Molecular Characterization of Organophosphorus Compounds in Wildfire Smoke Using 21-T Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry.

We present a detailed molecular characterization of organophosphorus compounds in ambient organic aerosol influenced by wildfire smoke. Biomass burning organic aerosol (BBOA) is an important source of phosphorus (P) to surface waters, where even a small imbalance in the P flux can lead to substantial effects on water quality, such as eutrophication, algal blooms, and oxygen depletion. We aimed to exploit the ultrahigh resolving power, mass accuracy, and sensitivity of Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) to explore the molecular composition of an ambient BBOA sample collected downwind of Pacific Northwest wildfires. The 21-T FT-ICR MS yielded 10 533 distinct formulae, which included molecular species comprising C, H, O, and P with or without N, i.e., organophosphorus compounds that have long been quantified in wildfire smoke but have not yet been characterized at the molecular level. The lack of detailed molecular characterization of organophosphorus compounds in BBOA is primarily due to their inherently low concentrations in aerosols and poor ionization efficiency in complex mixtures. We demonstrate that the exceptional sensitivity of the 21-T FT-ICR MS allows qualitative analysis of a previously uncharacterized fraction of BBOA without its selective concentration from the organic matrix, exemplifying the need for ultrahigh-resolution tools for a more detailed and accurate molecular depiction of such complex mixtures.

MFAssignR: Molecular formula assignment software for ultrahigh resolution mass spectrometry analysis of environmental complex mixtures.

Ultrahigh resolution mass spectrometry is widely used for nontargeted analysis of complex environmental and biological mixtures, such as dissolved organic matter, due to its unparalleled ability to provide accurate mass measurements. Accurate and efficient characterization of these mixtures is critical to being better able to evaluate their effect on human health and climate. This characterization requires accurate mass signals free from isobaric interferences, instrument noise, and mass measurement biases, allowing for molecular formula identification. To address this need, an open source post-processing pipeline for ultrahigh resolution mass spectra of environmental complex mixtures software was developed. MFAssignR contains functions that perform noise estimation, 13C and 34S polyisotopic mass filtering, mass measurement recalibration, and molecular formula assignment as part of a consistent data processing environment. Novel applications of mass defect analysis were used in the functions for noise estimation and isotope pair identification. Using formula extensions, exact mass measurements are converted to unambiguous molecular formulas via data dependent pathways, reducing a priori decisions. Optional molecular formula ambiguity and multiple non-oxygen heteroatoms are provided for custom user applications, including isotopically labeled reactive species, halogen-containing species, or tandem ultrahigh resolution mass spectrometry. This represents uncommon flexibility for an open-source software package. To evaluate the performance of MFAssignR, it was used to characterize a sample of biomass burning influenced organic aerosol and the results were compared to those from other available methods of molecular formula assignment and noise estimation. The differences between the methods are described here. Overall, the inclusion of a full pipeline of data preparation functions and the data-dependent ambiguity reductions in MFAssignR render excellent results and make MFAssignR well-suited for the consistent and efficient analysis of environmental complex mixtures. MFAssignR is publicly available via GitHub.

Determination of water-soluble and fat-soluble vitamins in tears and blood serum of infants and parents by liquid chromatography/mass spectrometry.

Tears serve as a viable diagnostic fluid with advantages including less invasive sample to collect and less complex to prepare for analysis. Several water-soluble and fat-soluble vitamins were detected and quantified in human tears and compared with blood serum levels. Samples from 15 family pairs, each pair consisting of a four-month-old infant and one parent were analyzed; vitamin concentrations were compared between tears and blood serum for individual subjects, between infants and parents, and against self-reported dietary intakes. Water-soluble vitamins B1, B2, B3 (nicotinamide), B5, B9 and fat-soluble vitamin E (α-tocopherol) were routinely detected in tears and blood serum while fat-soluble vitamin A (retinol) was detected only in blood serum. Water-soluble vitamin concentrations measured in tears and blood serum of single subjects were comparable, while higher concentrations were measured in infants compared to their parents. Fat-soluble vitamin E concentrations were lower in tears than blood serum with no significant difference between infants and parents. Serum vitamin A concentrations were higher in parents than infants. Population trends were compiled and quantified using a cross correlation factor. Strong positive correlations were found between tear and blood serum concentrations of vitamin E from infants and parents and vitamin B3 concentrations from parents, while slight positive correlations were detected for infants B3 and parents B1 and B2 concentrations. Correlations between infants and parents were found for the concentrations of B1, B2, B3, and E in tears, and the concentrations of B2, A, and E in blood serum. Stronger vitamin concentration correlations were found between infants and parents for the breast-fed infants, while no significant difference was observed between breast-fed and bottle-fed infants. This work is the first to demonstrate simultaneous vitamin A, B, and E detection and to quantify correlations between vitamin concentrations in tears and blood serum. Our results suggest that tears are a viable biofluid to monitor nutritional health because they sufficiently mirror blood serum data and may enhance the speed of deficiency diagnoses.

