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At least 397 records · Page 22

BOREAS TGB-5 Dissolved Organic Carbon Data from NSA Beaver Ponds

The BOReal Ecosystem-Atmosphere Study Trace Gas Biogeochemistry (BOREAS TGB-5) team collected several data sets related to carbon and trace gas fluxes and concentrations in the Northern Study Area (NSA). This data set contains concentrations of dissolved organic and inorganic carbon species from water samples collected at various NSA sites. In particular, this set covers the NSA Tower Beaver Pond Site and the NSA Gillam Road Beaver Pond Site, including data from all visits to open water sampling locations during the BOREAS field campaigns from April to September 1994. The data are provided in tabular ASCII files.

Bourbonniere, Rick↗

Manipulation of Microenvironment with a Built-in Electrochemical Actuator in Proximity of a Dissolved Oxygen Microsensor

Abstract - Biochemical sensors for continuous monitoring require dependable periodic self- diagnosis with acceptable simplicity to check its functionality during operation. An in situ self- diagnostic technique for a dissolved oxygen microsensor is proposed in an effort to devise an intelligent microsensor system with an integrated electrochemical actuation electrode. With a built- in platinum microelectrode that surrounds the microsensor, two kinds of microenvironments, called the oxygen-saturated or oxygen-depleted phases, can be created by water electrolysis depending on the polarity. The functionality of the microsensor can be checked during these microenvironment phases. The polarographic oxygen microsensor is fabricated on a flexible polyimide substrate (Kapton) and the feasibility of the proposed concept is demonstrated in a physiological solution. The sensor responds properly during the oxygen-generating and oxygen- depleting phases. The use of these microenvironments for in situ self-calibration is discussed to achieve functional integration as well as structural integration of the microsensor system.

Kim, Chang-Soo↗

Dissolved gases in perennially ice-covered lakes of the McMurdo Dry Valleys, Antarctica

Measurements of dissolved N2, O2, Ar, CO2, and CH4 were made in perennially ice-covered Lake Hoare. Results confirm previous reports that O2 concentrations in the upper water column exceed atmospheric equilibrium and that N2 and Ar are supersaturated throughout the water column. The mean supersaturation of N2 was found to be 2.0 (+/- 0.37) and Ar was 3.8 (+/- 1.1). The ratios of N2/Ar (20.3 +/- 13.8), and O2/Ar (22.5 +/- 4.0) at the ice-water interface are consistent with those previously measured, suggesting that bubble formation is the main process for removing gas from the lake. However, the saturations of N2 and Ar greatly exceed those previously predicted for degassing by bubble formation only at the ice-water interface. The data support the hypothesis that removal of gas by bubbles occurs in the water column to a depth of 11 m in Lake Hoare. CO2 concentration increases from near zero at the ice-water interface to 80-100 times saturation at and below the chemocline at c. 28 m. There is considerable variability in the gas concentrations throughout the water column; samples separated in depth by one metre may vary by more than 50% in gas content. It is likely that this phenomenon results from the lack of turbulent mixing in the water column. Methane (c. 2 micrograms l-1) was detected below the chemocline and immediately above the sediment/water interface at a depth of 30 m. Samples from lakes Vanda, Joyce, and Miers, also show supersaturations of O2, N2, and Ar at levels similar to levels found in Lake Hoare.

NASA Discipline Exobiology↗

Microscale characterization of dissolved organic matter production and uptake in marine microbial mat communities

Intertidal marine microbial mats exhibited biologically mediated uptake of low molecular weight dissolved organic matter (DOM), including D-glucose, acetate, and an L-amino acid mixture at trace concentrations. Uptake of all compounds occurred in darkness, but was frequently enhanced under natural illumination. The photosystem 2 inhibitor, 3-(3,4-dichlorophenyl)-1,1-dimethyl urea (DCMU) generally failed to inhibit light-stimulated DOM uptake. Occasionally, light plus DCMU-amended treatments led to uptake rates higher than light-incubated samples, possibly due to phototrophic bacteria present in subsurface anoxic layers. Uptake was similar with either 3H- or 14C-labeled substrates, indicating that recycling of labeled CO2 via photosynthetic fixation was not interfering with measurements of light-stimulated DOM uptake. Microautoradiographs showed a variety of pigmented and nonpigmented bacteria and, to a lesser extent, cyanobacteria and eucaryotic microalgae involved in light-mediated DOM uptake. Light-stimulated DOM uptake was often observed in bacteria associated with sheaths and mucilage surrounding filamentous cyanobacteria, revealing a close association of organisms taking up DOM with photoautotrophic members of the mat community. The capacity for dark- and light-mediated heterotrophy, coupled to efficient retention of fixed carbon in the mat community, may help optimize net production and accretion of mats, even in oligotrophic waters.

