Light–dark O2 dynamics in submerged leaves of C3 and C4 halophytes under increased dissolved CO2: clues for saltmarsh response to climate change

PubMed Central

Duarte, B.; Santos, D.; Silva, H.; Marques, J. C.; Caçador, I.; Sleimi, N.

2014-01-01

Waterlogging and submergence are the major constraints to which wetland plants are subjected, with inevitable impacts on their physiology and productivity. Global warming and climate change, as driving forces of sea level rise, tend to increase such submersion periods and also modify the carbonate chemistry of the water column due to the increased concentration of CO2 in the atmosphere. In the present work, the underwater O2 fluxes in the leaves of two abundant Mediterranean halophytes were evaluated at different levels of dissolved CO2. Photosynthetic enhancement due to increased dissolved CO2 was confirmed for both Halimione portulacoides and Spartina maritima, probably due to high tissue porosity, formation of leaf gas films and reduction of the oxygenase activity of Rubisco. Enhancement of the photosynthetic rates in H. portulacoides and S. maritima was concomitant with an increase in energy trapping and transfer, mostly due to enhancement of the carboxylation reaction of Rubisco, leading to a reduction of the energy costs for carbon fixation. Transposing these findings to the ecosystem, and assuming increased dissolved CO2 concentration scenarios, the halophyte community displays a new ecosystem function, increasing the water column oxygenation and thus reinforcing their role as principal primary producers of the estuarine system. PMID:25381259

ABIOTIC O{sub 2} LEVELS ON PLANETS AROUND F, G, K, AND M STARS: POSSIBLE FALSE POSITIVES FOR LIFE?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harman, C. E.; Kasting, J. F.; Schwieterman, E. W.

2015-10-20

In the search for life on Earth-like planets around other stars, the first (and likely only) information will come from the spectroscopic characterization of the planet's atmosphere. Of the countless number of chemical species terrestrial life produces, only a few have the distinct spectral features and the necessary atmospheric abundance to be detectable. The easiest of these species to observe in Earth's atmosphere is O{sub 2} (and its photochemical byproduct, O{sub 3}). However, O{sub 2} can also be produced abiotically by photolysis of CO{sub 2}, followed by recombination of O atoms with each other. CO is produced in stoichiometric proportions. Whethermore » O{sub 2} and CO can accumulate to appreciable concentrations depends on the ratio of far-ultraviolet (FUV) to near-ultraviolet (NUV) radiation coming from the planet's parent star and on what happens to these gases when they dissolve in a planet's oceans. Using a one-dimensional photochemical model, we demonstrate that O{sub 2} derived from CO{sub 2} photolysis should not accumulate to measurable concentrations on planets around F- and G-type stars. K-star, and especially M-star planets, however, may build up O{sub 2} because of the low NUV flux from their parent stars, in agreement with some previous studies. On such planets, a “false positive” for life is possible if recombination of dissolved CO and O{sub 2} in the oceans is slow and if other O{sub 2} sinks (e.g., reduced volcanic gases or dissolved ferrous iron) are small. O{sub 3}, on the other hand, could be detectable at UV wavelengths (λ < 300 nm) for a much broader range of boundary conditions and stellar types.« less

Effect of pH values on surface modification and solubility of phosphate bioglass-ceramics in the CaO-P 2O 5-Na 2O-SrO-ZnO system

NASA Astrophysics Data System (ADS)

Li, Xudong; Cai, Shu; Zhang, Wenjuang; Xu, Guohua; Zhou, Wei

2009-08-01

The bioactive glass-ceramics in the CaO-P 2O 5-Na 2O-SrO-ZnO system were synthesized by the sol-gel technique, and then chemically treated at different pH values to study the solubility and surface modification. Samples sintered at 650 °C for 4 h consisted of the crystalline phase β-Ca 2P 2O 7 and the glass matrix. After soaking in the solution at pH 1.0, the residual glass matrix on the surface appeared entirely dissolved and no new phase could be detected. Whereas at pH 3.0, web-like layer exhibiting peaks corresponding to CaP 2O 6 was formed and covered the entire surface of the sample. When conducted at pH 10.0, only part of the glass matrix was dissolved and a new phase Ca 4P 6O 19 was precipitated, forming the petaline layer. The chemical treatment can easily change the surface morphologies and phase composition of this bioactive glass-ceramics. The higher level of surface roughness resulting from the new-formed layer would improve the interface bonding and benefit for cell adhesion.

Effects of Bubble-Mediated Processes on Nitrous Oxide Dynamics in Denitrifying Bioreactors

NASA Astrophysics Data System (ADS)

McGuire, P. M.; Falk, L. M.; Reid, M. C.

2017-12-01

To mitigate groundwater and surface water impacts of reactive nitrogen (N), agricultural and stormwater management practices can employ denitrifying bioreactors (DNBs) as low-cost solutions for enhancing N removal. Due to the variable nature of hydrologic events, DNBs experience dynamic flows which can impact physical and biological processes within the reactors and affect performance. A particular concern is incomplete denitrification, which can release the potent greenhouse gas nitrous oxide (N2O) to the atmosphere. This study aims to provide insight into the effects of varying hydrologic conditions upon the operation of DNBs by disentangling abiotic and biotic controls on denitrification and N2O dynamics within a laboratory-scale bioreactor. We hypothesize that under transient hydrologic flows, rising water levels lead to air entrapment and bubble formation within the DNB porous media. Mass transfer of oxygen (O2) between trapped gas and liquid phases creates aerobic microenvironments that can inhibit N2O reductase (NosZ) enzymes and lead to N2O accumulation. These bubbles also retard N2O transport and make N2O unavailable for biological reduction, further enhancing atmospheric fluxes when water levels fall. The laboratory-scale DNB permits measurements of longitudinal and vertical profiles of dissolved constituents as well as trace gas concentrations in the reactor headspace. We describe a set of experiments quantifying denitrification pathway biokinetics under steady-state and transient hydrologic conditions and evaluate the role of bubble-mediated processes in enhancing N2O accumulation and fluxes. We use sulfur hexafluoride and helium as dissolved gas tracers to examine the impact of bubble entrapment upon retarded gas transport and enhanced trace gas fluxes. A planar optode sensor within the bioreactor provides near-continuous 2-D profiles of dissolved O2 within the bioreactor and allows for identification of aerobic microenvironments. We use qPCR to examine the relative abundance of the denitrifying genes nitrate reductase and NosZ within the bioreactor and explore gradients in denitrification biomarkers coinciding with denitrification intermediate profiles. Insights gained from this study will advance understanding of gas dynamics within environmental porous media.

Skin oxygen tension is improved by immersion in oxygen-enriched water.

PubMed

Reading, S A; Yeomans, M; Levesque, C

2013-12-01

The perceived health and physiologic functioning of skin depends on adequate oxygen availability. Economical and easily used therapeutic approaches to increase skin oxygenation could improve the subjective appearance of the skin as well as support the management of some cutaneous conditions related to chronic hypoxic ischaemia (e.g. ulcerative wounds). We have tested the hypothesis that the O2 partial pressure of skin (PskO2 ) increases during immersion in water enriched with high levels of dissolved oxygen. A commercially available device was used to produce water containing 45 to 65 mg L(-1) of dissolved O2 . Young adults (YA; n = 7), older adults (OA; n = 13) and older adults with diabetes (OAD; n = 11) completed different experiments that required them to immerse their feet in tap water (<2 mg L(-1) of O2 ; control) or O2 -enriched water (O2 -H2 O; experimental) for 30 min. Transcutaneous oximetry was used to measure PskO2 for 20 min pre- and post-immersion. Pre-immersion mean (standard deviation) PskO2 on the plantar surface of the big toe was 75 (10), 67 (10) and 65 (10) mmHg in YA, OA and OAD, respectively. Post-immersion PskO2 was 244 (25), 193 (28) and 205 (28) mmHg for the same groups. We also show that post-immersion PskO2 varies by location and with advancing age. Water is an effective vehicle for transporting dissolved O2 across the skin surface and could be used as a basis for development of economical therapeutic approaches that improve skin oxygen tension to support skin health and function. © 2013 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Expression of denitrification enzymes in response to the dissolved oxygen level and respiratory substrate in continuous culture of Pseudomonas stutzeri.

PubMed Central

Körner, H; Zumft, W G

1989-01-01

The onset and cessation of the synthesis of denitrification enzymes of Pseudomonas stutzeri were investigated by using continuous culture and defined dissolved oxygen levels covering the full range of transition from air saturation to complete anaerobiosis. Expression of nitrate reductase, nitrite reductase (cytochrome cd1), and N2O reductase was controlled by discrete oxygen levels and by the nature of the nitrogenous oxide available for respiration. N2O reductase was synthesized constitutively at a low level; for enhanced expression, oxygen concentrations were required to decrease below 5 mg of O2 per liter. The threshold values for synthesis of nitrate reductase and cytochrome cd1 in the presence of nitrate were ca. 5 and ca. 2.5 mg of O2 per liter, respectively. With nitrous oxide as the respiratory substrate, nitrite reductase was again the most sensitive to oxygen concentration; however, thresholds for all denitrification enzymes shifted to lower oxygen levels. Whereas the presence of nitrate resulted in maximum expression and nearly uniform induction of all reductases, nitrite and nitrous oxide stimulated preferably the respective enzyme catalyzing reduction. In the absence of a nitrogenous oxide, anaerobiosis did not induce enzyme synthesis to any significant degree. The accumulation of nitrite seen during both the aerobic-anaerobic and anaerobic-aerobic transition phases was caused by the differences in onset or cessation of synthesis of nitrate and nitrite reductases and an inhibitory effect of nitrate on nitrite reduction. Images PMID:2764573

Inhibitory Effect of Dissolved Silica on the H2O2 Decomposition by Iron(III) and Manganese(IV) Oxides: Implications for H2O2-based In Situ Chemical Oxidation

PubMed Central

Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

2011-01-01

The decomposition of H2O2 on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H2O2, because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand and montmorillonite that were pre-equilibrated with 0.05 – 1.5 mM SiO2 were significantly less reactive toward H2O2 decomposition than their original counterparts, with the H2O2 loss rates inversely proportional to the SiO2 concentration. In the goethite/H2O2 system, the overall •OH yield, defined as the percentage of decomposed H2O2 producing •OH, was almost halved in the presence of 1.5 mM SiO2. Dissolved SiO2 also slows the H2O2 decomposition on manganese(IV) oxide. The presence of dissolved SiO2 results in greater persistence of H2O2 in groundwater, lower H2O2 utilization efficiency and should be considered in the design of H2O2-based treatment systems. PMID:22129132

Nitrous oxide in fresh water systems: An estimate for the yield of atmospheric N2O associated with disposal of human waste

NASA Technical Reports Server (NTRS)

Kaplan, W. A.; Elkins, J. W.; Kolb, C. E.; Mcelroy, M. B.; Wofsy, S. C.; Duran, A. P.

1977-01-01

The N2O content of waters in the Potomac and Merrimack Rivers was measured on a number of occasions over the period April to July 1977. The concentrations of dissolved N2O exceeded those which would apply in equilibrium with air by factors ranging from about 46 in the Potomac to 1.2 in the Merrimack. Highest concentrations of dissolved N2O were associated with sewage discharges from the vicinity of Washington, D. C., and analysis indicates a relatively high yield, 1.3 to 11%, for prompt conversion of waste nitrogen to N2O. Measurements of dissolved N2O in fresh water ponds near Boston demonstrated that aquatic systems provide both strong sources and sinks for atmospheric N2O.

Dissolved organic matter and aluminum oxide nanoparticles synergistically cause cellular responses in freshwater microalgae.

PubMed

Ye, Nan; Wang, Zhuang; Wang, Se; Fang, Hao; Wang, Degao

2018-06-07

This study investigated the impact of dissolved organic matters (DOM) on the ecological toxicity of aluminum oxide nanoparticles (Al 2 O 3 NPs) at a relatively low exposure concentration (1 mg L -1 ). The unicellular green alga Scenedesmus obliquus was exposed to Al 2 O 3 NP suspensions in the presence of DOM (fulvic acid) at various concentrations (1, 10, and 40 mg L -1 ). The results show that the presence of DOM elevated the growth inhibition toxicity of Al 2 O 3 NPs towards S. obliquus in a dose-dependent manner. Moreover, the combination of DOM at 40 mg L -1 and Al 2 O 3 NPs resulted in a synergistic effect. The relative contribution of Al-ions released from Al 2 O 3 NPs to toxicity was lower than 5%, indicating that the presence of the particles instead of the dissolved ions in the suspensions was the major toxicity sources, regardless of the presence of DOM. Furthermore, DOM at 10 and 40 mg L -1 and Al 2 O 3 NPs synergistically induced the upregulation of intercellular reactive oxygen species levels and superoxide dismutase activities. Analysis of the plasma malondialdehyde concentrations and the observation of superficial structures of S. obliquus indicated that the mixtures of DOM and Al 2 O 3 NPs showed no significant effect on membrane lipid peroxidation damage. In addition, the presence of both DOM and Al 2 O 3 NPs contributed to an enhancement in both the mitochondrial membrane potential and the cell membrane permeability (CMP) in S. obliquus. In particular, Al 2 O 3 NPs in the presence of 10 and 40 mg L -1 DOM caused a greater increase in CMP compared to Al 2 O 3 NPs and DOM alone treatments. In conclusion, these findings suggest that DOM at high concentrations and Al 2 O 3 NPs synergistically interrupted cell membrane functions and triggered subsequent growth inhibition toxicity.

The impact of four decades of annual nitrogen addition on dissolved organic matter in a boreal forest soil

NASA Astrophysics Data System (ADS)

Rappe-George, M. O.; Gärdenäs, A. I.; Kleja, D. B.

2013-03-01

Addition of mineral nitrogen (N) can alter the concentration and quality of dissolved organic matter (DOM) in forest soils. The aim of this study was to assess the effect of long-term mineral N addition on soil solution concentration of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) in Stråsan experimental forest (Norway spruce) in central Sweden. N was added yearly at two levels of intensity and duration: the N1 treatment represented a lower intensity but a longer duration (43 yr) of N addition than the shorter N2 treatment (24 yr). N additions were terminated in the N2 treatment in 1991. The N treatments began in 1967 when the spruce stands were 9 yr old. Soil solution in the forest floor O, and soil mineral B, horizons were sampled during the growing seasons of 1995 and 2009. Tension and non-tension lysimeters were installed in the O horizon (n = 6), and tension lysimeters were installed in the underlying B horizon (n = 4): soil solution was sampled at two-week intervals. Although tree growth and O horizon carbon (C) and N stock increased in treatments N1 and N2, the concentration of DOC in O horizon leachates was similar in both N treatments and control. This suggests an inhibitory direct effect of N addition on O horizon DOC. Elevated DON and nitrate in O horizon leachates in the ongoing N1 treatment indicated a move towards N saturation. In B horizon leachates, the N1 treatment approximately doubled leachate concentrations of DOC and DON. DON returned to control levels, but DOC remained elevated in B horizon leachates in N2 plots nineteen years after termination of N addition. We propose three possible explanations for the increased DOC in mineral soil: (i) the result of decomposition of a larger amount of root litter, either directly producing DOC or (ii) indirectly via priming of old SOM, and/or (iii) a suppression of extracellular oxidative enzymes.

Productivity Estimation of Hypersaline Microbial Mat Communities - Diurnal Cycles of Dissolved Oxygen

NASA Astrophysics Data System (ADS)

Less, G.; Cohen, Y.; Luz, B.; Lazar, B.

