluxes of CO2 and H2O were measured with an infrared gas analyser (LiCOR 7500) and fluxes of ozone with a combination of a relative fast-response ozone analyser (ROFI) and a 2B absolute O3 instrument. Total particle number fluxes were measured with a condensation particle counter (TSI CPC 3785), and size-segregated fluxes over the size range 0.06 to 20 μm with a combination of an optical Ultrafine High Sensitivity Aerosol Spectrometer (UHSAS) and an Aerodynamic Particle Sizer Spectrometer (TSI APS3321). Ammonia (NH3) fluxes were measured for the first time above the urban environment using an Aerodyne compact quantum cascade laser (QCL). In addition, composition resolved aerosol fluxes were measured with an Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS), operated in a measurement container at the bottom of the tower, which subsampled from a 120 m long copper tube (15 mm OD). The analysis so far suggests that, due to often low wind speeds, fluxes were at times de-coupled from the surface. Fluxes normalised by CO2, a tracer for the amount of fossil fuel consumed, should be less sensitive to transport effects. However, not only fluxes, but also these CO2-ratioed fluxes are highly variable in both space and time, indicating a complex mix of sources, which will be further investigated. The organic aerosol fluxes were the largest we have recorded to date at any urban measurement site. Nitrate, sulphate, chloride and ammonium all showed emissions that followed a similar diurnal cycle as the organic aerosol. Much of this aerosol is likely to have been formed by chemistry below the measurement height, but it nevertheless indicates significant sources of the precursor gases within the footprint. Comparing the measured fluxes of gas-phase NH3 and aerosol NH+4, at 102 m the aerosol phase makes a significant contribution to the reduced nitrogen emission

Light absorption enhancement of black carbon in urban Beijing in summer

The light absorption enhancement (E-abs) of black carbon (BC) caused by non-BC materials is an important source of uncertainty in radiative forcing estimate, yet remains poorly understood in relatively polluted environment such as the megacity Beijing. Here BC absorption enhancement at 630 nm was in-situ measured using a ther-modenuder coupled with a soot particle aerosol mass spectrometer and a single scattering albedo monitor in Beijing in summer. The project average (+/- 1 sigma) E-abs was 1.59 ( +/- 0.26), suggesting a significant amplification of BC absorption due to coating materials. E-abs presented a clear daytime increase due to enhanced photochemical processing, and a strong dependence on the mass ratios of non-BC coatings to BC (R-BC). Our results showed that the increase in E(abs )as a function of R-BC was mainly caused by the increased contributions of secondary aerosol. Further analysis showed that the BC absorption enhancement in summer in Beijing was mainly associated with secondary formation of nitrate, sulfate and highly oxidized secondary organic aerosol (SOA), while the formation of freshly and less oxidized SOA appeared not to play an important role.Peer reviewe