Photochemical mobilization of dissolved hydrocarbon oxidation products from petroleum contaminated soil into a shallow aquifer activate human nuclear receptors.

Elevated non-volatile dissolved organic carbon (NVDOC) concentrations in groundwater (GW) monitoring wells under oil-contaminated hydrophobic soils originating from a pipeline rupture at the National Crude Oil Spill & Natural Attenuation Research Site near Bemidji, MN are documented. We hypothesized the elevated NVDOC is comprised of water-soluble photooxidation products transported from the surface to the aquifer. We use field and laboratory samples in combination with complementary analytical methods to test this hypothesis and determine the biological response to these products. Observations from optical spectroscopy and ultrahigh-resolution mass spectrometry reveal a significant correlation between the chemical composition of NVDOC leached from photochemically weathered soils and GW monitoring wells with high NVDOC concentrations measured in the aquifer beneath the contaminated soil. Conversely, the chemical composition from the uncontaminated soil photoleachate matches the NVDOC observed in the uncontaminated wells. Contaminated GW and photodissolution leachates from contaminated soil activated biological targets indicative of xenobiotic metabolism and exhibited potential for adverse effects. Newly formed hydrocarbon oxidation products (HOPs) from fresh oil could be distinguished from those downgradient. This study illustrates another pathway for dissolved HOPs to infiltrate GW and potentially affect human health and the environment.

Fragmentation analysis of water-soluble atmospheric organic matter using ultrahigh-resolution FT-ICR mass spectrometry.

Isolated water-soluble atmospheric organic matter (AOM) analytes extracted from radiation fogwater samples were analyzed using collision induced dissociation with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Tandem mass analysis was performed on several mass ranges between 100 and 400 Da to characterize the functional groups of AOM species. Compounds containing nitrogen and/or sulfur were targeted because of the high number of oxygen atoms contained in their molecular formulas. Due to the large number of isobaric ions in the precursor isolation ranges, large numbers of product ions resulted from collision induced dissociation. Common neutral losses were assigned by matching the molecular formulas of the expected product ions with the detected product ions within the appropriate mass spectra. Since polar functional groups are expected to affect the hygroscopic properties of aerosols, the losses of H(2)O, CO(2), CH(3)OH, HNO(3), CH(3)NO(3), SO(3), SO(4) and combinations of these were specifically targeted. Among the 421 compounds studied, the most frequently observed neutral losses were CO(2) (54%), H(2)O (43%) and CH(3)OH (40%). HNO(3) losses were observed for 63% of the studied nitrogen containing compounds and 33% of the studied compounds containing both nitrogen and sulfur. SO(3) losses were observed for 85% of the studied sulfur containing compounds and 42% of studied compounds containing both nitrogen and sulfur. A number of molecular formulas matching those of monoterpene ozonolysis SOA were observed; they include organonitrates, organosulfates, and nitroxy-organosulfates. Overall, the results of fragmentation analysis of 400+ individual molecular precursors elucidate the complexity and multifunctional nature of the isolated water-soluble AOM.

Analytical determination of the aerosol organic mass-to-organic carbon ratio.