2002-05-01

Hypersaline microbial mat communities (MMC) are the modern equivalents of the Archean stromatolities, the first photosynthetic organisms on Earth. An estimate of their oxygen production rate is important to the understanding of oxygen evolution on Earth ca. 2 b.y.b.p. Here we use the diurnal cycle of dissolved oxygen, O2/Ar ratio and the isotopic composition of dissolved oxygen to calculate net and gross primary productivity of MMC growing in a large scale (80 m2) experimental pan. The pan is inoculated with MMC taken from the Solar Lake, Sinai, Egypt and filled with 90\\permil evaporated Red Sea water brine up to a depth of ca. 0.25 m. It is equipped with computerized flow through system that is programmed to pump pan water at selected time intervals into a sampling cell fitted with dissolved oxygen, pH, conductivity and temperature sensors connected to a datalogger. Manual brine samples were taken for calibrating the sensors, mass spectrometric analyses and for measurements of additional relevant parameters. Dissolved oxygen concentrations fluctuate during the diurnal cycle being highly supersaturated except for the end of the night. The O2 curve varies seasonally and has a typical "shark fin" shape due to the MMC metabolic response to the shape of the diurnal light curve. The dissolved oxygen data were fitted to a smooth curve that its time derivative (dO2 /dt) is defined as: Z dO2 /dt=GP-R-k(O2(meas)- O2(sat)) where z is the depth (m); GP and R are the MMC gross production and respiration (mol m-2 d-1), respectively; k is the gas exchange coefficient (m d-1); O2(meas) and O2(sat) (mol L-1) are the measured and equilibrium dissolved oxygen concentrations, respectively. The high resolution sampling of the automated system produces O2 curves that enable the calculation of smooth and reliable time derivatives. The calculations yield net production values that vary between 1,000 10-6 to -100 10-6 mol O2 m-2 h-1 and day respiration rates between 60 10-6 to 30 10-6 mol O2 m-2 h-1 in summer and winter, respectively. Independent estimate of the gross productivity and respiration is provided by the oxygen isotopic measurements.

The effect of iron content and dissolved O2 on dissolution rates of clinopyroxene at pH 5.8 and 25°C: Preliminary results

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.; Drever, J.I.

1996-01-01

Dissolution experiments using augite (Mg0.87Ca0.85Fe0.19Na0.09Al0.03Si2O6) and diopside (Mg0.91Ca0.93Fe0.07Na0.03Al0.03Si2O6) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO2 through a solution of 0.01 M KHCO3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.

Cellular partitioning of nanoparticulate versus dissolved metals in marine phytoplankton.

PubMed

Bielmyer-Fraser, Gretchen K; Jarvis, Tayler A; Lenihan, Hunter S; Miller, Robert J

2014-11-18

Discharges of metal oxide nanoparticles into aquatic environments are increasing with their use in society, thereby increasing exposure risk for aquatic organisms. Separating the impacts of nanoparticle from dissolved metal pollution is critical for assessing the environmental risks of the rapidly growing nanomaterial industry, especially in terms of ecosystem effects. Metal oxides negatively affect several species of marine phytoplankton, which are responsible for most marine primary production. Whether such toxicity is generally due to nanoparticles or exposure to dissolved metals liberated from particles is uncertain. The type and severity of toxicity depends in part on whether phytoplankton cells take up and accumulate primarily nanoparticles or dissolved metal ions. We compared the responses of the marine diatom, Thalassiosira weissflogii, exposed to ZnO, AgO, and CuO nanoparticles with the responses of T. weissflogii cells exposed to the dissolved metals ZnCl2, AgNO3, and CuCl2 for 7 d. Cellular metal accumulation, metal distribution, and algal population growth were measured to elucidate differences in exposure to the different forms of metal. Concentration-dependent metal accumulation and reduced population growth were observed in T. weissflogii exposed to nanometal oxides, as well as dissolved metals. Significant effects on population growth were observed at the lowest concentrations tested for all metals, with similar toxicity for both dissolved and nanoparticulate metals. Cellular metal distribution, however, markedly differed between T. weissflogii exposed to nanometal oxides versus those exposed to dissolved metals. Metal concentrations were highest in the algal cell wall when cells were exposed to metal oxide nanoparticles, whereas algae exposed to dissolved metals had higher proportions of metal in the organelle and endoplasmic reticulum fractions. These results have implications for marine plankton communities as well as higher trophic levels, since metal may be transferred from phytoplankton through food webs vis à vis grazing by zooplankton or other pathways.

The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

NASA Astrophysics Data System (ADS)

Goenawan, Joshua; Trisanti, P. N.; Sumarno

2015-12-01

This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

The role of reactive oxygen species in the degradation of lignin derived dissolved organic matter

NASA Astrophysics Data System (ADS)

Waggoner, Derek C.; Wozniak, Andrew S.; Cory, Rose M.; Hatcher, Patrick G.

2017-07-01

Evidence suggests that reactive oxygen species (ROS) are important in transforming the chemical composition of the large pool of terrestrially-derived dissolved organic matter (DOM) exported from land to water annually. However, due to the challenges inherent in isolating the effects of individual ROS on DOM composition, the role of ROS in the photochemical alteration of DOM remains poorly characterized. In this work, terrestrial DOM was independently exposed to singlet oxygen (1O2), and superoxide (O2-rad under controlled laboratory conditions). Using ultra-high resolution mass spectrometry to track molecular level alterations of DOM by ROS, these findings suggest exposure to 1O2 (generated using Rose Bengal and visible light) removed formulas with an O/C > 0.3, and primarily resulted in DOM comprised of formulas with higher oxygen content, while O2-rad exposure (from KO2 in DMSO) removed formulas with O/C < 0.3 and produced aliphatic formulas (H/C > 1.5). Comparison of DOM altered by ROS in this study to riverine and coastal DOM showed that (20-80%) overlap in formulas, providing evidence for the role of ROS in shaping the composition of DOM exported from rivers to oceans.

Dissolved oxygen: Chapter 6

USGS Publications Warehouse

Senn, David; Downing-Kunz, Maureen; Novick, Emily

2016-01-01

Dissolved oxygen (DO) concentration serves as an important indicator of estuarine habitat condition, because all aquatic macro-organisms require some minimum DO level to survive and prosper. The instantaneous DO concentration, measured at a specific location in the water column, results from a balance between multiple processes that add or remove oxygen (Figure 6.1): primary production produces O2; aerobic respiration in the water column and sediments consumes O2; abiotic or microbially-mediated biogeochemical reactions utilize O2 as an oxidant (e.g., oxidation of ammonium, sulfide, and ferrous iron); O2 exchange occurs across the air:water interface in response to under- or oversaturated DO concentrations in the water column; and water currents and turbulent mixing transport DO into and out of zones in the water column. If the oxygen loss rate exceeds the oxygen production or input rate, DO concentration decreases. When DO losses exceed production or input over a prolonged enough period of time, hypoxia ((<2-3 mg/L) or anoxia can develop. Persistent hypoxia or anoxia causes stress or death in aquatic organism populations, or for organisms that can escape a hypoxic or anoxic area, the loss of habitat. In addition, sulfide, which is toxic to aquatic organisms and causes odor problems, escapes from sediments under low oxygen conditions. Low dissolved oxygen is a common aquatic ecosystem response to elevated organic

Novel Anaerobic Wastewater Treatment System for Energy Generation at Forward Operating Bases

DTIC Science & Technology

2016-08-01

every 5 minutes). Other automation features that come with the Bioflo include wet/dry level sensors, dissolved oxygen , pH, temperature and mixing...38 3.4.1 Operation at mesophilic temperature (35oC...38 ERDC/CERL TR-16-13 iv 3.4.2 Operation at ambient temperature (20 oC) ............................................................. 46

Dissolved carbon dioxide and oxygen concentrations in purge of vacuum-packaged pork chops and the relationship to shelf life and models for estimating microbial populations.

PubMed

Adams, K R; Niebuhr, S E; Dickson, J S

2015-12-01

The objectives of this study were to determine the dissolved CO2 and O2 concentrations in the purge of vacuum-packaged pork chops over a 60 day storage period, and to elucidate the relationship of dissolved CO2 and O2 to the microbial populations and shelf life. As the populations of spoilage bacteria increased, the dissolved CO2 increased and the dissolved O2 decreased in the purge. Lactic acid bacteria dominated the spoilage microflora, followed by Enterobacteriaceae and Brochothrix thermosphacta. The surface pH decreased to 5.4 due to carbonic acid and lactic acid production before rising to 5.7 due to ammonia production. A mathematical model was developed which estimated microbial populations based on dissolved CO2 concentrations. Scanning electron microscope images were also taken of the packaging film to observe the biofilm development. The SEM images revealed a two-layer biofilm on the packaging film that was the result of the tri-phase growth environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Structurally integrated organic light emitting device-based sensors for gas phase and dissolved oxygen.

PubMed

Shinar, Ruth; Zhou, Zhaoqun; Choudhury, Bhaskar; Shinar, Joseph

2006-05-24

A compact photoluminescence (PL)-based O2 sensor utilizing an organic light emitting device (OLED) as the light source is described. The sensor device is structurally integrated. That is, the sensing element and the light source, both typically thin films that are fabricated on separate glass substrates, are attached back-to-back. The sensing elements are based on the oxygen-sensitive dyes Pt- or Pd-octaethylporphyrin (PtOEP or PdOEP, respectively), which are embedded in a polystyrene (PS) matrix, or dissolved in solution. Their performance is compared to that of a sensing element based on tris(4,7-diphenyl-l,10-phenanthroline) Ru II (Ru(dpp)) embedded in a sol-gel film. A green OLED light source, based on tris(8-hydroxy quinoline Al (Alq3), was used to excite the porphyrin dyes; a blue OLED, based on 4,4'-bis(2,2'-diphenylviny1)-1,1'-biphenyl, was used to excite the Ru(dpp)-based sensing element. The O2 level was monitored in the gas phase and in water, ethanol, and toluene solutions by measuring changes in the PL lifetime tau of the O2-sensitive dyes. The sensor performance was evaluated in terms of the detection sensitivity, dynamic range, gas flow rate, and temperature effect, including the temperature dependence of tau in pure Ar and O2 atmospheres. The dependence of the sensitivity on the preparation procedure of the sensing film and on the PS and dye concentrations in the sensing element, whether a solid matrix or solution, were also evaluated. Typical values of the detection sensitivity in the gas phase, S(g) identical with tau(0% O2)/tau(100% O2), at 23 degrees C, were approximately 35 to approximately 50 for the [Alq3 OLED[/[PtOEP dye] pair; S(g) exceeded 200 for the Alq3/PdOEP sensor. For dissolved oxygen (DO) in water and ethanol, S(DO) (defined as the ratio of tau in de-oxygenated and oxygen-saturated solutions) was approximately 9.5 and approximately 11, respectively, using the PtOEP-based film sensor. The oxygen level in toluene was measured with PtOEP dissolved directly in the solution. That sensor exhibited a high sensitivity, but a limited dynamic range. Effects of aggregation of dye molecules, sensing film porosity, and the use of the OLED-based sensor arrays for O2 and multianalyte detection are also discussed.

Heterogeneity in a Suburban River Network: Understanding the Impact of Fluvial Wetlands on Dissolved Oxygen and Metabolism in Headwater Streams

NASA Astrophysics Data System (ADS)

Cain, J. S.; Wollheim, W. M.; Sheehan, K.; Lightbody, A.

2014-12-01

Low dissolved oxygen content in rivers threatens fish populations, aquatic organisms, and the health of entire ecosystems. River systems with high fluvial wetland abundance and organic matter, may result in high metabolism that in conjunction with low re-aeration rates, lead to low oxygen conditions. Increasing abundance of beaver ponds in many areas may exacerbate this phenomenon. This research aims to understand the impact of fluvial wetlands, including beaver ponds, on dissolved oxygen (D.O.) and metabolism throughout the headwaters of the Ipswich R. watershed, MA, USA. In several fluvial wetland dominated systems, we measured diel D.O. and metabolism in the upstream inflow, the surface water transient storage zones of fluvial wetland sidepools, and at the outflow to understand how the wetlands modify dissolved oxygen. D.O. was also measured longitudinally along entire surface water flow paths (x-y km long) to determine how low levels of D.O. propagate downstream. Nutrient samples were also collected to understand how their behavior was related to D.O. behavior. Results show that D.O. in fluvial wetlands has large swings with periods of very low D.O. at night. D.O. swings were also seen in downstream outflow, though lagged and somewhat attenuated. Flow conditions affect the level of inundation and the subsequent effects of fluvial wetlands on main channel D.O.. Understanding the D.O. behavior throughout river systems has important implications for the ability of river systems to remove anthropogenic nitrogen.

Constraints on the utility of MnO2 cartridge method for the extraction of radionuclides: A case study using 234Th

USGS Publications Warehouse

Baskaran, M.; Swarzenski, P.W.; Biddanda, B.A.

2009-01-01

[1] Large volume (102-103 L) seawater samples are routinely processed to investigate the partitioning of particle reactive radionuclides and Ra between solution and size-fractionated suspended particulate matter. One of the most frequently used methods to preconcentrate these nuclides from such large volumes involves extraction onto three filter cartridges (a prefilter for particulate species and two MnO2-coated filters for dissolved species) connected in series. This method assumes that the extraction efficiency is uniform for both MnO2-coated cartridges, that no dissolved species are removed by the prefilter, and that any adsorbed radionuclides are not desorbed from the MnO2-coated cartridges during filtration. In this study, we utilized 234Th-spiked coastal seawater and deionized water to address the removal of dissolved Th onto prefilters and MnO2-coated filter cartridges. Experimental results provide the first data that indicate (1) a small fraction of dissolved Th (<6%) can be removed by the prefilter cartridge; (2) a small fraction of dissolved Th (<5%) retained by the MnO2 surface can also be desorbed, which undermines the assumption of uniform extraction efficiency for Th; and (3) the absolute and relative extraction efficiencies can vary widely. These experiments provide insight on the variability of the extraction efficiency of MnO 2-coated filter cartridges by comparing the relative and absolute efficiencies and recommend the use of a constant efficiency on the combined activity from two filter cartridges connected in series for future studies of dissolved 234Th and other radionuclides in natural waters using sequential filtration/extraction methods. ?? 2009 by the American Geophysical Union.

Escherichia coli avoids high dissolved oxygen stress by activation of SoxRS and manganese-superoxide dismutase.

PubMed

Baez, Antonino; Shiloach, Joseph

2013-03-12

High concentrations of reactive oxygen species (ROS) were reported to cause oxidative stress to E. coli cells associated with reduced or inhibited growth. The high ROS concentrations described in these reports were generated by exposing the bacteria to H2O2 and superoxide-generating chemicals which are non-physiological growth conditions. However, the effect of molecular oxygen on oxidative stress response has not been evaluated. Since the use of oxygen-enriched air is a common strategy to support high density growth of E. coli, it was important to investigate the effect of high dissolved oxygen concentrations on the physiology and growth of E. coli and the way it responds to oxidative stress. To determine the effect of elevated oxygen concentrations on the growth characteristics, specific gene expression and enzyme activity in E. coli, the parental and SOD-deficient strain were evaluated when the dissolved oxygen (dO2) level was increased from 30% to 300%. No significant differences in the growth parameters were observed in the parental strain except for a temporary decrease of the respiration and acetate accumulation profile. By performing transcriptional analysis, it was determined that the parental strain responded to the oxidative stress by activating the SoxRS regulon. However, following the dO2 switch, the SOD-deficient strain activated both the SoxRS and OxyR regulons but it was unable to resume its initial growth rate. The transcriptional analysis and enzyme activity results indicated that when E. coli is exposed to dO2 shift, the superoxide stress regulator SoxRS is activated and causes the stimulation of the superoxide dismutase system. This enables the E. coli to protect itself from the poisoning effects of oxygen. The OxyR protecting system was not activated, indicating that H2O2 did not increase to stressing levels.

