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At least 163 records · Page 9

Diel mercury concentration variations in a mercury-impacted stream

Here, filtered and particulate mercury (Hg) and methylmercury (MMHg), and associated water chemistry parameters, were evaluated bi-hourly for several 30 h periods during the summer and winter seasons at several distinct locations (downstream forested, midstream urban/suburban, upstream industrial) along a creek contaminated with high levels of inorganic Hg to determine if biogeochemical Hg and MMHg cycles respond to the daily photocycle. In summer particulate Hg and MMHg concentrations doubled overnight (excluding the upstream industrial site) concurrent with increases in turbidity and total suspended sediment; no such pattern was evident in winter. Seasonal and diel changes in the activity of macrobiota affecting the suspension of contaminated sediments are likely responsible for these patterns as other potential explanatory variables (e.g., instrument drift, pH, discharge) could not account for the range and timing of our observations. Diel patterns in filtered Hg (Hg D ) were significant only at locations and times of the year when channel shading was not present and daytime concentrations increased 22–89% above nighttime minima likely caused by direct and indirect photochemical reactions. Relationships between Hg D and dissolved organic carbon (DOC) concentration or character were inconsistent between sites. Unlike Hg D , there were significant diel patterns in filtered MMHg (MMHg D ) at all sites and times of year, with summer concentrations peaking in mid to late afternoon while the timing differed in winter, with concentrations peaking after sunset. Daily variability in MMHg D concentration ranged between 25 and 75%. The results imply key controls on net methylation occur within the stream or on the stream bed and include factors such as small-scale temperature changes in the water column and photosynthetic activity of stream biofilm. With respect to stream monitoring, results from this study indicate (1) consistent timing in stream Hg and MMHg sampling is required for accurate assessment of long-term trends, (2) in situ measurements of turbidity can be used to quantify diel dynamics of both particulate Hg and MMHg concentrations, and (3) in situ fluorescing dissolved organic matter (FDOM), a potential proxy for DOC, was not capable of resolving diel dynamics of filtered Hg or MMHg.

54 ENVIRONMENTAL SCIENCES↗

The channel-source hypothesis: Empirical evidence for in-channel sourcing of dissolved organic carbon to explain hysteresis in a headwater mountain stream

Catchment hydrologists have long puzzled over the question: How can catchments rapidly generate storm flows and pulses of solutes in response to storm events? Conceptual models viewing catchments as composed of discrete source areas generating flow at unique time scales and with unique chemical characteristics have been used to explain the observed changes in flow and water chemistry. Surprisingly, those conceptual models usually do not treat the stream channel as one of the potential source areas. We propose the channel-source hypothesis in which the stream itself should be considered as a potential source with the same rigour as other contributing areas. We pose this in the spirit of the scientific use of the word: a hypothesis is not a proven idea but rather a provisional supposition serving as the basis for further study. We suggest that the channel should be considered as a potential source for dissolved organic carbon (DOC). Channels store substantial amounts of organic matter, and stream ecologists have long studied stream carbon cycling. From those studies, we know that leaching and decomposition can generate DOC from particulate organic carbon (POC). Further, POC is stored in channel ‘dead-zones’—regions of low flow velocity - that can be activated as flow velocity increases, thus releasing accumulated DOC during storms. All catchments are different; there is no reason to assume that channel sources are always important, in every catchment, in every storm. Thus, the channel-source hypothesis does not replace existing conceptual models. Instead, it adds another potential mechanism that may explain DOC dynamics observed in streams. The channel-source hypothesis has substantial implications for catchment studies examining sources of DOC in stream water or using DOC as a tracer to determine the locations of, and proportional contributions of, different source areas for streamflow generation.