Particulate matter (PM) with an aerodynamic diameter < or = 2.5 microm (PM2.5) was collected daily (mid-July 1998 to the end of December 1999) over a 24-hr sampling period in a mixed light industrial-residential area in Atlanta, GA, to provide a subset of data for the Aerosol Research and Inhalation Epidemiology Study (ARIES). This study included the measurement of organic carbon (OC), elemental carbon (EC), and individual organic compounds. OC and EC average mean concentrations were 4.50 +/- 0.33 and 2.08 +/- 0.19 microg/m3, respectively. The ratio of organic matter mass (OM) to OC in PM2.5 aerosols in Atlanta was measured using three different approaches: (1) solvent extract residue gravimetric masses to individual OC concentrations of sequential apolar to polar solvent extracts (dichloromethane, acetone, and water); (2) mass balance of the PM2.5 measured gravimetric mass minus the mass concentrations of the inorganic/elemental constituents to the total OC concentration; and (3) polar organic compound speciation with the concentration weighted ratio to the total OC concentration. We found very good agreement between approach 1 and 2. The average OM/OC ratio calculated from the extract residue mass was 2.14 +/- 0.17. The average OM/OC ratio determined by mass balance was 2.16 +/- 0.43 for the whole period. The concentration weighted ratio calculated from the concentrations of polar organic compounds ranged between 1.55 and 1.72, which was likely a lower limit for the ratio because of the limited number of the polar organic compounds that can be quantified using gas chromatographic methods. We found seasonal differences with an OM/OC range of 1.77 in December 1999 to 2.39 in July 1999. These results suggest that the previously accepted value of 1.4 for the OM/OC ratio was too low even for urban locations during the winter months. Molecular-level speciation of the PM2.5-associated organic compounds showed that the concentrations of the molecular markers for wood smoke represented approximately 12-15% of the total polar organic compound concentrations during the winter months.

Extensive Soot Compaction by Cloud Processing from Laboratory and Field Observations.

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

Transformations of dissolved organic matter induced by UV photolysis, Hydroxyl radicals, chlorine radicals, and sulfate radicals in aqueous-phase UV-Based advanced oxidation processes.

Considering the increasing identification of trace organic contaminants in natural aquatic environments, the removal of trace organic contaminants from water or wastewater discharge is an urgent task. Ultraviolet (UV) and UV-based advanced oxidation processes (AOPs), such as UV/hydrogen peroxide (UV/H2O2), UV/free chlorine and UV/persulfate, are attractive and promising approaches for the removal of these contaminants due to the high reactivity of active radical species produced in these UV-AOPs with a wide variety of organic contaminants. However, the removal efficiency of trace contaminants is greatly affected by the presence of background dissolved organic matter (DOM). In this study, we use ultrahigh resolution mass spectrometry to evaluate the transformation of a standard Suwanee River fulvic acid DOM isolate in UV photolysis and UV-AOPs. The use of probe compounds allows for the determination of the steady-state concentrations of active radical species in each UV-AOP. The changes in the H/C and O/C elemental ratios, double bond equivalents, and the low-molecular-weight transformation product concentrations of organic acids reveal that different DOM transformation patterns are induced by each UV-AOP. By comparison with the known reactivities of each radical species with specific organic compounds, we mechanistically and systematically elucidate the molecular-level DOM transformation pathways induced by hydroxyl, chlorine, and sulfate radicals in UV-AOPs. We find that there is a distinct transformation in the aliphatic components of DOM due to HO• in UV/H2O2 and UV/free chlorine. Cl• induced transformation of olefinic species is also observed in the UV/free chlorine system. Transformation of aromatic and olefinic moieties by SO4•- are the predominant pathways in the UV/persulfate system.

Separation of common organic and inorganic anions in atmospheric aerosols using a piperazine buffer and capillary electrophoresis.

The ability to monitor and quantify anionic components of aerosols is important for developing a better fundamental understanding of temporal and spatial variations in aerosol composition. Of the many methods that can be used to detect anions, capillary electrophoresis is among the most attractive ones because of its high separation efficiency, high resolving power for ionic compounds, and ability to be miniaturized for in-field monitoring. Here we present a method to baseline resolve common aerosol components nitrate, sulfate, chloride, and over two dozen organic acids in a single separation. A capillary electrophoresis separation utilizing a pH 5.78 piperazine buffer with 1,5-naphthalenedisulfonic acid as a probe for indirect UV absorbance detection was developed for this analysis. Previously, two different buffers were required to adequately separate all of these compounds. Electrophoretic mobilities, limits of detection, and migration time reproducibilities were measured for 38 organic and 8 inorganic anions. For solutions of low conductivity, detection limits for electrokinetic injections were found to be up to two orders of magnitude lower (0.2-0.4 microM) than those for pressure injection (1-45 microM). This separation was optimized and used for routine analysis of aqueous extracts of ambient atmospheric aerosols, but may be extended to other samples containing similar mixtures of anions.