Escherichia coli avoids high dissolved oxygen stress by activation of SoxRS and manganese-superoxide dismutase

PubMed Central

2013-01-01

Background High concentrations of reactive oxygen species (ROS) were reported to cause oxidative stress to E. coli cells associated with reduced or inhibited growth. The high ROS concentrations described in these reports were generated by exposing the bacteria to H2O2 and superoxide-generating chemicals which are non-physiological growth conditions. However, the effect of molecular oxygen on oxidative stress response has not been evaluated. Since the use of oxygen-enriched air is a common strategy to support high density growth of E. coli, it was important to investigate the effect of high dissolved oxygen concentrations on the physiology and growth of E. coli and the way it responds to oxidative stress. Results To determine the effect of elevated oxygen concentrations on the growth characteristics, specific gene expression and enzyme activity in E. coli, the parental and SOD-deficient strain were evaluated when the dissolved oxygen (dO2) level was increased from 30% to 300%. No significant differences in the growth parameters were observed in the parental strain except for a temporary decrease of the respiration and acetate accumulation profile. By performing transcriptional analysis, it was determined that the parental strain responded to the oxidative stress by activating the SoxRS regulon. However, following the dO2 switch, the SOD-deficient strain activated both the SoxRS and OxyR regulons but it was unable to resume its initial growth rate. Conclusion The transcriptional analysis and enzyme activity results indicated that when E. coli is exposed to dO2 shift, the superoxide stress regulator SoxRS is activated and causes the stimulation of the superoxide dismutase system. This enables the E. coli to protect itself from the poisoning effects of oxygen. The OxyR protecting system was not activated, indicating that H2O2 did not increase to stressing levels. PMID:23497217

Determination of exchangeable protons in natural organic matter using a home-made hydrogen/carbon analyser.

PubMed

Haiber, S; Barth, U

2001-01-01

A home made hydrogen/carbon analyser was used to determine the portion of exchangeable protons in aquatic humic substances. For this purpose, equal sample amounts were dissolved in H2O and D2O, respectively, dried and combusted in a stream of oxygen. The amount of water resulting from combustion was measured by an infrared detector which recorded the OH bending vibration of H2O. The bands stemming from HOD or D2O were not registered by the detection unit. Thus, combustion of organic samples containing exchangeable protons dissolved in D2O resulted in a significantly smaller signal compared to the signal observed for the same sample dissolved in H2O. The relative intensity loss of the H2O signal observed after combustion was used to derive the portion of exchangeable protons in a standard reference material, a humic substance isolated by the International Humic Substances Society (Suwannee River fulvic acid). According to this method about 20% of the sample protons could be identified as exchangeable protons. With regard to titration data the portion of protons bound to non acidic hydroxy functions could be estimated. The validity of this procedure was proved by combustion experiments using commercially available deuterated substances as well as organic model compounds dissolved in D2O and H2O, respectively.

Lifetime and dissolution kinetics of zinc oxide nanoparticles in aqueous media

NASA Astrophysics Data System (ADS)

Wang, Ning; Tong, Tiezheng; Xie, Minwei; Gaillard, Jean-François

2016-08-01

We have assessed the persistence and lifetime of ZnO nanoparticles (ZnO-NPs) by performing dissolution experiments in three different aqueous media. These experiments were performed at ZnO-NP concentration levels close to the solubility of zincite (˜8 μM or 650 μg l-1 of ZnO)—a concentration that is orders of magnitude higher than current estimated relevant environmental concentrations. The kinetics were followed by voltammetry, while maintaining the pH at about 7.5 using a CO2/N2 gas mixture to remove di-oxygen interference. Our results show that, under these conditions, ZnO-NPs readily dissolve with a lifetime expectancy that does not exceed 90 min. Water chemistry, especially the presence of dissolved organic matter (DOM), plays an important role in ZnO-NP dissolution. Dissolution rates significantly increase in the presence of strong chelating agents, EDTA and L-cysteine, while the addition of polymeric DOM, such as sodium alginate, has the opposite effect. Our results suggest that ZnO-NPs are unlikely to persist in natural aqueous media and that the toxicity should be primarily related to the released Zn2+ ions rather than effects commonly associated to the presence of nanoparticles.

Effect of nitrate concentration on filamentous bulking under low level of dissolved oxygen in an airlift inner circular anoxic-aerobic incorporate reactor.

PubMed

Su, Yiming; Zhang, Yalei; Zhou, Xuefei; Jiang, Ming

2013-09-01

This laboratory research investigated a possible cause of filamentous bulking under low level of dissolved oxygen conditions (dissolved oxygen value in aerobic zone maintained between 0.6-0.8 mg O2/L) in an airlift inner-circular anoxic-aerobic reactor. During the operating period, it was observed that low nitrate concentrations affected sludge volume index significantly. Unlike the existing hypothesis, the batch tests indicated that filamentous bacteria (mainly Thiothrix sp.) could store nitrate temporarily under carbon restricted conditions. When nitrate concentration was below 4 mg/L, low levels of carbon substrates and dissolved oxygen in the aerobic zone stimulated the nitrate-storing capacity of filaments. When filamentous bacteria riched in nitrate reached the anoxic zone, where they were exposed to high levels of carbon but limited nitrate, they underwent denitrification. However, when nonfilamentous bacteria were exposed to similar conditions, denitrification was restrained due to their intrinsic nitrate limitation. Hence, in order to avoid filamentous bulking, the nitrate concentration in the return sludge (from aerobic zone to the anoxic zone) should be above 4 mg/L, or alternatively, the nitrate load in the anoxic zone should be kept at levels above 2.7 mg NO(3-)-N/g SS.

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: I. The origin of thiosulfate in hot spring waters

USGS Publications Warehouse

Xu, Y.; Schoonen, M.A.A.; Nordstrom, D. Kirk; Cunningham, K.M.; Ball, J.W.

1998-01-01

Thiosulfate (S2O2-3), polythionate (SxO2-6), dissolved sulfide (H2S), and sulfate (SO2-4) concentrations in thirty-nine alkaline and acidic springs in Yellowstone National Park (YNP) were determined. The analyses were conducted on site, using ion chromatography for thiosulfate, polythionate, and sulfate, and using colorimetry for dissolved sulfide. Thiosulfate was detected at concentrations typically less than 2 ??mol/L in neutral and alkaline chloride springs with low sulfate concentrations (C1-/SO2-4 > 25). The thiosulfate concentration levels are about one to two orders of magnitude lower than the concentration of dissolved sulfide in these springs. In most acid sulfate and acid sulfate-chloride springs (Cl-/SO2-4 < 10), thiosulfate concentrations were also typically lower than 2 ??mol/L. However, in some chloride springs enriched with sulfate (Cl-/SO2-4 between 10 to 25), thiosulfate was found at concentrations ranging from 9 to 95 ??mol/L, higher than the concentrations of dissolved sulfide in these waters. Polythionate was detected only in Cinder Pool, Norris Geyser basin, at concentrations up to 8 ??mol/L, with an average S-chain-length from 4.1 to 4.9 sulfur atoms. The results indicate that no thiosulfate occurs in the deeper parts of the hydrothermal system. Thiosulfate may form, however, from (1) hydrolysis of native sulfur by hydrothermal solutions in the shallower parts (<50 m) of the system, (2) oxidation of dissolved sulfide upon mixing of a deep hydrothermal water with aerated shallow groundwater, and (3) the oxidation of dissolved sulfide by dissolved oxygen upon discharge of the hot spring. Upon discharge of a sulfide-containing hydrothermal water, oxidation proceeds rapidly as atmospheric oxygen enters the water. The transfer of oxygen is particularly effective if the hydrothermal discharge is turbulent and has a large surface area.

In vitro toxicity of zinc oxide nanoparticles: a review

NASA Astrophysics Data System (ADS)

Pandurangan, Muthuraman; Kim, Doo Hwan

2015-03-01

The toxic effect of ZnO nanoparticles is due to their solubility. ZnO nanoparticles dissolve in the extracellular region, which in turn increases the intracellular [Zn2+] level. The mechanism for increased intracellular [Zn2+] level and ZnO nanoparticles dissolution in the medium is still unclear. Cytotoxicity, increased oxidative stress, increased intracellular [Ca2+] level, decreased mitochondrial membrane potential, and interleukin-8 productions occur in the BEAS-2B bronchial epithelial cells and A549 alveolar adenocarcinoma cells following the exposure of ZnO nanoparticles. Confluent C2C12 cells are more resistant to ZnO nanoparticles compared to the sparse monolayer. Loss of 3T3-L1 cell viability, membrane leakage, and morphological changes occurs due to exposure of ZnO nanoparticles. ZnO nanoparticle induces cytotoxicity and mitochondrial dysfunction in RKO colon carcinoma cells. The occurrence of apoptosis, increased ROS level, reduced mitochondrial activity and formation of tubular intracellular structures are reported following exposure of ZnO nanoparticles in skin cells. Macrophages, monocytes, and dendritic cells are affected by ZnO nanoparticles. In addition, genotoxicity is also induced. The present review summarizes the literature on in vitro toxicity of ZnO nanoparticles (10-100 nm) on various cell lines.

In Situ Groundwater Denitrification in the Riparian Zone of a Short-Rotation Woody Crop Experimental Watershed

NASA Astrophysics Data System (ADS)

Jeffers, J. B.; Jackson, C. R.; Rau, B.; Pringle, C. M.; Matteson, C.

2017-12-01

The southeastern United States has potential to become a major producer of short rotation woody crops (SRWC) for the production of biofuels, but this will require converting to more intensive forest management practices that will increase nitrate (NO3-) loading and alter nitrogen cycling in nearby freshwater ecosystems. Water quality monitoring in an experimental short-rotation woody crop watershed in the Coastal Plain of South Carolina has shown increased concentrations of NO3- in groundwater but no evidence of increased NO3- in riparian groundwater or surface waters. Forested riparian areas established as streamside management zones (SMZ) are known to act as buffers to surface water bodies by mitigating nutrients. The objectives of this study were to quantify denitrification by measuring dinitrogen (N2) and nitrous oxide (N2O) concentrations along groundwater flow paths and analyze relationships between denitrification estimates, nutrients, and water chemistry parameters. A network of piezometers has been established in the Fourmile Experimental Watershed at the Department of Energy - Savannah River Site. Water samples were collected monthly and were analyzed for concentrations of nutrients (temperature, specific conductivity, dissolved oxygen, pH, dissolved organic carbon) and dissolved gases (N2, Ar, N2O). Preliminary data showed greater dissolved N2O concentrations than dissolved N2 concentrations in groundwater. The ratios of N2O to combined end products of denitrification (N2O / N2O+N2) ranged from 0.33 to 0.99. Mean N2O+N2 concentrations were greater in groundwater samples in the SRWC plot and along the SMZ boundary than along the ephemeral stream within the riparian zone. Correlations between water chemistry parameters and N2 concentrations are indicative of known biogeochemical driving factors of denitrification. Continued monthly sampling will be coupled with analysis of nutrient concentrations (NO3-, NH4+, TN) to help determine transport and processing of NO3- and production of dissolved gases within the groundwater system. Use of hydrologic models combined with dissolved gas concentrations will provide estimates of denitrification rates and indirect gaseous emissions.

Physiological and biochemical aspects of ozone toxicity to rainbow trout (Salmo gairdneri)

USGS Publications Warehouse

Wedemeyer, Gary A.; Nelson, Nancy C.; Yasutake, William T.

1979-01-01

An acute toxicity curve for dissolved ozone (O3) in soft water at 10 °C, using 10–13-cm rainbow trout (Salmo gairdneri) as the test species was calculated. The 96-h LC50 (95%, confidence interval) was 9.3 (8.1–10.6) μg/L. The lethal threshold level was about 8 μg/L mandating that a conservative margin of safety be used if ozone is employed as a fish disease control agent. Death apparently results from massive destruction of the gill lamellar epithelium together with a severe hydromineral imbalance. In partial chronic (3-mo) testing, 2 μg/L caused no significant biological damage while 5 μg/L caused some gill pathological changes and reduced feeding behavior. Accordingly, 2 μg/L is suggested as a provisional maximum safe exposure level, pending completion of life cycle studies. Thus, if ozone-treated water is discharged into the environment, dissolved O3 should be reduced to at least the 2 μg/L level to minimize adverse impacts on salmonids in receiving waters.

Distribution of dissolved green-house gases (CO2, CH4, N2O) in Lakes Edward and George: Results from the first field cruise of the HIPE project

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Morana, Cédric D. T.; Lambert, Thibault; Okello, William; Bouillon, Steven

2017-04-01

Inland waters (streams, rivers, lakes, reservoirs) are quantitatively important components of the global budgets of atmospheric emissions of long-lived greenhouse gases (GHGs) (CO2, CH4, N2O). Available data indicate that a very large fraction of CO2 and CH4 emissions from rivers and reservoirs occurs at tropical latitudes. Data on GHGs at tropical latitudes from lakes however are much more scarse, and the relative importance of emissions, in particular in Africa, remains to be determined. Large tropical lakes are net autotrophic (hence potentially sinks for atmospheric CO2) due generally low dissolved organic carbon concentrations, seasonally near constant light and temperature conditions, and generally deep water columns favourable for export of organic matter to depth. This sharply contrasts with their much better documented temperate and boreal counterparts, usually considered as CO2 sources to the atmosphere sustained by net heterotrophy. Here, we report a data-set of dissolved CO2, CH4, N2O obtained in October 2016 in Lakes Edward and George and adjacent streams and crater lakes in the frame of Belgian Science Policy (BELSPO) HIPE (Human impacts on ecosystem health and resources of Lake Edward, http://www.co2.ulg.ac.be/hipe/) project. Lake George and part of Lake Edward were sinks for atmospheric CO2 and N2O due to high primary production and denitrification in sediments, respectively, and modest sources of CH4 to the atmosphere. Sampled rivers and streams were oversaturated in CO2 and CH4 and close to atmospheric equilibrium with regards to N2O. Spatial variations within rivers and streams were related to elevation and vegetation characteristics on the catchments (savannah versus forest). Levels of CO2, CH4, and N2O were within the range of those we reported in other African rivers. Crater lakes acted as sinks for atmospheric CO2 and N2O but were extremely over-saturated in CH4, due to intense primary production sustained by cyanobacteria. These CH4 levels were much higher than what we have reported in other lakes and reservoirs elsewhere in Sub-Saharan Africa.

Testing and Validation Studies of the NSMII-Benthic Sediment Diagenesis Module

DTIC Science & Technology

2016-07-01

NSMII analytical vs. numerical solutions of sediment methane ............................ 27 3.2.4 Comparisons of the diagenesis rates of three sediment...26 Figure 12. Comparisons of NSMII analytical vs. numerical solutions of sediment methane : (a) layer 2’s CH4, (b...oxygen demand mg-O2 L-1 0-10 CH4 Methane mg-O2 L-1 On/Off HxS Total dissolved sulfides mg-O2 L-1 On/Off DO Dissolved oxygen mg-O2 L-1 On BSi

Titania/CnTAB Nanoskeleton as adsorbent and photocatalyst for removal of alkylphenols dissolved in water.

PubMed

Sakai, Toshio; Da Loves, Albar; Okada, Tomohiko; Mishima, Shozi

2013-03-15

We report here on the removal of alkylphenols (phenol, 4-n-propylphenol, 4-n-heptylphenol and 4-nonylphenol) dissolved in water using the composite particles of nanocrystalline titania and alkyltrimethylammonium bromide (CnH2n+1N(CH3)3Br, CnTAB; n=12, 14, 16 and 18) (named as TiO2/CnTAB Nanoskeleton) as adsorbents and photocatalysts. In particular, the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton in water was investigated in terms of hydrophobic interaction between alkylphenols and CnTAB, surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton. We revealed that CnTAB incorporated in the TiO2/CnTAB Nanoskeleton promotes the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton due to the hydrophobic interaction between alkylphenols and CnTAB. On the other hand, the surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton did not affect the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton. We also found that the alkylphenols dissolved in water were completely removed by the combination of adsorption and photocatalytic degradation by the TiO2/CnTAB Nanoskeleton under UV irradiation. These results prove that the TiO2/CnTAB Nanoskeleton acts as in tandem an adsorbent and a photocatalyst for removal of alkylphenols dissolved in water. Copyright © 2013 Elsevier B.V. All rights reserved.

Emissions of Water and Carbon Dioxide from Fossil-Fuel Combustion Contribute Directly to Ocean Mass and Volume Increases

NASA Astrophysics Data System (ADS)

Skuce, A. G.