54 ENVIRONMENTAL SCIENCES↗

Insight into the Competitive Adsorption Behavior of Polymer Chains in Silica Nanopores by Small-Angle Neutron Scattering

Processive hydrogenolysis catalysts, in which a metal nanoparticle (e.g., Pt) embedded at the bottom of a cylindrical silica nanopore can repeatedly cleave polymer chains and produce value-added hydrocarbon products, offer a potential solution for billions of tons of waste plastics. As the chain stays longer near the Pt catalysts, it would have a higher chance of getting cut, and therefore the molecular weight distribution of the product could be affected by the adsorption behavior of virgin chains (long polymers) versus cleaved chains (short polymers) into the nanopores. Further, this work reports a model study to understand the competitive adsorption behavior of the two different molecular weight polymers that are mixed, mimicking the reaction medium in the intermediate stage of the catalytic reaction. This study employs small-angle neutron scattering (SANS), which takes advantage of contrast differences between hydrogenous and deuterated polystyrenes to experimentally observe the relative composition of the two polymers in the silica nanopores. Our results reveal preferential adsorption of longer chains in the silica nanopores, which is consistent with the theoretical prediction in the literature for the case of the enthalpic attraction between polymers and pore walls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organic matter distribution in the icy environments of Taylor Valley, Antarctica

Glaciers can accumulate and release organic matter affecting the structure and function of associated terrestrial and aquatic ecosystems. Here we analyzed 18 ice cores collected from six locations in Taylor Valley (McMurdo Dry Valleys), Antarctica to determine the spatial abundance and quality of organic matter, and the spatial distribution of bacterial density and community structure from the terminus of the Taylor Glacier to the coast (McMurdo Sound). Our results showed that dissolved and particulate organic carbon (DOC and POC) concentrations in the ice core samples increased from the Taylor Glacier to McMurdo Sound, a pattern also shown by bacterial cell density. Fluorescence Excitation Emission Matrices Spectroscopy (EEMs) and multivariate parallel factor (PARAFAC) modeling identified one humic-like (C1) and one protein-like (C2) component in ice cores whose fluorescent intensities all increased from the Polar Plateau to the coast. The fluorescence index showed that the bioavailability of dissolved organic matter (DOM) also decreased from the Polar Plateau to the coast. Partial least squares path modeling analysis revealed that bacterial abundance was the main positive biotic factor influencing both the quantity and quality of organic matter. Marine aerosol influenced the spatial distribution of DOC more than katabatic winds in the ice cores. Certain bacterial taxa showed significant correlations with DOC and POC concentrations. Collectively, our results show the tight connectivity among organic matter spatial distribution, bacterial abundance and meteorology in the McMurdo Dry Valley ecosystem.

54 ENVIRONMENTAL SCIENCES↗

Soil organic matter, tree communities, and fungal communities across mycorrhizal gradients in the Eastern United States

We collected these data to investigate how mycorrhizal associations are related to soil C and N across four sites in the eastern U.S. broadleaf forest biome, which capture broad variability in climate and tree species. Our sites represented each of the four ecoregions in the eastern United States temperate forest—warm continental (New Hampshire), hot continental (Wisconsin), Prairie (Illinios), and subtropical (Georgia). This breadth naturally provided tree species diversity and allowed us to also investigate how soil C and N are related to canopy tree and EcM fungal community composition. Specifically, we analyzed the effects of mycorrhizal association, canopy tree family, and EcM fungal taxa on the proportion of C and N associated with soil minerals (MAOM) and bulk soil C:N. These are plot level data from forests in New Hampshire, Georgia, Wisconsin, and Illinois. The plots are 10 m in radius and vary across gradients of ectomycorrhizal tree basal area. Within each plot, data include the basal area of all trees >2 cm in diameter identified to species, the abundance of different fungal taxa based on ITS sequences, and the %C, %N, C:N of bulk soil and of soil density fractions (free light, occluded light, and particulate) as well as the proportion of soil C and N within each fraction. The soil data (both organic matter and fungal communities) are from the top 10 cm of the mineral soil. This also includes a meta-analysis of leaf litter k and C:N values for the tree species present in the forests.The "Tree_BA_ALL.csv" files include the basal area of all trees >2 cm in diameter at breast height within our 10 cm radii plots. The "Soil_Data_Final.csv" file contains the soil carbon and nitrogen in bulk and density fractions (concentrations as well as proportion for free light fraction (fLF), occluded light fraction (oLF), and heavy or dense fraction (HF), oxalate extractable iron and aluminum concentrations, as well as the geographic coordinates of each plot's location. The "FungiNonRelative.csv" file contains the abundances of fungal taxa identified via ITS sequencing for each plot (with the exception of 4 plots from GA where there was not enough quality DNA to extract).The "R_ReadyK.csv" and "R_Ready_CN.csv" files contain leaf litter decomposition constant (k) and C:N values from the literature for the tree species found at our sites.

