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At least 91 records · Page 5

Black Carbon in Estuarine and Coastal Ocean Dissolved Organic Matter

Black carbon (BC) in ultrafiltered high-molecular-weight DOM (UDOM) was measured in surface waters of Delaware Bay, Chesapeake Bay and the adjacent Atlantic Ocean (USA) to ascertain the importance of riverine and estuarine DOM as a source of BC to the ocean. BC comprised 5-72% of UDOM-C (27+/-l7%) and on average 8.9+/-6.5% of dissolved organic carbon (DOC) with higher values in the turbid region of the Delaware Estuary and lower yields in the river and coastal ocean. The spatial and seasonal distributions of BC along the salinity gradient of Delaware Bay suggest that the higher levels of BC in surface water UDOM originated from localized sources, possibly from atmospheric deposition or released from resuspended sediments. Black carbon comprised 4 to 7% of the DOC in the coastal Atlantic Ocean, revealing that river-estuary systems are important exporters of colloidal BC to the ocean. The annual flux of BC from Delaware Bay UDOM to the Atlantic Ocean was estimated at 2.4x10(exp 10) g BC yr(exp -1). The global river flux of BC through DOM to the ocean could be on the order of 5.5x1O(exp 12)g BC yr (exp -1). These results support the hypothesis that the DOC pool is the intermediate reservoir in which BC ages prior to sedimentary deposition.

Mannino, Antonio↗

Radiative Transfer Modeling of a Large Pool Fire by Discrete Ordinates, Discrete Transfer, Ray Tracing, Monte Carlo and Moment Methods

Five computational methods for solution of the radiative transfer equation in an absorbing-emitting and non-scattering gray medium were compared on a 2 m JP-8 pool fire. The temperature and absorption coefficient fields were taken from a synthetic fire due to the lack of a complete set of experimental data for fires of this size. These quantities were generated by a code that has been shown to agree well with the limited quantity of relevant data in the literature. Reference solutions to the governing equation were determined using the Monte Carlo method and a ray tracing scheme with high angular resolution. Solutions using the discrete transfer method, the discrete ordinate method (DOM) with both S(sub 4) and LC(sub 11) quadratures, and moment model using the M(sub 1) closure were compared to the reference solutions in both isotropic and anisotropic regions of the computational domain. DOM LC(sub 11) is shown to be the more accurate than the commonly used S(sub 4) quadrature technique, especially in anisotropic regions of the fire domain. This represents the first study where the M(sub 1) method was applied to a combustion problem occurring in a complex three-dimensional geometry. The M(sub 1) results agree well with other solution techniques, which is encouraging for future applications to similar problems since it is computationally the least expensive solution technique. Moreover, M(sub 1) results are comparable to DOM S(sub 4).

Jensen, K. A.↗

Satellite-Derived Distributions, Inventories and Fluxes of Dissolved and Particulate Organic Matter Along the Northeastern U.S. Continental Margin

Estuaries and the coastal ocean experience a high degree of variability in the composition and concentration of particulate and dissolved organic matter (DOM) as a consequence of riverine and estuarine fluxes of terrigenous DOM, sediments, detritus and nutrients into coastal waters and associated phytoplankton blooms. Our approach integrates biogeochemical measurements, optical properties and remote sensing to examine the distributions and inventories of organic carbon in the U.S. Middle Atlantic Bight and Gulf of Maine. Algorithms developed to retrieve colored DOM (CDOM), Dissolved (DOC) and Particulate Organic Carbon (POC) from NASA's MODIS-Aqua and SeaWiFS satellite sensors are applied to quantify the distributions and inventories of DOC and POC. Horizontal fluxes of DOC and POC from the continental margin to the open ocean are estimated from SeaWiFS and MODIS-Aqua distributions of DOC and POC and horizontal divergence fluxes obtained from the Northeastern North Atlantic ROMS model. SeaWiFS and MODIS imagery reveal the importance of estuarine outflow to the export of CDOM and DOC to the coastal ocean and a net community production of DOC on the shelf.