2014-12-01

The direct, non-climate, contribution of carbon dioxide and water emissions from fossil-fuel (FF) combustion to the volume and mass of the oceans has been omitted from estimates of sea-level rise (SLR) in IPCC reports. Following the method of Gornitz et al. (1997), H2O emissions are estimated using carbon emissions from the Carbon Dioxide Information Analysis Center, along with typical carbon and hydrogen contents of FF. Historic H2O emissions from 1750 to 2010 amount to 430 ±50 PgH2O, equivalent to 1.2 ±0.2 mmSLR. Sometime in this decade the volume of H2O from historic FF combustion will exceed the volume of Lake Erie (480 km3). CO2 dissolved in the ocean increases the seawater volume by 31-33 mL mol-1 CO2. From 1750 to 2010, 370 ±70 PgCO2 from FF combustion has dissolved in the oceans, causing 0.7 ±0.2 mmSLR. Combined H2O+CO2emissions from FF have therefore added 1.9 ±0.4 mm to sea levels in the Industrial Era. Combustion of FF in 2010 resulted in emissions of 32 PgCO2 and 12 ±1 PgH2O. SLR contributions for that year from FF emissions were 0.033 ±0.005 mm from H2O and 0.011±0.003 mm from dissolved CO2, a total rate of 0.044 ±0.008 mm yr-1. Emissions incorporated in socio-economic models underlying the RCP 8.5 and 2.6 scenarios are used along with concentration-driven CMIP5 Earth System Models results to estimate future sea-level rise from FF combustion. From 2010 to 2100, RCP8.5 and 2.6 models respectively produce 9 ±2 mmSLR and 5 ±1 mmSLR from FF H2O+CO2. For perspective, these amounts are larger than the modelled contributions from loss of glaciers in the Andes. The direct contribution of FF emissions to SLR is small (1-2%) relative to current rates and projected estimates under RCP scenarios up to 2100. The magnitude is similar to SLR estimates from other minor sources such as the melting of floating ice, land-use emissions and produced water from oil operations, none of which are currently included in SLR assessments. As uncertainties in observations and contributions are reduced, small contribution factors, hitherto neglected, will become relatively more important in balancing the books. ReferenceGornitz, V., C. Rosenzweig, and D. Hillel, 1997: Effects of anthropogenic intervention in the land hydrological cycle on global sea level rise. Global and Planetary Change, 14, 147-161. DOI: 10.1016/S0921-8181(96)00008-2

Synthesis of ultrafine powders by microwave heating

DOEpatents

Meek, T.T.; Sheinberg, H.; Blake, R.D.

1987-04-24

A method of synthesizing ultrafine powders using microwaves is described. A water soluble material is dissolved in water and the resulting aqueous solution is exposed to microwaves until the water has dissolved. The resulting material is an ultrafine powder. This method can be used to make Al/sub 2/O/sub 3/, NiO /plus/ Al/sub 2/O/sub 3/ and NiO as well as a number of other materials including GaBa/sub 2/Cu/sub 3/O/sub x/. 1 tab.

Investigation of the noble gas solubility in H 2O-CO 2 bearing silicate liquids at moderate pressure II: the extended ionic porosity (EIP) model

NASA Astrophysics Data System (ADS)

Nuccio, P. M.; Paonita, A.

2000-12-01

A semi-theoretical model is proposed to predict partitioning of noble gases between any silicate liquid and a H 2O-CO 2 gas phase with noble gas as a minor component, in a large range of pressures (at least up to 300 MPa). The model is based on the relationship between the concentration of dissolved noble gas and ionic porosity of the melt, found by Carroll and Stolper [Geochim. Cosmochim. Acta 57 (1993) 5039-5051] for H 2O-CO 2 free melts. It evaluates the effect of dissolved H 2O and CO 2 on the melt ionic porosity and, consequently on Henry's constants of noble gases. The fugacities of the noble gases in the H 2O-CO 2-noble gas mixtures are also considered in our equilibrium calculations of dissolved gas by using a modified Redlich-Kwong equation of state for the H 2O-CO 2-noble gas system. The formulated model (referred to as the extended ionic porosity model) clearly predicts a positive dependence of noble gas solubility on dissolved H 2O in melt, which becomes negligible when water concentration is higher than 3 wt%. Oppositely, noble gas solubility decreases as a consequence of increasing CO 2 in both basaltic and rhyolitic melts. The increase of noble gas solubility as a consequence of H 2O addition to the melt grows exponentially with the increase of the noble gas atomic size. As a result, although xenon solubility is much lower than the helium solubility in anhydrous melts, they become almost comparable at several percent of dissolved H 2O in the melt. On this basis, an exponential augmentation of the number of large free spaces in silicate liquid can be inferred in relation to increasing dissolved H 2O. Comparison between our predicted values and available experimental data [A. Paonita et al., Earth Planet. Sci. Lett. 181 (2000) 595-604] shows good agreement. At present, the EIP model is the unique tool which predicts how the main volatiles in magmatic systems affect the noble gas solubility in silicate melts, therefore it should be taken into account for future studies of noble gas fractionation in degassing natural magmas.

Geraniol attenuates hydrogen peroxide-induced liver fatty acid alterations in male rats.

PubMed

Ozkaya, Ahmet; Sahin, Zafer; Gorgulu, Ahmet Orhan; Yuce, Abdurrauf; Celik, Sait

2017-01-01

Hydrogen peroxide (H 2 O 2 ) is an oxidant agent and this molecule naturally occurs in the body as a product of aerobic metabolism. Geraniol is a plant-derived natural antioxidant. The aim of this study was to determine the role of geraniol on hepatic fatty acids alterations following H 2 O 2 -induced oxidative stress in male rats. After randomization, male Wistar rats were divided into four groups ( n = 7 each group). Geraniol (50 mg/kg, dissolved in corn oil) and H 2 O 2 (16 mg/kg, dissolved in distilled water) were administered by an intraperitoneal injection. Administrations were performed during 30 days with 1-day interval. Administration of H 2 O 2 resulted with a significant increase in malondialdehyde (MDA) and a significant decrease in glutathione (GSH) peroxidase glutathione level; geraniol restored its effects on liver. However, hepatic catalase (CAT) activities were significantly higher in H 2 O 2 , geraniol, and geraniol+H 2 O 2 groups than control group. The ratio of hepatic total saturated fatty acids increased in H 2 O 2 -treated animals compared with control. In addition, hepatic total unsaturated fatty acids reduced in H 2 O 2 group compared with control. The percentages of both hepatic total saturated and unsaturated fatty acids were not different between geraniol+H 2 O 2 and control groups. H 2 O 2 -induced oxidative stress may affect fatty acid composition in liver and body. Geraniol can partly restore oxidative hepatic damage because it cannot completely reverse the H 2 O 2 -induced increase in hepatic CAT activities. Moreover, this natural compound can regulate hepatic total saturated and unsaturated fatty acids percentages against H 2 O 2 -induced alterations.

In vitro immunotoxicology of quantum dots and comparison with dissolved cadmium and tellurium.

PubMed

Bruneau, Audrey; Fortier, Marlene; Gagne, Francois; Gagnon, Christian; Turcotte, Patrice; Tayabali, Azam; Davis, Thomas A; Auffret, Michel; Fournier, Michel

2015-01-01

The increasing use of products derived from nanotechnology has raised concerns about their potential toxicity, especially at the immunocompetence level in organisms. This study compared the immunotoxicity of cadmium sulfate/cadmium telluride (CdS/Cd-Te) mixture quantum dots (QDs) and their dissolved components, cadmium chloride (CdCl2 )/sodium telluride (NaTeO3 ) salts, and a CdCl2 /NaTeO3 mixture on four animal models commonly used in risk assessment studies: one bivalve (Mytilus edulis), one fish (Oncorhynchus mykiss), and two mammals (mice and humans). Our results of viability and phagocytosis biomarkers revealed that QDs were more toxic than dissolved metals for blue mussels. For other species, dissolved metals (Cd, Te, and Cd-Te mixture) were more toxic than the nanoparticles (NPs). The most sensitive species toward QDs, according to innate immune cells, was humans (inhibitory concentration [IC50 ] = 217 μg/mL). However, for adaptative immunity, lymphoblastic transformation in mice was decreased for small QD concentrations (EC50 = 4 μg/mL), and was more sensitive than other model species tested. Discriminant function analysis revealed that blue mussel hemocytes were able to discriminate the toxicity of QDs, Cd, Te, and Cd-Te mixture (Partial Wilk's λ = 0.021 and p < 0.0001). For rainbow trout and human cells, the immunotoxic effects of QDs were similar to those obtained with the dissolved fraction of Cd and Te mixture. For mice, the toxicity of QDs markedly differed from those observed with Cd, Te, and dissolved Cd-Te mixture. The results also suggest that aquatic species responded more differently than vertebrates to these compounds. The results lead to the recommendation that mussels and mice were most able to discriminate the effects of Cd-based NPs from the effects of dissolved Cd and Te at the immunocompetence level. © 2013 Wiley Periodicals, Inc.

Continuous monitoring of dissolved gases with membrane inlet mass spectrometry to fingerprint river biochemical activity

NASA Astrophysics Data System (ADS)

Vautier, Camille; Chatton, Eliot; Abbott, Benjamin; Harjung, Astrid; Labasque, Thierry; Guillou, Aurélie; Pannard, Alexandrine; Piscart, Christophe; Laverman, Anniet; Kolbe, Tamara; Massé, Stéphanie; de Dreuzy, Jean-Raynald; Thomas, Zahra; Aquilina, Luc; Pinay, Gilles

2017-04-01

Water quality in rivers results from biogeochemical processes in contributing hydrological compartments (soils, aquifers, hyporheic and riparian zones) and biochemical activity in the river network itself. Consequently, chemical fluxes fluctuate on multiple spatial and temporal scales, leading eventually to complex concentration signals in rivers. We characterized these fluctuations with innovative continuous monitoring of dissolved gases, to quantify transport and reaction processes occurring in different hydrological compartments. We performed stream-scale experiments in two headwater streams in Brittany, France. Factorial injections of inorganic nitrogen (NH4NO3), inorganic phosphate (P2O5) and multiple sources of labile carbon (acetate, tryptophan) were implemented in the two streams. We used a new field application of membrane inlet mass spectrometry to continuously monitor dissolved gases for multiple day-night periods (Chatton et al., 2016). Quantified gases included He, O2, N2, CO2, CH4, N2O, and 15N of dissolved N2 and N2O. We calibrated and assessed the methodology with well-established complementary techniques including gas chromatography and high-frequency water quality sensors. Wet chemistry and radon analysis complemented the study. The analyses provided several methodological and ecological insights and demonstrated that high frequency variations linked to background noise can be efficiently determined and filtered to derive effective fluxes. From a more fundamental point of view, the tested stream segments were fully characterized with extensive sampling of riverbeds and laboratory experiments, allowing scaling of point-level microbial and invertebrate diversity and activity on in-stream processing. This innovative technology allows fully-controlled in-situ experiments providing rich information with a high signal to noise ratio. We present the integrated nutrient demand and uptake and discuss limiting processes and elements at the reach and catchment scales. Eliot Chatton, Thierry Labasque, Jérôme de La Bernardie, Nicolas Guihéneuf, Olivier Bour, Luc Aquilina. 2016. Field Continuous Measurement of Dissolved Gases with a CF-MIMS: Applications to the Physics and Biogeochemistry of Groundwater Flow. Environ. Sci. Technol.

Reconciling "Whiffs" of O2 with the Archean MIF S Record: Insights from Sulfide Oxidation Experiments

NASA Astrophysics Data System (ADS)

Johnson, A.; Reinhard, C. T.; Romaniello, S. J.; Greaney, A. T.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2016-12-01

The Archean-Proterozoic transition is marked by the first appreciable accumulation of O2 in Earth's oceans and atmosphere at 2.4 billion years ago (Ga). However, this Great Oxidation Event (GOE) is not the first evidence for O2 in Earth's surface environment. Paleoredox proxies preserved in ancient marine shales (Mo, Cr, Re, U) suggest transient episodes of oxidative weathering before the GOE, perhaps as early as 3.0 Ga. One marine shale in particular, the 2.5 Ga Mount McRae Shale of Western Australia, contains a euxinic interval with Mo enrichments up to 50 ppm. This enrichment is classically interpreted as the result of oxidative weathering of sulfides on the continental surface. However, prior weathering models based on experiments suggested that sulfides require large amounts of O2 [>10-4 present atmospheric level (PAL) pO2] to produce this weathering signature, in conflict with estimates of Archean pO2 from non-mass-dependent (NMD) sulfur isotope anomalies (<10-5 PAL pO2). To reconcile these datasets, we conducted aqueous oxidation experiments of pyrite and molybdenite from 3 - 700 nM O2 (equivalent at equilibrium to 10-5 - 10-3 PAL) to measure oxidation kinetics as a function of the concentration of dissolved O2. We measured rates by injecting oxygenated water at a steady flow rate and monitoring dissolved O2 concentrations with LUMOS sensors. Our data extend the O2 range explored in pyrite oxidation experiments by three orders of magnitude and provide the first rates for molybdenite oxidation at O2 concentrations potentially analogous to those characteristic of the Archean atmosphere. Our results show that pyrite and molybdenite oxidize significantly more rapidly at lower O2 levels than previously thought. As a result, our revised weathering model demonstrates that the Mo enrichments observed in late Archean marine shales are potentially attainable at extremely low atmospheric pO2 values (e.g., <10-5 PAL), reconciling large sedimentary Mo enrichments with co-occurring NMD sulfur isotope anomalies.

Incinerator ash dissolution model for the system: Plutonium, nitric acid and hydrofluoric acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, E V

1988-06-01

This research accomplished two goals. The first was to develop a computer program to simulate a cascade dissolver system. This program would be used to predict the bulk rate of dissolution in incinerator ash. The other goal was to verify the model in a single-stage dissolver system using Dy/sub 2/O/sub 3/. PuO/sub 2/ (and all of the species in the incinerator ash) was assumed to exist as spherical particles. A model was used to calculate the bulk rate of plutonium oxide dissolution using fluoride as a catalyst. Once the bulk rate of PuO/sub 2/ dissolution and the dissolution rate ofmore » all soluble species were calculated, mass and energy balances were written. A computer program simulating the cascade dissolver system was then developed. Tests were conducted on a single-stage dissolver. A simulated incinerator ash mixture was made and added to the dissolver. CaF/sub 2/ was added to the mixture as a catalyst. A 9M HNO/sub 3/ solution was pumped into the dissolver system. Samples of the dissolver effluent were analyzed for dissolved and F concentrations. The computer program proved satisfactory in predicting the F concentrations in the dissolver effluent. The experimental sparge air flow rate was predicted to within 5.5%. The experimental percentage of solids dissolved (51.34%) compared favorably to the percentage of incinerator ash dissolved (47%) in previous work. No general conclusions on model verification could be reached. 56 refs., 11 figs., 24 tabs.« less

Direct oxygen removal technique for recycling titanium using molten MgCl2 salt.