54 ENVIRONMENTAL SCIENCES↗

Data and scripts associated with: “Burn severity and vegetation type control phosphorus concentration, molecular composition, and mobilization”

This data package is associated with the publication “Burn severity and vegetation type control phosphorus concentration, molecular composition, and mobilization” published in European Geophysical Union - Biogeosciences (Barnes et al. 2025). This study investigates how phosphorus (P) biogeochemistry is altered by burn severity in contrasting types of vegetation chars. This data package documents the workflow used to process and generate the main figures and statistics in the manuscript. The R scripts reference minimally processed P nuclear magnetic resonance (P-NMR) and X-ray absorption near edge structure (P-XANES) data, as well as fully processed data including total elemental composition of the solid chars, total elemental composition of the char leachates (particulate and aqueous phases), and leachate aqueous phase molybdate reactive P concentration. These source data and associated metadata can be found on ESS-DIVE at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1894135 (Grieger et al. 2022; v3). Files and scripts included in this data package finish the processing workflow for P-NMR and P-XANES data. These data can be used to gain a better understanding of bulk chemical changes in chars and their leachates, as well as detailed molecular changes to P. This data package is associated with the GitHub repository found at https://github.com/river-corridors-sfa/rcsfa-RC3-BSLE_P. This data package is comprised of a “data” folder and a series of data processing and analysis scripts. Details on how to recreate the workflow can be found in the Critical Details section of the readme and the “workflow_readme.md” file. The file-level metadata file (file ending in “flmd.csv”) lists all files contained in this data package and descriptions for each. The data dictionary (file ending in “dd.csv”) describes all tabular data columns and their respective definitions and units.

54 ENVIRONMENTAL SCIENCES↗

Airborne Measurements of Western U.S. Wildfire Emissions: Comparison with Prescribed Burning and Air Quality Implications

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total non methane organic compounds, and PM1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM1 emission estimate (1530 +/- 570 Gg/yr) is over 3 times that of the NEI PM2.5 estimate and is also higher than the PM2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions.

measured oxygenated volatile organic compounds↗

Use of Transmission Electron Microscopy for Analysis of Aerosol Particles and Strategies for Imaging Fragile Particles

For over 25 years, transmission electron microscopy (TEM) has provided a method for the study of aerosol particles with sizes from below the optical diffraction limit to several microns, resolving the particles as well as smaller features. The wide use of this technique to study aerosol particles has contributed important insights about environmental aerosol particle samples and model atmospheric systems. TEM produces an image that is a 2D projection of aerosol particles that have been impacted onto grids and, through associated techniques and spectroscopies, can contribute additional information such as the determination of elemental composition, crystal structure, and 3D particle structures. Soot, mineral dust, and organic/inorganic particles have all been analyzed using TEM and spectroscopic techniques. TEM, however, has limitations that are important to understand when interpreting data including the ability of the electron beam to damage and thereby change the structure and shape of particles, especially in the case of particles composed of organic compounds and salts. In this paper, we concentrate on the breadth of studies that have used TEM as the primary analysis technique. Another focus is on common issues with TEM and cryogenic-TEM. Insights for new users on best practices for fragile particles, that is, particles that are easily susceptible to damage from the electron beam, with this technique are discussed. Tips for readers on interpreting and evaluating the quality and accuracy of TEM data in the literature are also provided and explained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing f -Element Separations with ADAAM-EH: The Impact of Phase Modifiers and a DGA Aqueous Complexant