Mannino, A.↗

Data and scripts associated with “Riverine dissolved organic matter transformations increase with watershed area, water residence time, and Damköhler numbers in nested watersheds” (v2)

This data package is associated with the publication “Riverine dissolved organic matter transformations increase with watershed area, water residence time, and Damköhler numbers in nested watersheds” submitted to Biogeochemistry by Ryan et al., 2024 (DOI: https://doi.org/10.1007/s10533-024-01169-5). This study aims to investigate fundamental and transferable drivers of dissolved organic matter (DOM) diversity across five nested watersheds within the contiguous United States. DOM diversity was explored using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The samples and the unprocessed FTICR-MS data used in this study are publicly available on the Environmental System Science Data Infrastructure for a Virtual Ecosystem (ESS-DIVE) data repository (see DOIs below). The data for the Willamette, Gunnison, Connecticut, and Deschutes basins were collected as part of a collaboration between the Watershed Rules of Life (WROL) project and Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS). The data for the Yakima River basin (YRB) was collected by the PNNL River Corridor SFA. The raw, unprocessed FTICR-MS data with additional (meta)data can be found at doi:10.15485/1895159 for WROL samples and doi:10.15485/1898912 for YRB samples. This data package contains the processed data used in the associated manuscript. This package also contains ancillary geospatial, hydrological, and geochemical information that supports the interpretation of the FTICR-MS data within Ryan et al., 2024. This data package is associated with the GitHub repository found at https://github.com/WHONDRS-Hub/rcsfa-RC4-WROL-YRB_DOM_Diversity. This data package was originally published August 2024. It was updated January 2025 (modified files). See the change history in the readme more details. At the directory level, the data package is comprised of three folders: (1) data, (2) output, and (3) src; and five additional files including the data dictionary (file ending in "_dd.csv”) and file-level metadata (file ending in “_flmd.csv”). The “src” folder contains the scripts used to process the FTICR data, conduct the analyses, and produce the manuscript figures. The inputs for these scripts are in the “data” folder and the returned outputs in the “output” folder. Inputs include temporal and spatial metadata associated with the sampling efforts, processed FTICR data, and total and normalized putative biochemical transformations per sample. Outputs include cleaned and combined data presented as tables, descriptive statistics, and plots. The file-level metadata file lists all files contained in this data package and descriptions for each. The data dictionary describes the units and definitions for each tabular data column or row header.

54 ENVIRONMENTAL SCIENCES↗

Increasing temperature and flow management alter mercury dynamics in East Fork Poplar Creek

East Fork Poplar Creek (EFPC) is a mercury (Hg) contaminated creek in east Tennessee, USA. Stream restoration activities included the initiation of a flow management programme in 1996 in which water from a nearby lake was pumped to the head of the creek. We conducted regular water sampling for 2 years along the length of EFPC during active flow management and for 5 years after flow management stopped. Total Hg and total monomethylmercury (MMHg) concentration and flux decreased in the uppermost reaches of EFPC that were closest to the point of water addition. Most water quality parameters, including DOC concentration, remained unchanged after flow management termination. Nevertheless, SUVA 254 , a measure of dissolved organic matter (DOM) composition, increased and coincided with increased dissolved Hg (Hg D ) concentration and flux and decreased Hg solid-water partitioning coefficients throughout EFPC. Higher SUVA 254 and Hg D concentration have potential implications for bioavailability and MMHg production. Total and dissolved MMHg concentrations increased in lower reaches of EFPC after the end of flow management and these increases were most pronounced during spring and early summer when biota are more susceptible to exposure and uptake. A general warming trend in the creek after active flow management ended likely acted in concert with higher Hg D concentration to promote higher MMHg concentration. Total and dissolved MMHg concentrations were positively correlated with water temperature above a threshold value of 10°C. Concentration changes for Hg and MMHg could not be accounted for by changes in creek discharge that accompanied the cessation of flow management. In addition to the changing DOM composition in-stream, other watershed-scale factors likely contributed to the observed patterns, as these changes occurred over months rather than instantaneously after flow management stopped. Nevertheless, similar changes in MMHg have not been observed in a tributary to EFPC.