PubMed

Okabe, Toru H; Hamanaka, Yuki; Taninouchi, Yu-Ki

2016-08-15

Deoxidation of Ti, or direct removal of O dissolved in metallic Ti, is known to be extremely difficult when Mg is used as the deoxidizing agent. This difficulty arises because the chemical potential of O2, pO2, under Mg/MgO equilibrium is high (approximately 10(-41) atm at 1200 K) and is equivalent to that of Ti containing ∼2 mass% O at 1200 K. Therefore, when deoxidizing Ti to the commercial level of high-grade pure Ti (below 0.05 mass% O) using an Mg reductant at 1200 K, the activity of the reaction product MgO (aMgO) must be decreased to below ∼0.025, which is difficult in practice. In this study, the removal of O in Ti in molten MgCl2 salt using an electrochemical technique was examined at ∼1173 K with the objective of obtaining Ti containing less than 0.05 mass% O. Ti samples and graphite electrodes immersed in molten MgCl2 served as the cathode and anode, respectively. A constant voltage was applied between the electrodes using an external DC source. Molten MgCl2 was employed to produce the deoxidizing agent Mg and to facilitate deoxidation of Ti by decreasing the activity of the reaction product MgO. By applying a voltage of approximately 3.1 V between the electrodes, the chemical potential of Mg in the molten MgCl2 was increased at the surface of the Ti cathode, and the Ti samples were deoxidized. The resulting O species, mainly formed O(2-) dissolved in the molten MgCl2, was removed from the molten salt by reacting with the C anode to form CO (or CO2) gas. Ti wires containing 0.12 mass% O were deoxidized to less than 0.02 mass% O. In some cases, the O concentration in the Ti samples was reduced to the level of 0.01 mass%, which cannot be accomplished using the conventional Kroll process. The possible application of this deoxidation technique to practical industrial recycling processes is discussed.

Oxygen Carbon Dynamics within the Hyporheic Zone of a Headwater Stream

NASA Astrophysics Data System (ADS)

Pennington, R.; Haggerty, R.; Wondzell, S. M.; Serchan, S. P.; Reeder, W. J.; Tonina, D.

2016-12-01

Streams and rivers influence global carbon fluxes; on an aerial basis, they have disproportionately high export rates compared to land. Various mechanisms exist for the movement of terrestrially derived carbon to the stream network including transport of organic and inorganic carbon with groundwater and hillslope runoff. A secondary process that has received little attention is carbon dynamics of hyporheic flow along flow paths that pass beneath the vegetated riparian zone. Through use of high frequency monitoring of dissolved inorganic carbon and dissolved oxygen we find that the riparian zone is a net source of carbon throughout the year. Increases in DIC relative stream water are generally more than double decreases in O2 on a molar basis. Metabolic quotients of C to O2 are close to 1.0, therefore respiration of dissolved or particulate organic carbon along flow paths would result in an equal magnitude increase in inorganic carbon to decrease in O2. Diffusion from the high CO2 soil atmosphere into hyporheic water has been considered, however 2-D reactive transport modeling using PFLOTRAN indicates that soil diffusion processes are unlikely to produce observed increases in carbon and that alternative transport mechanisms including root respiration or diel water level fluctuations are necessary for mass balance. Results of the analysis will feed into a comprehensive distributed model of the system that explores carbon dynamics at the reach scale.

Temporal variations in dissolved selenium in Lake Kinneret (Israel)

USGS Publications Warehouse

Nishri, A.; Brenner, I.B.; Hall, G.E.M.; Taylor, Howard E.

1999-01-01

Selenium is an essential micronutrient for the growth of the dinoflagellate Peridinium gatunense that dominates the spring algal bloom in Lake Kinneret (LK). The relationship between the levels of dissolved selenium species and the occurance of algal blooms in this lake was studied. During algal blooms of P. gatunense in spring and of the blue-green Aphanizomenon ovalisporum in fall (in 1994) the concentration of epilimnetic dissolved organic Se (Se(org)) increased whereas that of selenite (SeIV) decreased, to levels below the limit of detection: 5 ng/l. The disappearance of SeIV during these blooms is attributed to algal uptake and it is suggested that the growth of both algae may have depended on Se(org) regeneration. A budget performed for selenate (SeVI) suggests that this species is also consumed by algae but to a lesser extent than SeIV (in 1994 ~40% of the epilimnetic load). During the stratification period the hypolimnion of Lake Kinneret becomes anoxic, with high levels of dissolved sulfide. The affects of this environment on the distribution of Se oxy-anions, selenite (SeIV) and selenate(SeVI), were also studied. At the onset of thermal stratification (March) about 35% of the lake inventory of both Se oxidized species are entrapped in the hypolimnion. During stages of oxygen depletion and H2S accumulation, SeIV is completely and SeVI partially removed from this layer. The removal is attributed to reduction followed by formation of particulate reduced products, such as elemental selenium Se(o). The ratio between SeVI to total dissolved selenium (SE(T)) in water sources to the lake is ~0.84, about twice the corresponding ratio in the lake (~0.44, during holomixis). In the lake about 75% of annual SeVI inflow from external sources undergoes reduction to selenide (Se-II) and Se(o) through epilimnetic algal assimilation and hypolimnetic anoxic reduction, respectively. It is suggested that the latter oxidation of the dissolved organic selenide released from biogenic particles and of Se(o) only to the tetravalent species is the cause for the lower ratio of SeVI/Se(T) in the lake.

Effect of Biological and Mass Transfer Parameter Uncertainty on N₂O Emission Estimates from WRRFs.

PubMed

Song, Kang; Harper, Willie F; Takeuchi, Yuki; Hosomi, Masaaki; Terada, Akihiko

2017-07-01

  This research used the detailed activated sludge model (ASM) to investigate the effect of parameter uncertainty on nitrous oxide (N2O) emissions from biological wastewater treatment systems. Monte Carlo simulations accounted for uncertainty in the values of the microbial growth parameters and in the volumetric mass transfer coefficient for dissolved oxygen (kLaDO), and the results show that the detailed ASM predicted N2O emission of less than 4% (typically 1%) of the total influent loading. Uncertainties in kLaDO were further investigated in experiments, which showed that lower values of kLaDO generated higher soluble N2O levels. The detailed ASM likely requires revision to account for abiotic reactions and other factors that cause higher levels of N2O emission.

δ34S and δ18O of dissolved sulfate as biotic tracer of biogeochemical influences on arsenic mobilization in groundwater in the Hetao Plain, Inner Mongolia, China.

PubMed

Li, M D; Wang, Y X; Li, P; Deng, Y M; Xie, X J

2014-12-01

Environmental isotopology of sulfur and oxygen of dissolved sulfate in groundwater was conducted in the Hetao Plain, northwestern China, aiming to better understand the processes controlling arsenic mobilization in arsenic-rich aqueous systems. A total of 22 groundwater samples were collected from domestic wells in the Hetao Plain. Arsenic concentrations ranged from 11.0 to 388 μg/L. The δ(34)S-SO4 and δ(18)O-SO4 values of dissolved sulfate covered a range from +1.48 to +22.4‰ and +8.17‰ to +14.8‰ in groundwater, respectively. The wide range of δ(34)S-SO4 values reflected either an input of different sources of sulfate, such as gypsum dissolution and fertilizer application, or a modification from biogeochemical process of bacterial sulfate reduction. The positive correlation between δ(34)S-SO4 and arsenic concentrations suggested that bacteria mediated processes played an important role in the mobilization of arsenic. The δ(18)O-SO4 values correlated non-linearly with δ(34)S-SO4, but within a relatively narrow range (+8.17 to +14.8‰), implying that complexities inherent in the sulfate-oxygen (O-SO4(2-)) origins, for instance, water-derived oxygen (O-H2O), molecular oxygen (O-O2) and isotope exchanging with dissolved oxides, are accounted for oxygen isotope composition of dissolved sulfate in groundwater in the Hetao Plain.

Sediment-water fluxes of dissolved inorganic carbon, O2,nutrients, and N2 from the hypoxic region of the Louisianacontinental shelf

EPA Science Inventory

Sediment fluxes of dissolved inorganic carbon (DIC), O2, nutrients, and N2 (denitrification) were measured on the Louisiana Continental Shelf during six cruises from 2005 to 2007. On each cruise, three to seven stations were occupied in regions of the shelf that experience summer...

A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts.

PubMed

Stolper, Daniel A; Keller, C Brenhin

2018-01-18

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O 2 ) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe 3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts

NASA Astrophysics Data System (ADS)

Stolper, Daniel A.; Keller, C. Brenhin

2018-01-01

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O2) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

Evaluating the Impact of Changes in Oceanic Dissolved Oxygen on Marine Nitrous Oxide

NASA Astrophysics Data System (ADS)

Suntharalingam, Parvadha; Buitenhuis, Erik; Schmidtko, Sunke; Andrews, Oliver; LeQuere, Corinne

2013-04-01

Emissions of the greenhouse gas nitrous-oxide (N2O) from oceanic oxygen minimum zones (OMZs) in the Equatorial Pacific and Northwest Indian Ocean are believed to provide a significant portion of the global oceanic flux to the atmosphere. Mechanisms of marine N2O production and consumption in these regions display significant sensitivity to ambient oxygen, with high yields at low oxygen levels (O2 < 50 micromol/L), and N2O depletion via denitrification in anoxic zones. These OMZ regions display large gradients in sub-surface N2O, and high rates of N2O turnover that far exceed those observed in the open ocean. Recent studies have suggested that possible expansion of oceanic OMZs in a warming climate, could lead to significant changes in N2O emissions from these zones. In this analysis we employ a global ocean biogeochemistry model (NEMO-PlankTOM), which includes representation of the marine N2O cycle, to explore the impact of changes in dissolved oxygen on the ocean-atmosphere N2O flux. We focus on the period 1960-2000, and evaluate the impact of estimated changes in ocean oxygen from two alternative sources : (a) the observationally-based upper-ocean oxygen distributions and trends of Stramma et al. [2012]; (b) simulated oxygen distributions and temporal variations from a set of CMIP5 Earth System models. We will inter-compare the oceanic N2O estimates derived from these alternative scenarios of ocean de-oxygenation. We will also discuss the implications of our results for the ability to reliably predict changes in N2O emissions under potential expansion of oceanic OMZs, particularly in view of the recently noted discrepancies between observed and modeled trends in oceanic oxygen by Stramma et al. [2012].

Biodegradation potential of MTBE in a fractured chalk aquifer under aerobic conditions in long-term uncontaminated and contaminated aquifer microcosms.

PubMed

Shah, Nadeem W; Thornton, Steven F; Bottrell, Simon H; Spence, Michael J

2009-01-26

The potential for aerobic biodegradation of MTBE in a fractured chalk aquifer is assessed in microcosm experiments over 450 days, under in situ conditions for a groundwater temperature of 10 degrees C, MTBE concentration between 0.1 and 1.0 mg/L and dissolved O2 concentration between 2 and 10 mg/L. Following a lag period of up to 120 days, MTBE was biodegraded in uncontaminated aquifer microcosms at concentrations up to 1.2 mg/L, demonstrating that the aquifer has an intrinsic potential to biodegrade MTBE aerobically. The MTBE biodegradation rate increased three-fold from a mean of 6.6+/-1.6 microg/L/day in uncontaminated aquifer microcosms for subsequent additions of MTBE, suggesting an increasing biodegradation capability, due to microbial cell growth and increased biomass after repeated exposure to MTBE. In contaminated aquifer microcosms which also contained TAME, MTBE biodegradation occurred after a shorter lag of 15 or 33 days and MTBE biodegradation rates were higher (max. 27.5 microg/L/day), probably resulting from an acclimated microbial population due to previous exposure to MTBE in situ. The initial MTBE concentration did not affect the lag period but the biodegradation rate increased with the initial MTBE concentration, indicating that there was no inhibition of MTBE biodegradation related to MTBE concentration up to 1.2 mg/L. No minimum substrate concentration for MTBE biodegradation was observed, indicating that in the presence of dissolved O2 (and absence of inhibitory factors) MTBE biodegradation would occur in the aquifer at MTBE concentrations (ca. 0.1 mg/L) found at the front of the ether oxygenate plume. MTBE biodegradation occurred with concomitant O2 consumption but no other electron acceptor utilisation, indicating biodegradation by aerobic processes only. However, O2 consumption was less than the stoichiometric requirement for complete MTBE mineralization, suggesting that only partial biodegradation of MTBE to intermediate organic metabolites occurred. The availability of dissolved O2 did not affect MTBE biodegradation significantly, with similar MTBE biodegradation behaviour and rates down to ca. 0.7 mg/L dissolved O2 concentration. The results indicate that aerobic MTBE biodegradation could be significant in the plume fringe, during mixing of the contaminant plume and uncontaminated groundwater and that, relative to the plume migration, aerobic biodegradation is important for MTBE attenuation. Moreover, should the groundwater dissolved O2 concentration fall to zero such that MTBE biodegradation was inhibited, an engineered approach to enhance in situ bioremediation could supply O2 at relatively low levels (e.g. 2-3 mg/L) to effectively stimulate MTBE biodegradation, which has significant practical advantages. The study shows that aerobic MTBE biodegradation can occur at environmentally significant rates in this aquifer, and that long-term microcosm experiments (100s days) may be necessary to correctly interpret contaminant biodegradation potential in aquifers to support site management decisions.

The combined effects of oxygen availability and salinity on physiological responses and scope for growth in the green-lipped mussel Perna viridis.

PubMed

Wang, Youji; Hu, Menghong; Wong, Wai Hing; Shin, Paul K S; Cheung, Siu Gin

2011-01-01

Mussels were maintained for 4 weeks under different combinations of dissolved oxygen concentration (1.5, 3.0 and 6.0 mg O2 l(-1)) and salinity (15, 20, 25 and 30) in a 3×4 factorial design experiment. Clearance rate (CR), absorption efficiency (AE), respiration rate (RR) and scope for growth (SFG) decreased with decreasing salinity and dissolved oxygen concentration (DO), while excretion rate (ER) increased with decreasing salinity and increasing DO. The O:N ratio was <10 at salinities of 15 and 20, irrespective of DO levels. SFG was negative in most of the treatments, except for those under 6.0 mg O2 l(-1) or at a salinity of 30 when DO was lower. The results may help explain the distribution pattern of Perna viridis in Hong Kong waters and provide guidelines for mussel culture site selection. Copyright © 2011 Elsevier Ltd. All rights reserved.

Gene transcription patterns and energy reserves in Daphnia magna show no nanoparticle specific toxicity when exposed to ZnO and CuO nanoparticles.

PubMed

Adam, Nathalie; Vergauwen, Lucia; Blust, Ronny; Knapen, Dries

2015-04-01

There is still a lot of contradiction on whether metal ions are solely responsible for the observed toxicity of ZnO and CuO nanoparticles to aquatic species. While most experiments have studied nanoparticle effects at organismal levels (e.g. mortality, reproduction), effects at lower levels of biological organization may clarify the role of metal ions, nanoparticles and nanoparticle aggregates. In this study, the effect of ZnO and CuO nanoparticles was tested at two lower levels: energy reserves and gene transcription and compared with zinc and copper salts. Daphnia magna was exposed during 96h to 10% immobilization concentrations of all chemicals, after which daphnids were sampled for determination of glycogen, lipid and protein concentration and for a differential gene transcription analysis using microarray. The dissolved, nanoparticle and aggregated fraction in the medium was characterized. The results showed that ZnO nanoparticles had largely dissolved directly after addition to the test medium. The CuO nanoparticles mostly formed aggregates, while only a small fraction dissolved. The exposure to zinc (both nano and metal salt) had no effect on the available energy reserves. However, in the copper exposure, the glycogen, lipid and protein concentration in the exposed daphnids was lower than in the unexposed ones. When comparing the nanoparticle (ZnO or CuO) exposed daphnids to the metal salt (zinc or copper salt) exposed daphnids, the microarray results showed no significantly differentially transcribed gene fragments. The results indicate that under the current exposure conditions the toxicity of ZnO and CuO nanoparticles to D. magna is solely caused by toxic metal ions. Copyright © 2015 Elsevier Inc. All rights reserved.

Occurrence of hexavalent chromium in ground water in the western Mojave Desert, California

USGS Publications Warehouse

Ball, J.W.; Izbicki, J.A.