Recent investigations have used a 2-ethylhexyl diamide amine (ADAAM-EH) for Am/Cm separations in combination with N,N,N ',N '-tetraethyldiglycolamide as an aqueous complexant to achieve an unprecedented separation factor of 41. The aim of this research effort is to understand the speciation of trivalent lanthanide (Ln) and actinide (An) ions in the organic phase of an ADAAM-EH extraction system, both with and without phase modifiers (PM) (1-octanol and tri-n-butyl phosphate (TBP)). Leveraging spectroscopic techniques in combination with distribution ratio measurements provides an understanding of organic phase f-element ligand complexation. In the absence of PM, Ln is extracted in a stoichiometric 1:1 [M(ADAAM-EH) 1 (NO 3 ) x (H 2 O) 1 ](NO 3 ) 3-x complex. The addition of 1-octanol at 20 vol % results in multiple species present. One of the species is the same as the no PM case, and the other species results in an increased -OH coordination to the inner sphere, potentially displacing some NO 3 . In the case of TBP, increasing concentration results in additional red-shifted bands in the UV-visible spectra, suggesting the complexation of additional ligands of either ADAAM-EH or TBP. Finally, the new system knowledge obtained by and spectroscopic experiments will provide benchmarking information for computational studies of the inner- and outer-sphere coordination environments of f-element cations and insights into ADAAM-EH adduct formation with PM, like 1-octanol and TBP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new approach for measuring the carbon and oxygen content of atmospherically relevant compounds and mixtures

Abstract. Due to its complexity, gas- and particle-phase organic carbon in the atmosphere is often classified by its bulk physicochemical properties. However, there is a dearth of robust, moderate-cost approaches to measure the bulk chemical composition of organic carbon in the atmosphere. This is particularly true for the degree of oxygenation, which critically affects the properties and impacts of organic carbon but for which routine measurement approaches are lacking. This gap has limited the understanding of a wide range of atmospheric components, including particulate matter, the mass of which is monitored worldwide due to its health and environmental effects but the chemical characterization of which requires relatively high capital costs and complex operation by highly trained technical personnel. In this work, we demonstrate a new approach to estimate the mass of carbon and oxygen in analytes and mixtures that relies only on robust, moderate-cost detectors designed for use with gas chromatography. Organic compounds entering a flame ionization detector were found to be converted with approximately complete efficiency to CO2, which was analyzed downstream using an infrared detector to measure the mass of carbon analyzed. The ratio of the flame ionization detector (FID) signal generated to CO2 formed (FID∕CO2) was shown to be strongly correlated (R2=0.89) to the oxygen-to-carbon ratio (O∕C) of the analyte. Furthermore, simple mixtures of analytes behaved as the weighted average of their components, indicating that this correlation extends to mixtures. These properties were also observed to correlate well with the sensitivity of the FID estimated by structure activity relationships (quantified as the relative effective carbon number). The relationships between measured FID∕CO2, analyte O∕C, and FID sensitivity allow the estimation of one property from another with <15 % error for mixtures and <20 % error for most individual analytes. The approach opens the possibility of field-deployable, autonomous measurement of the carbon and oxygen content of particulate matter using time-tested, low-maintenance detectors, though such an application would require some additional testing on complex mixtures. With some instrumental modifications, similar measurements on gas-phase species may be feasible. Moreover, the potential expansion to additional gas chromatography detectors may provide concurrent measurement of other elements (e.g., sulfur, nitrogen).