NASA Discipline Exobiology↗

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.

NASA Discipline Exobiology↗

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↗

Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fed production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate.

Johnson, M. S.↗

Estimating the Distribution of Colored Dissolved Organic Matter During the Southern Ocean Gas Exchange Experiment Using Four-Dimensional Variational Data Assimilation

We diagnosed the effect of various physical processes on the distribution of mixed-layer colored dissolved organic matter (CDOM) and a sulfur hexauoride (SF6) tracer during the Southern Ocean Gas Exchange Experiment (SO GasEx). The biochemical upper ocean state estimate uses in situ and satellite biochemical and physical data in the study region, including CDOM (absorption coefcient and spectral slope), SF6, hydrography, and sea level anomaly. Modules for photobleaching of CDOM and surface transport of SF6 were coupled with an ocean circulation model for this purpose. The observed spatial and temporal variations in CDOM were captured by the state estimate without including any new biological source term for CDOM, assuming it to be negligible over the 26 days of the state estimate. Thermocline entrainment and photobleaching acted to diminish the mixed-layer CDOM with time scales of 18 and 16 days, respectively. Lateral advection of CDOM played a dominant role and increased the mixed-layer CDOM with a time scale of 12 days, whereas lateral diffusion of CDOM was negligible. A Lagrangian view on the CDOM variability was demonstrated by using the SF6 as a weighting function to integrate the CDOM elds. This and similar data assimilation methods can be used to provide reasonable estimates of optical properties, and other physical parameters over the short-term duration of a research cruise, and help in the tracking of tracer releases in large-scale oceanographic experiments, and in oceanographic process studies.

Del Castillo, C. E.↗

Estuarine Dissolved Organic Carbon Flux from Space: With Application to Chesapeake and Delaware Bays

This study uses a neural network model trained with in situ data, combined with satellite data and hydrodynamic model products, to compute the daily estuarine export of dissolved organic carbon (DOC) at the mouths of Chesapeake Bay (CB) and Delaware Bay (DB) from 2007 to 2011. Both bays show large flux variability with highest fluxes in spring and lowest in fall as well as interannual flux variability (0.18 and 0.27 Tg C/year in 2008 and 2010 for CB; 0.04 and 0.09 Tg C/year in 2008 and 2011 for DB). Based on previous estimates of total organic carbon (TOCexp) exported by all Mid-Atlantic Bight estuaries (1.2 Tg C/year), the DOC export (CB + DB) of 0.3 Tg C/year estimated here corresponds to 25% of the TOCexp. Spatial and temporal covariations of velocity and DOC concentration provide contributions to the flux, with larger spatial influence. Differences in the discharge of fresh water into the bays (74 billion m(exp3)/year for CB and 21 billion m9exp3)/year for DB) and their geomorphologies are major drivers of the differences in DOC fluxes for these two systems. Terrestrial DOC inputs are similar to the export of DOC at the bay mouths at annual and longer time scales but diverge significantly at shorter time scales (days to months). Future efforts will expand to the Mid-Atlantic Bight and Gulf of Maine, and its major rivers and estuaries, in combination with coupled terrestrial-estuarine-ocean biogeochemical models that include effects of climate change, such as warming and CO2 increase.

Signorini, Sergio↗

Estuarine Dissolved Organic Carbon Flux From Space: With Application to Chesapeake and Delaware Bays