54 ENVIRONMENTAL SCIENCES↗

A History of Molecular Level Analysis of Natural Organic Matter by FTICR Mass Spectrometry and The Paradigm Shift in Organic Geochemistry

Natural organic matter (NOM) is a complex mixture of biogenic molecules resulting from the deposition and transformation of plant and animal matter. It has long been recognized that NOM plays an important role in many geological, geochemical, and environmental processes. Of particular concern is the fate of NOM in response to a warming climate in environments that have historically sequestered carbon (e.g., peatlands and swamps) but may transition to net carbon emitters. In this review, we will highlight developments in the application of high-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) in identifying the individual components of complex NOM mixtures, focusing primarily on the fraction that is dissolved in natural waters (dissolved organic matter or DOM). We will first provide some historical perspective on developments in FTICR technology that made molecular-level characterizations of DOM possible. In conclusion, a variety of applications of the technique will then be described, followed by our view of the future of high-field FTICR MS in carbon cycling research, including a particularly exciting metabolomic approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isotope Exchange between Mercuric [Hg(II)] Chloride and Hg(II) Bound to Minerals and Thiolate Ligands: Implications for Enriched Isotope Tracer Studies

Enriched mercury (Hg) stable isotopes have been widely used as tracers in field and laboratory investigations of Hg(II) biogeochemical transformations such as methylation and demethylation. Few studies, however, have considered concurrent isotope exchange reactions between newly spiked and pre-existing Hg(II) in environmental matrices, which may alter redistribution and thus transformation of the spiked and pre-existing Hg(II). Using enriched 198 Hg [as mercuric Hg(II) or HgCl n species], this study investigated isotope exchange between 198 Hg and pre-existing Hg(II) bound to metacinnabar (β-HgS), sediments, low-molecular-weight (LMW) thiols, and dissolved organic matter (DOM). The impact of isotope exchange on methylmercury production in the presence of organic ligands was also evaluated with an iron-reducing bacterium Geobacter sulfurreducens PCA in a phosphate buffered solution (pH 7.4). Here, we found that spiked 198 Hg readily exchanged with mineral-bound ambient Hg(II) despite concurrent Hg(II) adsorption and immobilization on the solids. Rapid exchange (<3 min) was also observed between spiked 198 Hg and 200 Hg pre-equilibrated with LMW thiols and DOM in solution. While the exchange did not cause net changes in Hg(II) chemical speciation, it resulted in redistribution of Hg(II) isotopes bound to the ligands and thus an apparently similar methylation rate and magnitude of the spiked 198 Hg and pre-existing 200 Hg by PCA cells when 198 Hg and 200 Hg were added at 1:1 ratio. These observations underscore the importance of isotope exchange when an enriched Hg isotope is applied in environmental matrices, as the exchange could potentially lead to biased rate calculations of Hg(II) transformation and bioaccumulation and thus risk assessments of new Hg(II) input to the natural ecosystems.

58 GEOSCIENCES↗

Molecular Transformation of Dissolved Organic Matter during the Processes of Wildfire, Alum Coagulation, and Disinfection Using ESI(-) and ESI(+) FT-ICR MS

Forest fires alter the quality of terrestrial dissolved organic matter (DOM) flushed into source water, which could be further changed during alum coagulation and serve as potential disinfection byproduct (DBP) precursors in water facilities. To unveil this molecular transformation, we applied 12T Fourier transform ion cyclotron resonance mass spectrometry on a controlled study which used the leachates of black and white ashes (collected immediately after the 2013 Rim Fire, CA) along with unburned white fir (Abies concolor) and ponderosa pine (Pinus ponderosa). Here, results showed that the assigned features in DOM from burned ashes had a smaller molecular weight (MW), contained more unsaturated, aromatic, and oxidized and less fraction of labile compounds, and were enriched with nitrogen, relative to unburned litters. After alum coagulation, we observed the disappeared features with higher MW and S/C and N/C atom ratios than the resistant features. During the following disinfections, the disappeared features serving as the potential DBP precursors had higher MW and unsaturation degree, contained more S- and N-containing functionalities, and were more aromatic, compared to the resistant features. Our study suggested organic compounds with small MW and high aromaticity as the targets for water facilities to improve post-fire drinking water quality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