42 ENGINEERING↗

Gulf of Mexico Air Quality: CALIPSO Support for Gulf of Mexico Air Quality Relating to the Deepwater Horizon Oil Spill

On April 20, 2010, an oil platform belonging to BP exploded and leaked a huge volume of oil into the Gulf of Mexico. In an effort to control the spread of the oil, BP applied dispersants such as Corexit and conducted in-situ burnings of the oil. This catastrophe created a complex chain of events that affected not only the fragile water and land ecosystems, but the humans who breathe the air every day. Thousands of people were exposed to fumes associated with oil vapors from the spill, burning of the oil, and the toxic mixture of dispersants. While aiding in clean-up efforts, local fishermen were directly exposure to fumes when working on the Gulf. A notable amount of Gulf Coast residents were also exposed to the oil fumes as seasonal southeasterly winds blew vapors toward land. The Volatile Organic Compounds (VOC) found in oil vapors include: benzene, toluene, ethyl benzene, xylene, naphthalene, hydrogen sulfide and particulate matter (PM). Increases in water temperature and sunlight due to the summer season allow for these VOCs and PM to evaporate into the air more rapidly. Aside from the VOCs found in oil vapors, the dispersant being used to break up the oil is highly toxic and is thought to be even more toxic than the oil itself (EPA website, 2010). To protect human health, the environment, and to make informed policy decisions relevant to the spill, the EPA Region 6 has continuously monitored the affected areas carefully for levels of pollutants in the outdoor air that are associated with petroleum products and the burning of oil along the coast. In an effort to prevent, prepare for, and respond to future oil spills that occur in and around inland waters of the United States, the EPA has been working with local, state, and federal response partners. Air quality measurements were collected by the EPA at five active monitoring systems stationed along the coast.

Nguyen, Myngoc T.↗

Near-canopy horizontal concentration heterogeneity of semivolatile oxygenated organic compounds and implications for 2-methyltetrols primary emissions

Semivolatile oxygenated organic compounds (SV-OVOCs) are important atmospheric species, in particular for the production and chemistry of atmospheric particulate matter and related impacts on air quality and climate. In this study, SV-OVOCs were collected in the horizontal plane of the roughness layer over the tropical forest in the central Amazon during the wet season of 2018. A sampler mounted to a copter-type, hovering unmanned aerial vehicle was used. Underlying the collection region, a plateau forest transitioned into a slope forest across several hundred meters. The concentrations of pinonic and pinic acids, which are monoterpene oxidation products, had no statistical difference over the two forests. By comparison, across the study period, differences in the concentration of 2-methyltetrols, which are products of isoprene oxidation, ranged from -70% to +480% over the two forests. The chemical lifetime of 2-methyltetrols in the atmosphere is sufficiently long that heterogeneity in the isoprene emission rate from the two forests followed by atmospheric oxidation does not explain the concentration heterogeneity of 2-methyltetrols. Standing waves and local meteorology also cannot account for the heterogeneity. Of the possibilities considered, the most plausible explanation is the direct emission from the forest of 2-methyltetrols produced through biological processes within the plants. Under this explanation, the rate of direct SV-OVOC emissions should be modulated by forest type and related environmental stressors. Direct emissions of SV-OVOCs should be more broadly considered for constraining and improving models of atmospheric composition, transport, and chemistry over tropical forests.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Characterisation of Suspended Particles in the Mackenzie River Plume (Canadian Arctic Ocean) and Implications for Ocean Colour Remote Sensing