This study uses a neural network model trained with in situ data, combined with satellite data and hydrodynamic model products, to compute the daily estuarine export of dissolved organic carbon (DOC) at the mouths of Chesapeake Bay (CB) and Delaware Bay (DB) from 2007 to 2011. Both bays show large flux variability with highest fluxes in spring and lowest in fall as well as interannual flux variability (0.18 and 0.27 Tg C/year in 2008 and 2010 for CB; 0.04 and 0.09 Tg C/year in 2008 and 2011 for DB). Based on previous estimates of total organic carbon (TOCexp) exported by all Mid-Atlantic Bight estuaries (1.2 Tg C/year), the DOC export (CB + DB) of 0.3 Tg C/year estimated here corresponds to 25% of the TOCexp. Spatial and temporal covariations of velocity and DOC concentration provide contributions to the flux, with larger spatial influence. Differences in the discharge of fresh water into the bays (74 billion cu. m/year for CB and 21 billion cu. m/year for DB) and their geomorphologies are major drivers of the differences in DOC fluxes for these two systems. Terrestrial DOC inputs are similar to the export of DOC at the bay mouths at annual and longer time scales but diverge significantly at shorter time scales (days to months). Future efforts will expand to the Mid-Atlantic Bight and Gulf of Maine, and its major rivers and estuaries, in combination with coupled terrestrial-estuarine-ocean biogeochemical models that include effects of climate change, such as warming and CO2 increase.

Estuarine DOC export↗

Evaluation of Retrieving Chlorophyll a Concentration and Colored Dissolved Organic Matter Absorption from Satellite Ocean Color Remote Sensing in the Coastal Waters of Hokkaido, Japan

Coastal ecosystems are important in biogeochemical cycles, because they provide many pathways for chemical elements and compounds to flow between the physical environment and living organisms. The spatial and temporal scales of the biotic and abiotic interactions establish the inherent dynamics of the coastal zone and the requirement for high-resolution investigations. Using match-up data collected in Hokkaido coastal waters, the study herein evaluated the performance of deriving chlorophyll (Chl) a concentration and colored dissolved organic matter (CDOM) absorption (a(sub CDOM)) as a function of wavelength (λ) from satellite observations. The Japanese Aerospace Exploration Agency (JAXA) Second generation GLobal Imager (SGLI), which has 250 m spatial resolution, was compared with other satellite ocean color (OC) sensors. Our results show that the standard SGLI OC4 algorithm with the 530 nm band provided the best performance for Chl a retrievals, and the end-member analysis (EMA) technique improved the estimation of a(sub CDOM)(λ) . Overall differences between in situ radiometric data and satellite retrievals suggest that additional challenges remain, especially in the ultraviolet and blue spectral domains which are useful for studying CDOM and harmful algae blooms in coastal waters. To fulfill applications wherein high-quality remote sensing data are required, the improvement of the atmospheric correction is a likely research area where additional accomplishment will be beneficial for satellite observations of optically complex coastal waters.

SGLI/GCOM-C↗

Relation between Soil Order and Sorptive Capacity for Dissolved Organic Carbon

Soils have historically been considered a temporary sink for organic C, but deeper soils may serve as longer term C sinks due to the sorption of dissolved organic C (DOC) onto Fe- and clay-rich mineral soil particles. This project provides an improved understanding and predictive capability of the physical and chemical properties of deep soils that control their sorptive capacities for DOC. Two hundred thirteen subsurface soil samples (72 series from five orders) were selected from the eastern and central United States. A characterized natural DOC source was added to the soils, and the Langmuir sorption equation was fitted to the observed data by adjusting the maximum DOC sorption capacity (Q{sub max}) and the binding coefficient (k). Different isotherm shapes were observed for Ultisols, Alfisols, and Mollisols due to statistically significant differences in the magnitude of k, while Q{sub max} was statistically invariant among these three orders. Linear regressions were performed on the entire database and as a function of soil order to correlate Langmuir fitted parameters with measured soil properties, e.g., pH, clay content, total organic C (TOC), and total Fe oxide content. Together, textural clay and Fe oxide content accounted for 35% of the variation in Q{sub max} in the database, and clay was most important for Alfisols and Ultisols. The TOC content, however, accounted for 27% of the variation in Q{sub max} in Mollisols. Soil pH accounted for 45% of the variation in k for the entire database, 41% for Mollisols, and 22% for Alfisols. Our findings demonstrate that correlations between Langmuir parameters and soil properties are different for different soil orders and that k is a more sensitive parameter for DOC sorption than is Q{sub max} for temperate soils from the central and eastern United States.