D-Egg: a dual PMT optical module for IceCube

The D-Egg, an acronym for "Dual optical sensors in an Ellipsoid Glass for Gen2," is one of the optical modules designed for future extensions of the IceCube experiment at the South Pole. The D-Egg has an elongated-sphere shape to maximize the photon-sensitive effective area while maintaining a narrow diameter to reduce the cost and the time needed for drilling of the deployment holes in the glacial ice for the optical modules at depths up to 2700 m. The D-Egg design is utilized for the IceCube Upgrade, the next stage of the IceCube project also known as IceCube-Gen2 Phase 1, where nearly half of the optical sensors to be deployed are D-Eggs. With two 8-inch high-quantum efficiency photomultiplier tubes (PMTs) per module, D-Eggs offer an increased effective area while retaining the successful design of the IceCube digital optical module (DOM). The convolution of the wavelength-dependent effective area and the Cherenkov emission spectrum provides an effective photodetection sensitivity that is 2.8 times larger than that of IceCube DOMs. The signal of each of the two PMTs is digitized using ultra-low-power 14-bit analog-to-digital converters with a sampling frequency of 240 MSPS, enabling a flexible event triggering, as well as seamless and lossless event recording of single-photon signals to multi-photons exceeding 200 photoelectrons within 10 ns. Mass production of D-Eggs has been completed, with 277 out of the 310 D-Eggs produced to be used in the IceCube Upgrade. In this paper, we report the design of the D-Eggs, as well as the sensitivity and the single to multi-photon detection performance of mass-produced D-Eggs measured in a laboratory using the built-in data acquisition system in each D-Egg optical sensor module.

47 OTHER INSTRUMENTATION↗

Demethylation or Sorption? The Fate of Methylmercury in the Presence of Manganese Dioxide

Manganese oxide (MnO 2 ) amendments to mercury (Hg)-contaminated sediment have been shown to decrease methylmercury (MeHg) concentrations in sediment porewater. In the absence of solid-phase MeHg measurements, it is unclear whether the decreased porewater concentrations are due to inhibition of methylation, adsorption of the MeHg to the MnO 2 , demethylation of MeHg catalyzed by the MnO 2 , or some combination of these mechanisms. We conducted controlled laboratory experiments to determine whether MeHg losses from solution in the presence of amorphous MnO 2 are due to sorption or demethylation. In this work, we quantified MeHg in the dissolved phase and solid phase and found that no demethylation occurred. We used batch and isotherm experiments to determine MeHg sorption efficiency to MnO 2 in a variety of solutions with varying ionic strength and dissolved organic matter (DOM) concentration. Isotherms over an initial concentration range of 5–500 ng/L of MeHg showed no saturation effects. Increasing ionic strength from 0.012 M to 0.1 M produced relatively minor decreases in MeHg sorption. Increasing DOM concentrations from 0.64 to 16.4 mg C/L yielded substantial decreases in MeHg sorption. Under the experimental conditions, MnO2 is a less efficient MeHg sorbent compared to other sorbent materials, such as Thiol-SAMMS®, activated carbon, and biochar.

42 ENGINEERING↗

Isotopically resolved neutron total cross sections at intermediate energies

The neutron total cross sections σ tot of 16,18 O, 58 64 Ni, 103 Rh, and 112,124 Sn have been measured at the Los Alamos Neutron Science Center from low to intermediate energies (3 ≤ E lab ≤ 450 MeV) by leveraging wave-form-digitizer technology. The σ tot relative differences between isotopes are presented, revealing additional information about the isovector components needed for an accurate optical-model description away from stability. Digitizer-enabled σ tot -measurement techniques are discussed and a series of uncertainty-quantified dispersive optical model (DOM) analyses using these new data is presented, validating the use of the DOM for modeling light systems ( 16,18 O) and systems with open neutron shells ( 58,64 Ni and 112,124 Sn). Here, the valence-nucleon spectroscopic factors extracted for each isotope reaffirm the usefulness of high-energy proton reaction cross sections for characterizing depletion from the mean-field expectation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Effects of nitrogen fertilization and bioenergy crop type on topsoil organic carbon and total Nitrogen contents in middle Tennessee USA