2004-01-01

About 200 samples from selected public supply, domestic, and observation wells completed in alluvial aquifers underlying the western Mojave Desert were analyzed for total dissolved Cr and Cr(VI). Because Cr(VI) is difficult to preserve, samples were analyzed by 3 methods. Chromium(VI) was determined in the field using both a direct colorimetric method and EPA method 218.6, and samples were speciated in the field for later analysis in the laboratory using a cation-exchange method developed for the study described in this paper. Comparison of the direct colorimetric method and EPA method 218.6 with the new cation-exchange method yielded r2 values of 0.9991 and 0.9992, respectively. Total dissolved Cr concentrations ranged from less than the 0.1 ??g/l detection limit to 60 ??g/l, and almost all the Cr present was Cr(VI). Near recharge areas along the mountain front pH values were near neutral, dissolved O2 concentrations were near saturation, and Cr(VI) concentrations were less than the 0.1 ??g/l detection limit. Chromium(VI) concentrations and pH values increased downgradient as long as dissolved O 2 was present. However, low Cr(VI) concentrations were associated with low dissolved O2 concentrations near ground-water discharge areas along dry lakes. Chromium(VI) concentrations as high as 60 ??g/l occurred in ground water from the Sheep Creek fan alluvial deposits weathered from mafic rock derived from the San Gabriel Mountains, and Cr(VI) concentrations as high as about 36 ??g/l were present in ground water from alluvial deposits weathered from less mafic granitic, metamorphic, and volcanic rocks. Chromium(III) was the predominant form of Cr only in areas where dissolved O2 concentrations were less than 1 mg/l and was detected at a median concentration of 0.1 ??g/l, owing to its low solubility in water of near-neutral pH. Depending on local hydrogeologic conditions and the distribution of dissolved O2, Cr(VI) concentrations may vary considerably with depth. Samples collected under pumping conditions from different depths within wells show that Cr(VI) concentrations can range from less than the 0.1 ??g/l detection limit to 36 ??g/l in a single well and that dissolved O2 concentrations likely control the concentration and redox speciation of Cr in ground water.

Phase relations among K-feldspar, muscovite and H2O at 1.0 GPa and 800°C: Implications for metasediment dissolution and melting at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Fineman, D.; Manning, C. E.

2016-12-01

Melting and solubility of K-feldspar (ksp) and muscovite (mus) were investigated in the system KSi3O6.5 -Al2O3 - H2O at 1.0 GPa and 800 °C with rapid-quench piston-cylinder techniques. Equilibrium assemblages of ksp, mus, silicate liquid (L) and aqueous fluid (V) were deduced from optical and scanning electron microscopy. Quenched silicate liquids and aqueous fluids were distinguished using the methodology of Burnham and Jahns (1962, Am J Sci, 260, 721) and Makhluf et al. (2016, CMP, in press). Experiments on a range of bulk compositions constrain the locations of the V, ksp+V, ms+V, and ksp+L+V fields. This allowed geometrical constraints to be placed on additional phase boundaries in the ternary system. The results show that ksp dissolves incongruently in H2O, with residual liquid or ms depending on the fluid-rock ratio. In contrast, ms dissolves congruently in H2O and KSi3O6.5 -H2O solutions with up to 25 wt% KSi3O6.5. Results indicate that stable hydrous liquid at these conditions has an Al content intermediate between ksp and ms. There is no stable liquid along the ksp-H2O join, consistent with results of Goldsmith and Peterson (1990, Am Min, 75, 1362). All data are consistent with the stability of a supercritical fluid on the KAlSi3O8 -H2O join, with 5-10 wt% dissolved Al2O3. Compositional constraints imply that the liquid phase contains 25 wt% H2O and coexists with a V phase containing 25 wt% dissolved solutes. This in turn implies critical mixing of the fluid phases at higher temperature, which is similar to the systems NaAlSi3O8-H2O and simple granite-H2O. Our results help constrain the conditions of production of supercritical granitic-H2O fluids systems in deep crustal and subduction zone settings.

Surface micro-dissolve method of imparting self-cleaning property to cotton fabrics in NaOH/urea aqueous solution

NASA Astrophysics Data System (ADS)

Fan, Tao; Hu, Ruimin; Zhao, Zhenyun; Liu, Yiping; Lu, Ming

2017-04-01

A simple and economical micro-dissolved process of embedding titanium dioxide (TiO2) nanoparticles into surface zone of cotton fabrics was developed. TiO2 was coated on cotton fabrics in 7% wt NaOH/12% wt urea aqueous solution at low temperature. Photocatalytic efficiency of cotton fabrics treated with TiO2 nanoparticles was studied upon measuring the photocatalytic decoloration of Rhodamine B (RhB) under ultraviolet irradiation. Self-cleaning property of cotton fabric coated with TiO2 was evaluated with color depth of samples (K/S value). The treated fabrics were characterized using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectroscopy (FITR), tensile strength, stiffness and whiteness. The results indicated, TiO2 nanoparticles could be embedded on the surface layer of cotton fabrics throuth surface micro-dissolve method. Treated cotton fabrics possessed distinct photocatalytic efficiency and self-cleaning properties. Tensile strength and whiteness of modified cotton fabrics appeared moderately increasement.

Shifting nitrous oxide source/sink behaviour in a subtropical estuary revealed by automated time series observations

NASA Astrophysics Data System (ADS)

Reading, Michael J.; Santos, Isaac R.; Maher, Damien T.; Jeffrey, Luke C.; Tait, Douglas R.

2017-07-01

The oceans are a major source of the potent greenhouse gas nitrous oxide (N2O) to the atmosphere. However, little information is available on how estuaries and the coastal ocean may contribute to N2O budgets, and on the drivers of N2O in aquatic environments. This study utilised five time series stations along the freshwater to marine continuum in a sub-tropical estuary in Australia (Coffs Creek, Australia). Each time series station captured N2O, radon (222Rn, a natural submarine groundwater discharge tracer), dissolved nitrogen, and dissolved organic carbon (DOC) concentrations for a minimum of 25 h. The use of automated time series observations enabled spatial and tidal-scale variability of N2O to be captured. Groundwater was highly enriched in N2O (up to 306 nM) compared to the receiving surface water. Dissolved N2O supersaturation as high as 386% (27.4 nM) was observed in the upstream freshwater and brackish water areas which represented only a small (∼13%) proportion of the total estuary area. A large area of N2O undersaturation (as low as 53% or 3.9 nM) was observed in the mangrove-dominated lower estuary. This undersaturated area likely resulted from N2O consumption due to nitrate/nitrite (NOx) limitation in mangrove sediments subject to shallow porewater exchange. Overall, the estuary was a minor source of N2O to the atmosphere as the lower mangrove-dominated estuary sink of N2O counteracted groundwater-dominated source of N2O in the upper estuary. Average area-weighted N2O fluxes at the water-air interface approached zero (0.2-0.7 μmol m-2 d-1, depending on piston velocity model used), and were much lower than nitrogen-rich Northern Hemisphere estuaries that are considered large sources of N2O to the atmosphere. This study revealed a temporally and spatially diverse estuary, with areas of N2O production and consumption related to oxygen and total dissolved nitrogen availability, submarine groundwater discharge, and uptake within mangroves.

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH.

PubMed

Hong, Jun; Lu, Sijia; Zhang, Caixiang; Qi, Shihua; Wang, Yanxin

2011-09-01

A new Vis-Fe(0)-H(2)O(2)-citrate-O(2) system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L(-1) of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L(-1) of H(2)O(2), 12.6g of Fe(0) and 1.0 mmol L(-1) of citrate at pH 7.5. Results showed that, in 1h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe(0) surface was found to be at a very low level as <5.4 μmol L(-1). Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe(0)-H(2)O(2)-citrate-O(2) system, which accounted for 75% of substrate removal in 3h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe(0)>H(2)O(2)>citrate>Vis>O(2). This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations. Copyright © 2011 Elsevier Ltd. All rights reserved.

Nitrous Oxide Cycling in the Eastern Tropical South Pacific as Inferred from Isotopic and Isotopomeric Data.

NASA Astrophysics Data System (ADS)

Vedamati, J.; Chang, B. X.; Peters, B. D.; Forbes, M. S.; Mordy, C.; Warner, M. J.; Devol, A.; Ward, B. B.; Casciotti, K. L.

2014-12-01

Marine sources of nitrous oxide (N2O), an important greenhouse gas, account for up to 25% of global emissions, out of which 25-75% originates from oxygen minimum zones (OMZs). The Eastern Tropical South Pacific (ETSP) OMZ is characterized by low to undetectable oxygen concentrations within the water column and is known to be a region of intense N2O cycling. However, the balance of processes regulating N2O production and emissions is still uncertain. The isotopic composition of dissolved N2O is a tracer of its production, transport, and consumption processes in the ocean. Here we use concentration, isotopic and isotopomeric measurements of dissolved N2O collected during cruise NBP1305 to the ETSP in 2013 to examine the processes affecting the distribution of N2O throughout the water column. Dissolved N2O concentrations ranged between 42-65 nmol/L at the edges of the oxycline while ranging between 6 -20 nmol/L at the core of the OMZ. The nitrogen and oxygen isotopic composition of dissolved N2O (reported as δ15N vs air N2 and δ18O vs VSMOW in units of ‰, respectively) displayed maxima coincident with the OMZ core. δ15N of N2O ranged between 14 - 22‰, δ18O of N2O ranged between 68 - 100‰ while site preference of N2O ranged between 39 - 60‰ at the OMZ core. Based on the T-S plot and N2O concentration profiles, there appears to be a strong correlation between N2O and water mass features within the OMZ. Thus, the differences in δ15N and δ18O of N2O along the north- south transect within the OMZ core may be related to differences in N2O production-consumption mechanisms along with N2O transport. Within the OMZ, the δ18O: δ15N relationship is also much lower than the 2.5:1 ratio expected for N2O consumption via denitrification, leading us to believe that both production and consumption processes are likely to be at play.

Hydrogen peroxide measurements in recreational marine bathing waters in Southern California, USA.

PubMed

Clark, Catherine D; De Bruyn, Warren J; Hirsch, Charlotte M; Jakubowski, Scott D

2010-04-01

Hydrogen peroxide (H(2)O(2)) was measured in the surf zone at 13 bathing beaches in Southern California, USA. Summer dry season concentrations averaged 122 +/- 38 nM with beaches with tide pools having lower levels (50-90 nM). No significant differences were observed for ebb waters at a salt marsh outlet vs. a beach (179 +/- 20 vs. 163 +/- 26 nM), and between ebb and flood tides at one site (171 +/- 24 vs. 146 +/- 42 nM). H(2)O(2) levels showed little annual variation. Diel cycling was followed over short (30 min; 24 h study) and long (d) time scales, with maximum afternoon concentration = 370 nM and estimated photochemical production rate of 44 nM h(-1). There was no correlation between the absorbance coefficient at 300 nm (used as a measure of chromophoric dissolved organic matter (CDOM) levels) and H(2)O(2). H(2)O(2) concentrations measured in this study are likely sufficient to inhibit fecal indicator bacteria in marine recreational waters through indirect photoinactivation. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Spatial variability in groundwater N2 and N2O in the San Joaquin River

NASA Astrophysics Data System (ADS)

Hinshaw, S.; Dahlgren, R. A.

2010-12-01

The San Joaquin River is surrounded by nearly 2 million acres of irrigated agricultural land. Groundwater inputs from agricultural areas can have severe negative effects on water quality with high nitrate concentrations being a major concern. Riparian zones are important ecological habitats that mitigate nitrogen loading from groundwater discharging into rivers primarily by denitrification. Denitrification is a permanent removal of nitrate by anaerobic microbial communities via the reduction to NO, N2O and N2. However, previous studies have shown that these areas can be source of N2O emissions. Although removal of nitrate through denitrification is advantageous from a water quality perspective, N2O is a harmful greenhouse gas. This study aimed to investigate nitrogen dynamics and dissolved N gases in surface and groundwater of the riparian zones of the San Joaquin River. Excess N2 and N2O concentrations were measured in surface and groundwater at 4 locations along a 33 km reach of the river. Samples were collected within bank sediments and 5 transect points across the river at depth intervals between 2-3 cm and 150 cm. Dissolved N2 and Ar were measured by membrane inlet mass spectrometry and used to estimate excess dissolved N2 concentrations. Dissolved N2O concentrations were measured using the headspace equilibrium technique and analyzed with a gas chromatograph. Both N2 uptake and excess N2 were present, ranging from -3.40 to 8.65 N2 mg/L with a median concentration of 1.20 N2 mg/L. Significantly lower concentrations of N2O were present ranging from 0.0 to 0.12 N2O mg/L. Deeper groundwater sites had significantly higher N2 and N2O concentrations coinciding with decreased O2. The presence of excess N2 and low N2O concentrations documents the importance of denitrification in removing nitrate from groundwater. Further investigation will examine N2O emissions from riparian soils and benthic sediments using static chambers and focus on nitrogen pathways that contribute to high ammonium concentrations with increasing depth.

Triple oxygen isotope composition of photosynthetic oxygen

NASA Astrophysics Data System (ADS)

van der Meer, Anne; Kaiser, Jan

2013-04-01

The measurement of biological production rates is essential for our understanding how marine ecosystems are sustained and how much CO2 is taken up through aquatic photosynthesis. Traditional techniques to measure marine production are laborious and subject to systematic errors. A biogeochemical approach based on triple oxygen isotope measurements in dissolved oxygen (O2) has been developed over the last few years, which allows the derivation of gross productivity integrated over the depth of the mixed layer and the time-scale of O2 gas exchange (Luz and Barkan, 2000). This approach exploits the relative 17O/16O and 18O/16O isotope ratio differences of dissolved O2 compared to atmospheric O2 to work out the rate of biological production. Two parameters are key for this calculation: the isotopic composition of dissolved O2 in equilibrium with air and the isotopic composition of photosynthetic oxygen. Recently, a controversy has emerged in the literature over these parameters (Kaiser, 2011) and one of the goals of this research is to provide additional data to resolve this controversy. In order to obtain more information on the isotopic signature of biological oxygen, laboratory experiments have been conducted to determine the isotopic composition of oxygen produced by different phytoplankton cultures.

An experimental study of ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite: a strong dependence on H2O in the melt

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2017-06-01

The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+-Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785-850 °C and 80-185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni-NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+-Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

USGS Publications Warehouse

Apps, J.A.; Zheng, Lingyun; Spycher, N.; Birkholzer, J.T.; Kharaka, Y.; Thordsen, J.; Kakouros, E.; Trautz, R.

2011-01-01

Food-grade CO2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1-2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca+2-driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO2 dissolution appears to compete for sorption with anionic species such as HAsO4-2, potentially increasing dissolved As levels in groundwater. ?? 2011 Published by Elsevier Ltd.

Simulated nitrogen deposition reduces CH4 uptake and increases N2O emission from a subtropical plantation forest soil in southern China.

PubMed

Wang, Yongsheng; Cheng, Shulan; Fang, Huajun; Yu, Guirui; Xu, Minjie; Dang, Xusheng; Li, Linsen; Wang, Lei

2014-01-01

To date, few studies are conducted to quantify the effects of reduced ammonium (NH4+) and oxidized nitrate (NO3-) on soil CH4 uptake and N2O emission in the subtropical forests. In this study, NH4Cl and NaNO3 fertilizers were applied at three rates: 0, 40 and 120 kg N ha(-1) yr(-1). Soil CH4 and N2O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0-20 cm depth was measured weekly to examine the regulation to soil CH4 and N2O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH4+-N concentrations, but high levels of applied NH4Cl and NaNO3 fertilizers significantly increased soil NO3(-)-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH4 uptake, but significantly promoted soil N2O emission by 403% to 762%. Furthermore, NH4+-N fertilizer application had a stronger inhibition to soil CH4 uptake and a stronger promotion to soil N2O emission than NO3(-)-N application. Also, both soil CH4 and N2O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH4 uptake and N2O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH4 uptake and N2O emission.

Greenhouse gases dissolved in soil solution - often ignored, but important?