Data representing two separate LC-MS methods for detection and quantification of water-soluble and fat-soluble vitamins in tears and blood serum.

Two separate liquid chromatography (LC)-mass spectrometry (MS) methods were developed for determination and quantification of water-soluble and fat-soluble vitamins in human tear and blood serum samples. The water-soluble vitamin method was originally developed to detect vitamins B1, B2, B3 (nicotinamide), B5, B6 (pyridoxine), B7, B9 and B12 while the fat-soluble vitamin method detected vitamins A, D3, 25(OH)D3, E and K1. These methods were then validated with tear and blood serum samples. In this data in brief article, we provide details on the two LC-MS methods development, methods sensitivity, as well as precision and accuracy for determination of vitamins in human tears and blood serum. These methods were then used to determine the vitamin concentrations in infant and parent samples under a clinical study which were reported in "Determination of Water-Soluble and Fat-Soluble Vitamins in Tears and Blood Serum of Infants and Parents by Liquid Chromatography/Mass Spectrometry DOI:10.1016/j.exer.2016.12.007 [1]". This article provides more details on comparison of vitamin concentrations in the samples with the ranges reported in the literature along with the medically accepted normal ranges. The details on concentrations below the limits of detection (LOD) and limits of quantification (LOQ) are also discussed. Vitamin concentrations were also compared and cross-correlated with clinical data and nutritional information. Significant differences and strongly correlated data were reported in [1]. This article provides comprehensive details on the data with slight differences or slight correlations.

Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol.

A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.

Water-soluble atmospheric organic matter in fog: exact masses and chemical formula identification by ultrahigh-resolution fourier transform ion cyclotron resonance mass spectrometry.

The detailed molecular composition of water-soluble atmospheric organic matter (AOM) contained in fog water was studied by use of electrospray ionization ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. We identified 1368 individual molecular masses in the range of 100-400 Da from negative-ion spectra obtained after reversed-phase extraction with a hydrophilic solid phase sorbent. The detected organic anions are multifunctional with a variety of oxygenated functional groups. We observe organic nitrogen, organic sulfur, and organic nitrogen-sulfur compounds as well as many species with only C, H, and O elemental composition. Analysis of the double bond equivalents (DBE = the number of rings plus the number of double bonds to carbon) suggests that these compound structures range from highly aliphatic to aromatic with DBE values of 1-11. The compounds range in their extent of oxidation with oxygen to carbon ratios from 0.2 to 2 with an average value of 0.43. Several homologous series of compounds and multifunctional oligomers were identified in this AOM. The high extent of homologous series of compounds likely originates from primary components that have become oxidized. The multifunctional oligomers appear to represent atmospheric processing of primary and secondary compounds. The isolated water-soluble components identified here are amphiphilic, meaning that they contain both hydrophilic oxygenated functional groups and hydrophobic aliphatic and aromatic structural moieties. Despite the high number of compounds with very high oxygen content, 60% of assigned chemical formulas have measured organic mass-to-organic carbon ratios

Emissions of levoglucosan, methoxy phenols, and organic acids from prescribed burns, laboratory combustion of wildland fuels, and residential wood combustion.

Biomass combustion emissions make a significant contribution to the overall particulate pollution in the troposphere. Wildland or prescribed burns and residential wood combustion emissions can vary due to differences in fuel, season, time of day, and the nature of the combustion. Inadequate understanding of the relevance of these biomass combustion emissions is due to the lack of characterization of open combustion emissions and the limited understanding of the differences between these and residential wood combustion. To provide new insight to biomass combustion emissions, sampling was conducted in several types of conditions. Semi-volatile organic compounds (SVOC) were collected during four separate prescribed burns in three different ecosystems, Mariposa Sequoia Grove within Yosemite National Park, CA, desert brushes of central rural Nevada, and Toiyabye National Forest near Lake Tahoe, NV. SVOC samples were also collected under controlled conditions for several wildland fuels, including conifer needles, wildland grasses, and sagebrush. Fireplace emissions from simulated residential wood combustion were also collected and are included here for comparison. A high degree of variability was found in the emissions of organic carbon, elemental carbon, levoglucosan, methoxy phenols, and organic acids. The variability in the emissions of levoglucosan does not correlate with the PM2.5 gravimetric mass and thus may affect source apportionment estimates.