Nitrogen (N) fertilization affects bioenergy crop growth and productivity and consequently carbon (C) and N contents in soil, it however remains unclear whether N fertilization and crop type individually or interactively influence soil organic carbon (SOC) and total N (TN). In a three-year long fertilization experiment in switchgrass (SG: Panicum virgatum L.) and gamagrass (GG: Tripsacum dactyloides L.) croplands in Middle Tennessee USA, soil samples (0–15cm) were collected in plots with no N input (NN), low N input (LN: 84 kg N ha -1 yr -1 in urea) and high N input (HN: 168 kg N ha -1 yr -1 in urea). Besides SOC and TN, the aboveground plant biomass was also quantified. In addition to a summary of published root morphology data based on a separated mesocosm experiment, the root leachable dissolved organic matter (DOM) of both crops was also measured using archived samples. Results showed no significant interaction of N fertilization and crop type on SOC, TN or plant aboveground biomass (ABG). Relative to NN, HN (not LN) significantly increased SOC and TN in both crops. Though SG showed a 15–68% significantly higher ABG than GG, GG showed a 9.3–12% significantly higher SOC and TN than SG. The positive linear relationships of SOC or TN with ABG were identified for SG. However, GG showed structurally more complex and less readily decomposed root DOM, a larger root volume, total root length and surface area than SG. Collectively, these suggested that intensive N fertilization could increase C and N stocks in bioenergy cropland soils but these effects may be more likely mediated by the aboveground biomass in SG and root chemistry and morphology in GG. Future studies are expected to examine the root characteristics in different bioenergy croplands under the field fertilization experiment.

54 ENVIRONMENTAL SCIENCES↗

The Influence of Microbial Priming Effects on the Hydro-bio-geochemistry of Large River Reservoirs

River-tributary confluences, where diverse organic matter (OM) sources mix, are considered aquatic critical zones for biogeochemical cycling. Here we evaluate dissolved OM composition and bioavailability in the mainstem of the Columbia River and three of its tributaries (Snake, Yakima, and Walla Walla rivers) along a hydrologic gradient in the Columbia River drainage basin using a variety of bulk and molecular level measurements. Field replicates and mixtures representing river-tributary confluences were incubated in the dark for 15 days to investigate the response of the microbial community to varying OM quantity/composition. The Columbia, Snake, and Yakima rivers did not differ in dissolved organic carbon (DOC), fluorescent dissolved OM (fDOM), or Chlorophyll-a (Chl-a) concentrations. However, the Walla Walla River had significantly greater DOC, fDOM, and Chl-a concentrations, indicative of greater contributions from algal DOM. FT-ICR-MS spectra for Walla Walla had significantly more peaks corresponding to amino sugars, carbohydrates and proteins while the Columbia River had more peaks for lignin, unsaturated hydrocarbons, and condensed aromatics. When incubated for 15 days in the dark, total DOC did not decrease for any of the river samples. DOC did decrease, however, in a mix representing the confluence of the Columbia and Walla Walla rivers, suggesting the microbial consortia of the Columbia River were primed by the Walla Walla River OM. OM composition was significantly different for several compound classes (e.g., lignin, protein, and tannin) following the incubations of unmixed river and tributary samples. However, the microbial community in the Walla Walla-Columbia mixture appeared to be indiscriminate of the molecular structure of the DOM as the compound class distribution did not change significantly. This provides preliminary evidence that the heterotrophs in river-tributary critical zones remineralize diverse OM structures.

54 ENVIRONMENTAL SCIENCES↗

Impacts of Hurricane Disturbance on Water Quality across the Aquatic Continuum of a Blackwater River to Estuary Complex