54 ENVIRONMENTAL SCIENCES↗

Prediction of Total Dissolved Gas (TDG) at Hydropower Dams throughout the Columbia

The network of dams throughout the Columbia River Basin (CRB) are managed for irrigation, hydropower production, flood control, navigation, and fish passage that frequently result in both voluntary and involuntary spillway releases. The entrainment of air in spillway releases and the subsequent exchange of atmospheric gasses into solution during passage through the stilling basin cause elevated levels of total dissolved gas (TDG) saturation. Physical processes that affect TDG exchange at hydropower facilities have been characterized throughout the CRB in site-specific studies and at real-time water quality monitoring stations. These data have been used to develop predictive models of TDG exchange which are site specific and account for the fate of spillway and powerhouse flows in the tailrace channel and resultant transport and exchange in route to the downstream dam. Currently, there exists a need to summarize the findings from operational and structural TDG abatement programs conducted throughout the CRB and for the development of a generalized prediction model that pools data collected at multiple projects with similar structural attributes. A generalized TDG exchange model can be tuned to specific projects and coupled with water regulation models to allow for the formulation of optimal water regulation schedules subject to water quality constraints for TDG supersaturation. It is proposed to develop a methodology for predicting TDG levels downstream of hydropower facilities with similar structural properties as a function of a set of variables that affect TDG exchange; such as tailwater depth, spill discharge and pattern, project head, and entrainment of powerhouse releases.

13 HYDRO ENERGY↗

Rapid Field Measurement of Dissolved Inorganic Carbon Based on CO{sub 2} Analysis

Dissolved inorganic carbon (DIC) is commonly measured in water and is an important parameter for understanding carbonate equilibrium, carbon cycling, and water-rock interaction. While accurate measurements can be made in the analytical laboratory, we have developed a rapid, portable technique that can be used to obtain accurate and precise data in the field as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

36 MATERIALS SCIENCE↗

Why dissolved organic matter (DOM) enhances photodegradation of methylmercury

Methylmercury (MeHg) is known to degrade photochemically, but it remains unclear what roles naturally dissolved organic matter (DOM) and complexing organic ligands play in MeHg photodegradation. Here we investigate the rates and mechanisms of MeHg photodegradation using DOM samples with varying oxidation states and origins as well as organic ligands with known molecular structures. All DOM and organic ligands increased MeHg photodegradation under solar irradiation, but the first-order rate constants varied depending on the oxidation state of DOM and the type and concentration of the ligands. Compounds containing both thiols and aromatics (e.g., thiosalicylate and reduced DOM) increased MeHg degradation rates far greater than those containing only aromatic or thiol functional groups (e.g., salicylate or glutathione). Our results suggest that, among other factors, the synergistic effects of thiolate and aromatic moieties in DOM greatly enhance MeHg photodegradation.

demethylation↗

Foam-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

Foam-based adsorbents and a related method of manufacture are provided. The foam-based adsorbents include polymer foam with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the foam-based adsorbents includes irradiating polymer foam, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Foam-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predation Susceptibility of Juvenile Fall Chinook Salmon Exposed to Sudden Temperature Changes and Slightly Supersaturated Dissolved Gas

High mortality of hatchery-reared juvenile fall Chinook salmon emigrating from the Clearwater River was previously measured at the confluence of the Snake and Clearwater rivers; however, the causative mechanism of mortality is unknown. To elucidate potential mechanisms, the predation susceptibility of juvenile fall Chinook salmon was assessed during simulated passage from the Clearwater River and through the confluence of the Clearwater and Snake rivers, with and without cool water flow augmentation. Emigrant-sized juvenile salmon were acclimated to temperatures typical of the Clearwater River when cool water augmentation is discharged from Dworshak Dam (10°C to 17°C) and during temperatures that would be present without augmentation (17°C to 24°C), and were then exposed to smallmouth bass within temperatures typical of the Snake River in summer (17°C to 24°C). Slightly supersaturated total dissolved gas concentrations of 105% were also simulated to more closely approximate gas conditions of both rivers in summer. Predation susceptibility of juvenile salmon acclimated at 10°C or 17°C and exposed to predators at 17°C did not differ. However, for salmon exposed to predators at 24°C, predation susceptibility was arguably higher for juvenile salmon acclimated at 10°C (a 14°C increase) than for salmon acclimated at 17°C or 24°C (7°C and 0°C increases, respectively). These results indicate that predation susceptibility may be higher when a relatively large temperature difference exists between the Clearwater and Snake rivers; that is, when cool water flow augmentation is occurs in summer. However, further research is needed to determine if high confluence mortality measured in previous studies is related to cool water augmentation and, ultimately, whether or not this mortality has a population-level effect on the dynamics of wild Snake River fall Chinook salmon.

fall Chinook salmon↗