Climate change significantly impacts Arctic shelf regions in terms of air temperature, ultraviolet radiation, melting of sea ice, precipitation, thawing of permafrost and coastal erosion. Direct consequences have been observed on the increasing Arctic river flow and a large amount of organic carbon sequestered in soils at high latitudes since the last glacial maximum can be expected to be delivered to the Arctic Ocean during the coming decade. Monitoring the fluxes and fate of this terrigenous organic carbon is problematic in such sparsely populated regions unless remote sensing techniques can be developed and proved to be operational. The main objective of this study is to develop an ocean colour algorithm to operationally monitor dynamics of suspended particulate matter (SPM) on the Mackenzie River continental shelf (Canadian Arctic Ocean) using satellite imagery. The water optical properties are documented across the study area and related to concentrations of SPM and particulate organic carbon (POC). Robust SPM and POC : SPM proxies are identified, such as the light backscattering and attenuation coefficients, and relationships are established between these optical and biogeochemical parameters. Following a semi-analytical approach, a regional SPM quantification relationship is obtained for the inversion of the water reflectance signal into SPM concentration. This relationship is reproduced based on independent field optical measurements. It is successfully applied to a selection of MODIS satellite data which allow estimating fluxes at the river mouth and monitoring the extension and dynamics of the Mackenzie River surface plume in 2009, 2010 and 2011. Good agreement is obtained with field observations representative of the whole water column in the river delta zone where terrigenous SPM is mainly constrained (out of short periods of maximum river outflow). Most of the seaward export of SPM is observed to occur within the west side of the river mouth. Future work will require the validation of the developed SPM regional algorithm based on match-ups with field measurements, then the routine application to ocean colour satellite data in order to better estimate the fluxes and fate of SPM and POC delivered by the Mackenzie River to the Arctic Ocean.

Mackenzie River plume↗

Effects of Site and Magnetic Disorder on the Oxygen Vacancy Formation and Electronic and Optical Properties of La x Sr 1– x CoO 3–δ and SrFe y Co 1– y O 3–δ [plus supplemental information]

Disorder is an inevitable issue in practical applications of perovskites with the A-site occupied by La/Sr and the B-site occupied by Co/Fe. We performed density functional theory calculations to reveal the site and magnetic disorder effect on the oxygen vacancy formation and the electronic and optical properties of La x Sr 1–x CoO 3–δ and SrFe y Co 1–y O 3–δ systems. Generally, site disorder has little influence on the physical properties we studied, while magnetic disorder has a property-dependent effect for La A-site and Fe B-site doping of SrCoO 3 . Compared to ordered ferromagnetic (FM) calculations, disordered paramagnetic (PM) results can better describe the high-temperature behavior of lattice expansion and the multiple spin states of Co ions in La x Sr 1–x CoO 3 . The oxygen vacancy formation energy results show that the magnetic disorder has a more remarkable effect on SrFe y Co 1–y O 3–δ systems with a robust magnetic order than that on the La x Sr 1–x CoO 3–δ systems with a fragile magnetic order. The electronic structures in the PM phase have less spin polarization and broadened bands, by which the optical absorptions from the single spin channel transition in the FM phase have an obvious change in the magnitude and/or the trend. Furthermore, our work provides guidance for where and why to consider the disorder.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of Road Salt Aerosol Driving Inland Wintertime Atmospheric Chlorine Chemistry

Inland sources of particulate chloride for atmospheric nitryl chloride (ClNO2) formation remain unknown and unquantified, hindering air quality assessments. Globally each winter, tens of millions of tons of road salt are spread on roadways for deicing. Here, we identify road salt aerosol as the primary chloride aerosol source, accounting for 80–100% of ClNO 2 formation, at an inland urban area in the wintertime. This study provides experimental evidence of the connection between road salt and air quality through the production of this important reservoir for nitrogen oxides and chlorine radicals, which significantly impact atmospheric composition and pollutant fates. A numerical model was employed to quantify the contributions of chloride sources to ClNO 2 production. The traditional method for simulating ClNO 2 considers chloride to be homogeneously distributed across the atmospheric particle population; yet, we show that only a fraction of the particulate surface area contains chloride. Our new single-particle parametrization considers this heterogeneity, dramatically lowering overestimations of ClNO 2 levels that have been routinely reported using the prevailing methods. The identification of road salt as a ClNO 2 source links this common deicing practice to atmospheric composition and air quality in the urban wintertime environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