Hurricanes cause landscape-scale disturbances that affect biogeochemical cycling and water quality in coastal ecosystems. During Hurricane Irma’s passage through northern Florida, water movements driven by wind velocities up to 105 km h-1 caused a salinity peak in an estuary/blackwater river complex. Water quality was monitored across the 15 km site to detect the magnitude and duration of disturbance. Saline water intruded 15 km inland into a freshwater portion of the river that peaked at a salinity of 2 psu. Due to the volume of precipitation from the hurricane, significant runoff of freshwater and dissolved organic matter (DOM) caused a decrease in salinity, dissolved oxygen (DO), and Chlorophyll-a concentrations while increasing turbidity and fluorescent dissolved organic matter (fDOM). The disturbance caused rapid changes observed by in-situ water quality monitors over a 3-week period, but some effects persisted for longer periods as shown by 3-month weekly water sampling. This disturbance caused shifts in DOM loading, altered salinity dynamics, and reshaped landscapes due to wind and wave surge both in upland marsh and downstream estuary. Hurricane disturbance temporarily and abruptly alters the aquatic continuum, and observations of system response can help us understand the mechanisms associated with ecosystem resilience and recovery.

54 ENVIRONMENTAL SCIENCES↗

Black Carbon in Estuarine and Coastal Ocean Dissolved Organic Matter

Analysis of high-molecular-weight dissolved organic matter (DOM) from two estuaries in the northwest Atlantic Ocean reveals that black carbon (BC) is a significant component of previously uncharacterized DOM, suggesting that river-estuary systems are important exporters of recalcitrant dissolved organic carbon to the ocean.

Mannino, Antonio↗

Investigating the Impact of UV Radiation on High-Altitude Shallow Lake Habitats, Life Diversity, and Life Survival Strategies: Clues for Mars' Past Habitability Potential?

We present data and results from an ongoing project of astrobiological high-altitude expeditions investigating the highest and least explored perennial lakes on Earth in the Bolivian and Chilean Andes, including several volcanic crater lakes nearing and beyond 6,000 m in elevation. In the next five years, they will provide the first integrated long-term astrobiological characterization and monitoring of lacustrine environments and their biology for such altitude. These extreme lakes are natural laboratories. They provide the field data missing beyond 4,000 m to complete our understanding of terrestrial lakes and biota. Research on the effects of UV has been performed in lower altitude lakes and models of UV flux over time are being developed. Lakes showing a high content of dissolved organic material (DOM) shield organisms from UV. DOM acts as a natural sunscreen as it influences the water transparency, therefore is a determinant of photic zone depth. In sparsely vegetated alpine areas, lakes are clearer and offer less protection from UV to organisms living in the water. Transparent water and high UV irradiance may maximize the penetration and effect of UV radiation. Shallow-water communities in these lakes are particularly sensitive to UV radiation. The periphyton can live on various susbtrates. While on rocks, it includes immobile species that cannot seek low UV refuges unlike sediment-dwelling periphyton or alpine phytoflagellates which undergo vertical migration. Inhibition of algal photosynthesis by UV radiation has been documented in laboratory and showed that phytoplankton production is reduced by formation of nucleic acid lesions or production of peroxides and free oxygen radicals. of peroxides and free oxygen radicals. Our project is providing the field data that is missing from natural laboratories beyond 4,000 m and will complement the vision of the effects of UV on life and its adaptation modes (or lack thereof).

Cabrol, A.↗

A Numerical Investigation of the Extinction of Low Strain Rate Diffusion Flames by an Agent in Microgravity

Our goal has been to investigate the influence of both dilution and radiation on the extinction process of nonpremixed flames at low strain rates. Simulations have been performed by using a counterflow code and three radiation models have been included in it, namely, the optically thin, the narrowband, and discrete ordinate models. The counterflow flame code OPPDIFF was modified to account for heat transfer losses by radiation from the hot gases. The discrete ordinate method (DOM) approximation was first suggested by Chandrasekhar for solving problems in interstellar atmospheres. Carlson and Lathrop developed the method for solving multi-dimensional problem in neutron transport. Only recently has the method received attention in the field of heat transfer. Due to the applicability of the discrete ordinate method for thermal radiation problems involving flames, the narrowband code RADCAL was modified to calculate the radiative properties of the gases. A non-premixed counterflow flame was simulated with the discrete ordinate method for radiative emissions. In comparison with two other models, it was found that the heat losses were comparable with the optically thin and simple narrowband model. The optically thin model had the highest heat losses followed by the DOM model and the narrow-band model.

Puri, Ishwar K.↗