NASA Astrophysics Data System (ADS)

Weymann, Daniel; Brueggemann, Nicolas; Puetz, Thomas; Vereecken, Harry

2014-05-01

Flux measurements of climate-relevant trace gases from soils are frequently undertaken in contemporary ecosystem studies and substantially contribute to our understanding of greenhouse gas balances of the biosphere. While the great majority of such investigations builds on closed chamber and eddy covariance measurements, where upward gas fluxes to the atmosphere are measured, fewest concurrently consider greenhouse gas dissolution in the seepage and leaching of dissolved gases via the vadose zone to the groundwater. Here we present annual leaching losses of dissolved N2O and CO2 from arable, grassland, and forest lysimeter soils from three sites differing in altitude and climate. We aim to assess their importance in comparison to direct N2O emission, soil respiration, and further leaching parameters of the C- and N cycle. The lysimeters are part of the Germany-wide lysimeter network initiative TERENO-SoilCan, which investigates feedbacks of climate change to the pedosphere on a long-term scale. Soil water samples were collected weekly from different depths of the profiles by means of suction cups. A laboratory pre-experiment proved that no degassing occurred under those sampling conditions. We applied the headspace equilibration technique to determine dissolved gas concentrations by gas chromatography. The seepage water of all lysimeters was consistently supersaturated with N2O and CO2 compared to water equilibrated ambient air. In terms of N2O, leaching losses increased in the ascending order forest, grassland, and arable soils, respectively. In case of the latter soils, we observed a strong variability of N2O, with dissolved concentrations up to 23 μg N L-1. However, since seepage discharge of the arable lysimeters was comparatively small and mostly limited to the hydrological winter season, leached N2O appeared to be less important than direct N2O emissions. In terms of dissolved CO2,our measurements revealed considerable leaching losses from the mountainous forest and grassland soils, based on concentrations up to 24 mg C L-1 and high seepage discharge. Such losses turned out to be similarly important like soil respiration, particularly during winter when temperature-dependent soil respiration declined. In conclusion, the results of the first year of our measurements provide evidence that dissolved greenhouse gases should be considered in studies which aim to assess full greenhouse gas balances, particularly in ecosystems where hydrological conditions favour microbial activity and high leaching losses.

Spatial and temporal shifts in gross primary productivity, respiration, and nutrient concentrations in urban streams impacted by wastewater treatment plant effluent

NASA Astrophysics Data System (ADS)

Ledford, S. H.; Toran, L.

2017-12-01

Impacts of wastewater treatment plant effluent on nutrient retention and stream productivity are highly varied. The working theory has been that large pulses of nutrients from plants may hinder in-stream nutrient retention. We evaluated nitrate, total dissolved phosphorus, and dissolved oxygen in Wissahickon Creek, an urban third-order stream in Montgomery and Philadelphia counties, PA, that receives effluent from four wastewater treatment plants. Wastewater treatment plant effluent had nitrate concentrations of 15-30 mg N/L and total dissolved phosphorus of 0.3 to 1.8 mg/L. Seasonal longitudinal water quality samples showed nitrate concentrations were highest in the fall, peaking at 22 mg N/L, due to low baseflow, but total dissolved phosphorous concentrations were highest in the spring, reaching 0.6 mg/L. Diurnal dissolved oxygen patterns above and below one of the treatment plants provided estimates of gross primary productivity (GPP) and ecosystem respiration (ER). A site 1 km below effluent discharge had higher GPP in April (80 g O2 m-2 d-1) than the site above the plant (28 g O2 m-2 d-1). The pulse in productivity did not continue downstream, as the site 3 km below the plant had GPP of only 12 g O2 m-2 d-1. Productivity fell in June to 1-2 g O2 m-2 d-1 and the differences in productivity above and below plants were minimal. Ecosystem respiration followed a similar pattern in April, increasing from -17 g O2 m-2 d-1 above the plant to -47 g O2 m-2 d-1 1 km below the plant, then decreasing to -8 g O2 m-2 d-1 3 km below the plant. Respiration dropped to -3 g O2 m-2 d-1 above the plant in June but only fell to -9 to -10 g O2 m-2 d-1 at the two downstream sites. These findings indicate that large nutrient pulses from wastewater treatment plants spur productivity and respiration, but that these increases may be strongly seasonally dependent. Examining in-stream productivity and respiration is critical in wastewater impacted streams to understanding the seasonal and spatial variability of nutrient stresses so that limitations on discharge can be better targeted.

Measured Fluid Flow in an Active H2O-CO2 Geothermal Well as an Analog to Fluid Flow in Fractures on Mars: Preliminary Report

NASA Technical Reports Server (NTRS)

Kieffer, Susan W.; Brown, K. L.; Simmons, Stuart F.; Watson, Arnold

2004-01-01

Water in the Earth's crust generally contains dissolved gases such as CO2. Models for both 'Blue Mars' (H2O-driven processes) and 'White Mars' (CO2-driven processes) predict liquid H2O with dissolved CO2 at depth. The fate of dissolved CO2 as this mixture rises toward the surface has not been quantitatively explored. Our approach is a variation on NASA's 'Follow the Water' as we 'Follow the Fluid' from depth to the surface in hydrothermal areas on Earth and extrapolate our results to Mars. This is a preliminary report on a field study of fluid flow in a producing geothermal well. For proprietary reasons, the name and location of this well cannot be revealed, so we have named it 'Earth1' for this study.

Regional-scale controls on dissolved nitrous oxide in the Upper Mississippi River

USGS Publications Warehouse

Turner, P.A.; Griffis, T.J.; Baker, J.M.; Lee, X.; Crawford, John T.; Loken, Luke C.; Venterea, R.T.

2016-01-01

The U.S. Corn Belt is one of the most intensive agricultural regions of the world and is drained by the Upper Mississippi River (UMR), which forms one of the largest drainage basins in the U.S. While the effects of agricultural nitrate (NO3-) on water quality in the UMR have been well documented, its impact on the production of nitrous oxide (N2O) has not been reported. Using a novel equilibration technique, we present the largest data set of freshwater dissolved N2O concentrations (0.7 to 6 times saturation) and examine the controls on its variability over a 350 km reach of the UMR. Driven by a supersaturated water column, the UMR was an important atmospheric N2O source (+68 mg N2ONm-2 yr-1) that varies nonlinearly with the NO3-concentration. Our analyses indicated that a projected doubling of the NO3-concentration by 2050 would cause dissolved N2O concentrations and emissions to increase by about 40%.

Photocatalytic degradation of E. coliform in water.

PubMed

Sun, Darren Delai; Tay, Joo Hwa; Tan, Koh Min

2003-08-01

This study aims to further investigate the total mineralization of the bacteria to the extent of death and cell-mass inactivation using a TiO2-Fe2O3 membrane photocatalytic oxidation reactor. Experimental results clearly indicated that dissolved oxygen (DO), hydraulic retention time (HRT) and concentration of the model bacteria (Escherichia coliform) affected the removal efficiency. It was found that the ultimate removal efficiency was 99% at DO level of 21.34 mg/l, HRT at 60s and high concentration of E. coli at 10(9)CFU/ml. The morphologic studies also showed that E. coliform could be further mineralized into CO2 and H2O. Dissolved organic carbon, pH and gas chromatograph analysis had justified most importantly the evolution of CO2. Experimental results revealed that the photomineralization rate of E. coliform followed pseudo-first-order kinetics by the role of DO. The derived empirical models were found consistent with the proposed reaction pathways of a combined UV breakdown on mass cell and a dual-site Langmuir-Hinshelwood mechanism where the rate-controlling step is the surface interaction between the adsorbed cleavage bacterial cells and hydroxyl radicals.

Ability of rabbit alveolar macrophages to dissolve metals.

PubMed

Lundborg, M; Lind, B; Camner, P

1984-01-01

Manganese dioxide particles, 0.1-0.5 micron, were added to samples of 2-3 X 10(6) rabbit alveolar macrophages. The amount of manganese added and dissolved from the particles, over periods of 0, 1, 3, and 5 days, was determined by flame atomic absorption spectrophotometry. Macrophages from six rabbits received about 10 micrograms of Mn, macrophages from two rabbits about 30 micrograms, and macrophages from another two rabbits about 100 micrograms. Over periods of 1, 3, and 5 days the macrophages in all three dose groups dissolved two to three times more Mn than was dissolved in control experiments. In control experiments solubility was studied in the medium without macrophages. Macrophages cultivated 3 days before the addition of MnO2 dissolved the particles within another 2 days to an extent similar to that in the control experiments. The ability of the macrophages to dissolve MnO2 particles might be related to the low pH values in the phagosomes. Studies of the ability of macrophages from various species to dissolve metal particles as well as of pH values in their phagosomes might lead to a better understanding of alveolar clearance of metal particles.

Extent and persistence of secondary water quality impacts after enhanced reductive bioremediation

USGS Publications Warehouse

Borden, Robert C.; Jason M. Tillotson,; Ng, Gene-Hua Crystal.; Bekins, Barbara A.; Kent, Douglas B.; Curtis, Gary P.

2017-01-01

Electron donor (ED) addition can be very effective in stimulating enhanced reductive bioremediation (ERB) of a wide variety of groundwater contaminants. However, ERB can result in Secondary Water Quality Impacts (SWQIs) including decreased levels of dissolved oxygen (O2), nitrate (NO3- ), and sulfate (SO42- ), and elevated levels of dissolved manganese (Mn2+), dissolved iron (Fe2+), methane (CH4), sulfide (S2- ), organic carbon, and naturally occurring hazardous compounds (e.g., arsenic). Fortunately, this ‘plume’ of impacted groundwater is usually confined within the original contaminant plume and is unlikely to adversely impact potable water supplies. This report summarizes available information on processes controlling the production and natural attenuation of SWQI parameters and can be used as a guide in understanding the magnitude, areal extent, and duration of SWQIs in ERB treatment zones and the natural attenuation of SWQI parameters as the dissolved solutes migrate downgradient with ambient groundwater flow. This information was compiled from a wide variety of sources including a survey and statistical analysis of SWQIs from 47 ERB sites, geochemical model simulations, field studies at sites where organic-rich materials have entered the subsurface (e.g., wastewater, landfill leachate, and hydrocarbon plumes), and basic information on physical, chemical, and biological processes in the subsurface. This information is then integrated to provide a general conceptual model of the major processes controlling SWQI production and attenuation.

Mobility of nutrients and trace metals during weathering in the late Archean

NASA Astrophysics Data System (ADS)

Hao, Jihua; Sverjensky, Dimitri A.; Hazen, Robert M.

2017-08-01

The evolution of the geosphere and biosphere depends on the availability of bio-essential nutrients and trace metals. Consequently, the chemical and isotopic variability of trace elements in the sedimentary record have been widely used to infer the existence of early life and fluctuations in the near-surface environment on the early Earth, particularly fluctuations in the redox state of the atmosphere. In this study, we applied late Archean weathering models (Hao et al., 2017), developed to estimate the behavior of major elements and the composition of late Archean world average river water, to explore the behavior of nutrient and trace metals and their potential for riverine transport. We focused on P, Mn, Cr, and Cu during the weathering of olivine basalt. In our standard late Archean weathering model (pCO2,g = 10-1.5 bars, pH2,g = 10-5.0 bars), crustal apatite was totally dissolved by the acidic rainwater during weathering. Our model quantitatively links the pCO2,g of the atmosphere to phosphate levels transported by rivers. The development of late Archean river water (pH = 6.4) resulted in riverine phosphate of at least 1.7 μmolar, much higher than at the present-day. At the end of the early Proterozoic snowball Earth event when pCO2,g could be 0.01-0.10 bars, river water may have transported up to 70 μmolar phosphate, depending on the availability of apatite, thereby stimulating high levels of oxygenic photosynthesis in the marine environment. Crustal levels of Mn in olivine dissolved completely during weathering, except at large extents of weathering where Mn was stored as a component of a secondary carbonate mineral. The corresponding Mn content of river water, about 1.2 μmolar, is higher than in modern river water. Whiffs of 10-5 mole O2 gas or HNO3 kg-1 H2O resulted in the formation of pyrolusite (MnO2) and abundant hematite and simultaneous dramatic decreases in the concentration of Mn(II) in the river water. Chromite dissolution resulted in negligible dissolved Cr in Archean river water. However, amorphous Cr(OH)3 representing easily-weatherable Cr-bearing minerals dissolved totally during the weathering simulations, resulting in concentrations of Cr(III) in the river water of up to 0.14 μmolar, higher than at the present-day. Late Archean weathering of accessory chalcopyrite produced chalcocite and bornite, and extremely low concentrations of Cu (<10-15 molar) because of the low solubilities of the copper sulfides. However, pulses of either O2,g or HNO3 produced native copper, chalcocite, and bornite, much more hematite, and river water containing levels of dissolved Cu comparable to the present-day. Copper mineralogy predicted by weathering models might provide a new correlation with evidence from studies of copper mineral evolution. Overall, our results implied that the redox state of the atmosphere, the pH of surface waters, and the availability of easily-weatherable minerals are all important factors controlling the dissolution of trace elements in river water. Interpretation of the sedimentary signatures of trace elements should consider not only the redox state but also the pH and availability of accessory minerals.

Impact fracture experiments simulating interstellar grain-grain collisions

NASA Technical Reports Server (NTRS)

Freund, Friedemann; Chang, Sherwood; Dickinson, J. Thomas

1990-01-01

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

Effect of exposure to sunlight and phosphorus-limitation on bacterial degradation of coloured dissolved organic matter (CDOM) in freshwater.

PubMed

Kragh, Theis; Søndergaard, Morten; Tranvik, Lars

2008-05-01

This study reports on the interacting effect of photochemical conditioning of dissolved organic matter and inorganic phosphorus on the metabolic activity of bacteria in freshwater. Batch cultures with lake-water bacteria and dissolved organic carbon (DOC) extracted from a humic boreal river were arranged in an experimental matrix of three levels of exposure to simulated sunlight and three levels of phosphorus concentration. We measured an increase in bacterial biomass, a decrease in DOC and bacterial respiration as CO(2) production and O(2) consumption over 450 h. These measurements were used to calculate bacterial growth efficiency (BGE). Bacterial degradation of DOC increased with increasing exposure to simulated sunlight and availability of phosphorus and no detectable growth occurred on DOC that was not pre-exposed to simulated sunlight. The outcome of photochemical degradation of DOC changed with increasing availability of phosphorus, resulting in an increase in BGE from about 5% to 30%. Thus, the availability of phosphorus has major implications for the quantitative transfer of carbon in microbial food webs.

A comparison of disinfection by-products formation during sequential or simultaneous disinfection of surface waters with chlorine dioxide and chlor(am)ine.

PubMed

Shi, Yanwei; Ling, Wencui; Qiang, Zhimin

2013-01-01

The effect of chlorine dioxide (ClO2) oxidation on the formation of disinfection by-products (DBPs) during sequential (ClO2 pre-oxidation for 30 min) and simultaneous disinfection processes with free chlorine (FC) or monochloramine (MCA) was investigated. The formation of DBPs from synthetic humic acid (HA) water and three natural surface waters containing low bromide levels (11-27 microg/L) was comparatively examined in the FC-based (single FC, sequential ClO2-FC, and simultaneous ClO2/FC) and MCA-based (single MCA, ClO2-MCA, and ClO2/MCA) disinfection processes. The results showed that much more DBPs were formed from the synthetic HA water than from the three natural surface waters with comparative levels of dissolved organic carbon. In the FC-based processes, ClO2 oxidation could reduce trihalomethanes (THMs) by 27-35% and haloacetic acids (HAAs) by 14-22% in the three natural surface waters, but increased THMs by 19% and HAAs by 31% in the synthetic HA water after an FC contact time of 48 h. In the MCA-based processes, similar trends were observed although DBPs were produced at a much lower level. There was an insignificant difference in DBPs formation between the sequential and simultaneous processes. The presence of a high level of bromide (320 microg/L) remarkably promoted the DBPs formation in the FC-based processes. Therefore, the simultaneous disinfection process of ClO2/MCA is recommended particularly for waters with a high bromide level.

Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

Removal of H 2S via an iron catalytic cycle and iron sulfide precipitation in the water column of dead end tributaries

NASA Astrophysics Data System (ADS)

Ma, Shufen; Noble, Abigail; Butcher, Derek; Trouwborst, Robert E.; Luther, George W., III

2006-11-01

The oxidation and precipitation of H 2S were investigated in Torquay Canal and Bald Eagle Creek, two tributaries of northern Rehoboth Bay, one of the Delaware Inland Bays. These man-made dead end canals develop seasonal anoxia and have been the site of past fish kills and harmful algal blooms. The canals have multiple holes over 5.5 m deep compared to an average low tide depth of 2 m. In situ determination for dissolved O 2, H 2S and other Fe and S redox species were conducted with a solid-state Au/Hg microelectrode in 2003 and 2004. Laboratory analyses of discrete samples were also performed to measure dissolved and particulate Fe, Mn, and S 8 to follow the seasonal dynamics of O, S, Fe and Mn redox species. Our results indicate that the water in the holes becomes stratified with O 2 decreasing with depth and H 2S increasing with depth. Dissolved Fe was as high as 30 μM whereas dissolved Mn was only 0.2 μM in the water column, indicating that Fe is the dominant metal involved in S redox cycling and precipitation. In surface oxic waters, the dominant form of Fe was particulate Fe(III) (oxy)hydroxides. When seasonal anoxia developed, Fe(III) (oxy)hydroxides were reduced by H 2S to Fe(II) at the oxic-anoxic interface. The Fe(II) reduced from particulate Fe can be re-oxidized to Fe(III) by O 2 above and at the interface to form a catalytic cycle to oxidize H 2S. Elemental S is the predominant oxidation product and was as high as 30 μM level (as S 0) at the interface. When the system was stable, the Fe catalytic cycle prevented H 2S from being released into surface waters during seasonal anoxia. However, when storms came, the water column was overturned and H 2S was released to the surface water. The reaction rates for the Fe catalytic cycle are not fast enough and the concentration of Fe was not high enough to regulate the high concentration of H 2S in surface waters during storm and mixing events.

Biodegradability of nonaqueous-phase liquids affects the mineralization of phenanthrene in soil because of microbial competition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morrison, D.E.; Alexander, M.

1997-08-01

A study was conducted to determine the effects of biodegradability of nonaqueous-phase liquids (NAPLs) and microbial competition on the biodegradation in soil of a constituent of the NAPLs. The rates of mineralization of phenanthrene dissolved in 8 mg of 2,2,4,4,6,8,8-heptamethylnonane (HMN), di(2-ethylhexyl) phthalate (DEHP), or pristane per g of soil were faster than the rates when the compound was dissolved in hexadecane or dodecane. Addition of inorganic N and P to the soil increased the mineralization rate in the first two but not the last two NAPLs. N and P addition did not enhance mineralization of phenanthrene when added inmore » 500 {micro}g of hexadecane, pristane, or HMN per g of soil. Hexadecane was rapidly degraded, pristane was slowly metabolized, DEHP was still slower, and HMN was not mineralized in the test period. Mixing the soil stimulated mineralization of phenanthrene dissolved in HMN but not in hexadecane. Mineralization of phenanthrene dissolved in HMN was the same if the gas phase contained 21%, 2.1%, or traces of O{sub 2}. In contrast, the biodegradation of phenanthrene dissolved in hexadecane, although the same at 21 and 2.1% O{sub 2}, was not observed if traces of O{sub 2} were present. The mineralization was slower in unshaken soil-water mixtures if phenanthrene was added in hexadecane than in HMN or pristane, but the rates with the 3 NAPLs were increased by shaking the suspensions. The authors suggest that the biodegradability of major components of NAPLs and microbial competition for N, P, or O{sub 2} will have a major impact on the rate of transformation of minor constituents of NAPLs.« less

Mega-solubility of quartz resulting from highly alkaline fluids produced by dissolved albite in H2O at deep crustal conditions

NASA Astrophysics Data System (ADS)

Makhluf, A. R.; Manning, C. E.

2017-12-01

Models of H2O-rich fluids equilibrated with rocks at high P and T fail to predict the high solubilities observed experimentally, chiefly because thermodynamic data for the most abundant solutes is lacking. We investigated the effects of dissolved albite (Ab) on the solubility of quartz (Qz) at 1.0 GPa and 675-900 °C using a piston-cylinder apparatus to quantify possible mineral buffering or enhancement effects. We found a very large enhancement effect on the solubility of Qz when dissolved in dilute aqueous Ab solutions. SiO2 concentrations are similar to Qz solubility in strongly alkaline KOH solutions. At the highest temperature of 900 °C, we found that the solubility of Qz in 1.0 molal Ab solution increases by of factor of 4.5 over that in pure H2O, which corresponds to 10.7 molal SiO2. The nearly identical solubility of Qz in KOH(aq) and Ab solutions of the same concentration, P, and T, strongly suggest that NaOH(aq) liberated from NaAlSi3O8 in H2O fluids effects SiO2 solubility in a similar manner to that of KOH(aq). The deprotonated silica dimer was found to be a key species responsible for the high solubility of Qz in KOH(aq) and is likely responsible for the high solubility of Qz in Ab solutions. While the binaries Qz-H2O, Ab-H2O, and Qz-Ab are well known at 1.0 GPa, little data exists on the ternary system. The new results help quantify the ternary relations in the Ab-Qz-H2O system, which can be used as a simple model for liquid-vapor immiscibility granitic magmas. In addition, these highly alkaline solute-rich aqueous fluids suggest a mechanism for Ab-Qz metasomatism in subduction zones, such as in the Catalina schist (Bebout and Barton 1993), which provides an alternative to high P-T magmas. Our results show that subduction zone and metasomatic fluids may be much more alkaline and have significantly higher dissolving power than previously thought.

Geochemical evolution of acidic ground water at a reclaimed surface coal mine in western Pennsylvania

USGS Publications Warehouse

Cravotta,, Charles A.

1991-01-01

Concentrations of dissolved sulfate and acidity in ground water increase downflow in mine spoil and underlying bedrock at a reclaimed surface coal mine in the bituminous field of western Pennsylvania. Elevated dissolved sulfate and negligible oxygen in ground water from bedrock about 100 feet below the water table suggest that pyritic sulfur is oxidized below the water table, in a system closed to oxygen. Geochemical models for the oxidation of pyrite (FeS2) and production of sulfate (SO42-) and acid (H+) are presented to explain the potential role of oxygen (O2) and ferric iron (Fe3+) as oxidants. Oxidation of pyrite by O2 and Fe3+ can occur under oxic conditions above the water table, whereas oxidation by Fe3+ also can occur under anoxic conditions below the water table. The hydrated ferric-sulfate minerals roemerite [Fe2+Fe43+(SO4)4·14H2O], copiapite [Fe2+Fe43+(SO4)6(OH)2·20H20], and coquimbite [Fe2(SO4)3·9H2O] were identified with FeS2 in coal samples, and form on the oxidizing surface of pyrite in an oxic system above the water table. These soluble ferric-sulfate 11 salts11 can dissolve with recharge waters or a rising water table releasing Fe3+, SO42-. and H+, which can be transported along closed-system ground-water flow paths to pyrite reaction sites where O2 may be absent. The Fe3+ transported to these sites can oxidize pyritic sulfur. The computer programs WATEQ4F and NEWBAL were used to compute chemical speciation and mass transfer, respectively, considering mineral dissolution and precipitation reactions plus mixing of waters from different upflow zones. Alternative mass-balance models indicate that (a) extremely large quantities of O2, over 100 times its aqueous solubility, can generate the observed concentrations of dissolved SO42- from FeS2, or (b) under anoxic conditions, Fe3+ from dissolved ferric-sulfate minerals can oxidize FeS2 along closed-system ground-water flow paths. In a system open to O2, such as in the unsaturated zone, the aqueous solubility of O2 is not limiting, and oxidation of pyrite by O2 and Fe3+ accounts for most SO42- and Fe2+ observed in acidic ground water. However, in a system closed to O2, such as in the saturated zone, O2 solubility is limiting; hence, ferric oxidation of pyrite is a reasonable explanation for the observed elevated SO42- with increasing depth below the water table.

Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

DOE PAGES

Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui; ...

2017-12-05

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. Here, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO 4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K 2(UO 2) 6O 4(OH) 6·8H 2O]- and becquerelite [Ca(UO 2) 6O 4(OH) 6·8H 2O]-like species.more » Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO 2) 2O 4(HSiO 4) 2•0.5(H 2O)]-like species of uranium at 180 and 365 days. When present, PO 4 exerted a direct and strong control over U speciation. Furthermore, the detection of meta-ankoleite, [K 2(UO 2) 2O 4(PO 4) 2·6H 2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO 4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO 4 present, nearly all uranium would have precipitated in the upper soil.« less

Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. In this study, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO(4)(-)reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K-2(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-and becquerelite [Ca(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-like species. Subsequent further removal of uranium coincided withmore » that of Si and accumulation of boltwoodite, [(K, Na)(UO2)(2)O-4(HSiO4)(2)center dot 0.5(H2O)]-like species of uranium at 180 and 365 days. When present, PO4 exerted a direct and strong control over U speciation. The detection of meta-ankoleite, [K-2(UO2)(2)O-4(PO4)(2)center dot 6H(2)O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO4 present, nearly all uranium would have precipitated in the upper soil.« less

Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. Here, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO 4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K 2(UO 2) 6O 4(OH) 6·8H 2O]- and becquerelite [Ca(UO 2) 6O 4(OH) 6·8H 2O]-like species.more » Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO 2) 2O 4(HSiO 4) 2•0.5(H 2O)]-like species of uranium at 180 and 365 days. When present, PO 4 exerted a direct and strong control over U speciation. Furthermore, the detection of meta-ankoleite, [K 2(UO 2) 2O 4(PO 4) 2·6H 2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO 4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO 4 present, nearly all uranium would have precipitated in the upper soil.« less

Production of NO2/-/ and N2O by nitrifying bacteria at reduced concentrations of oxygen

NASA Technical Reports Server (NTRS)

Goreau, T. J.; Kaplan, W. A.; Wofsy, S. C.; Mcelroy, M. B.; Valois, F. W.; Watson, S. W.

1980-01-01

The influence of oxygen concentration on the production of NO2(-) and N2O by nitrifying marine bacteria of the genus Nitrosomonas is investigated. Pure cultures of the ammonium-oxiding bacteria isolated from the Western Tropical Atlantic Ocean were grown at oxygen partial pressures from 0.005 to 0.2 atm, and concentrations of N2O in the air above the growth medium and dissolved NO2(-) were determined. Decreasing oxygen concentrations are observed to induce a marked decrease in NO2(-) production rates and increase in N2O evolution, leading to an increase of the relative yield of N2O with respect to NO2(-) from 0.3% to nearly 10%. Similar yields of N2O at atmospheric oxygen levels are found for nitrifying bacteria of the genera Nitrosomonas, Nitrosolobus, Nitrosospira and Nitrosococcus, while nitrite-oxydizing bacteria and a dinoflagellate did not produce detectable quantities of N2O. Results support the view that nitrification is a major source of N2O in the environment.

Uranium biogeochemistry across the redox transition zone of a permanently stratified fjord: Framvaren, Norway

USGS Publications Warehouse

Swarzenski, P.W.; McKee, B.A.; Skei, J.M.; Todd, J.F.

1999-01-01

During August 1995, the vertical concentration profile of dissolved and particulate uranium exhibited strong non-conservative characteristics in the upper 30 m of Framvaren Fjord. There was a pronounced peak in both particulate (> 0.2 ??m; 1.09 nM) and dissolved (< 0.2 ??m; 17.06 nM) uranium in the finely stratified waters at the O2/H2S interface which is positioned well within the euphotic zone at about 20-21 m. Such concentration maxima at the redox boundary are also observed for dissolved organic carbon (DEC), Sr and Ba. Dissolved U levels seen in the water column from 18 m down to 30 m exceeded the high salinity (salinity = 35) U concentrations (13.63 ?? 0.84 nM; Chen, J.H., Edwards, R.L., Wasserburg, G.L., 1986. 238U, 234U and 232Th in seawater. Earth Planet Sci. Lett. 80, 241-251.) observed uniformly in the open ocean. A prolific population of S microbes (e.g., Chromatium, Chlorobium sp.) flourishes at the O2/H2S interface. The source of elevated U at the redox boundary must be due to microbial uptake and subsequent release processes rather than dilution from oceanic uranium. Uranium oxidation state determinations in waters from 1, 22 and 30 m depth reveal that reduced U(IV) is not present in significant abundance, and that the chemical and/or biological reduction of hexavalent uranium is largely inhibited. Our results suggest that U and other trace constituents such as DOC, Sr, Ba, Fe(II), Mn(II) are greatly modified by direct and indirect microbial transformation reactions which are most concentrated across the redox transition zone in Framvaren Fjord.

Reduction of adsorbed As(V) on nano-TiO2 by sulfate-reducing bacteria.

PubMed

Luo, Ting; Ye, Li; Ding, Cheng; Yan, Jinlong; Jing, Chuanyong

2017-11-15

Reduction of surface-bound arsenate [As(V)] and subsequent release into the aqueous phase contribute to elevated As in groundwater. However, this natural process is not fully understood, especially in the presence of sulfate-reducing bacteria (SRB). Gaining mechanistic insights into solid-As(V)-SRB interactions motivated our molecular level study on the fate of nano-TiO 2 bound As(V) in the presence of Desulfovibrio vulgaris DP4, a strain of SRB, using incubation and in situ ATR-FTIR experiments. The incubation results clearly revealed the reduction of As(V), either adsorbed on nano-TiO 2 or dissolved, in the presence of SRB. In contrast, this As(V) reduction was not observed in abiotic control experiments where sulfide was used as the reductant. Moreover, the reduction was faster for surface-bound As(V) than for dissolved As(V), as evidenced by the appearance of As(III) at 45h and 75h, respectively. ATR-FTIR results provided direct evidence that the surface-bound As(V) was reduced to As(III) on TiO 2 surfaces in the presence of SRB. In addition, the As(V) desorption from nano-TiO 2 was promoted by SRB relative to abiotic sulfide, due to the competition between As(V) and bacterial phosphate groups for TiO 2 surface sites. This competition was corroborated by the ATR-FTIR analysis, which showed inner-sphere surface complex formation by bacterial phosphate groups on TiO 2 surfaces. The results from this study highlight the importance of indirect bacteria-mediated As(V) reduction and release in geochemical systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Microfluidic dissolved oxygen gradient generator biochip as a useful tool in bacterial biofilm studies.

PubMed

Skolimowski, Maciej; Nielsen, Martin Weiss; Emnéus, Jenny; Molin, Søren; Taboryski, Rafael; Sternberg, Claus; Dufva, Martin; Geschke, Oliver

2010-08-21

A microfluidic chip for generation of gradients of dissolved oxygen was designed, fabricated and tested. The novel way of active oxygen depletion through a gas permeable membrane was applied. Numerical simulations for generation of O(2) gradients were correlated with measured oxygen concentrations. The developed microsystem was used to study growth patterns of the bacterium Pseudomonas aeruginosa in medium with different oxygen concentrations. The results showed that attachment of Pseudomonas aeruginosa to the substrate changed with oxygen concentration. This demonstrates that the device can be used for studies requiring controlled oxygen levels and for future studies of microaerobic and anaerobic conditions.

Exceptional capability of nanosized CeO(2) materials to "dissolve" lanthanide oxides established by time-gated excitation and emission spectroscopy.

PubMed

Tiseanu, Carmen; Parvulescu, Vasile; Avram, Daniel; Cojocaru, Bogdan; Sanchez-Dominguez, Margarita

2014-05-28

The atomic scale homogeneity of Ce and Zr oxygen bonds represents the main reason for enhanced total oxygen storage capability of CeO2-ZrO2 (Ce/Zr = 1) as compared to that of CeO2. Here, we demonstrate that the addition of 10% Eu(3+) by wet impregnation on preformed nanosized CeO2-ZrO2 (Ce/Zr = 1) followed by calcination induces a remarkable homogeneity of 10% Eu(3+)-CeO2-ZrO2 solid solution. By use of time-resolved emission and excitation spectroscopies, the improvement of the nanoscale chemical and structural homogeneity of 10% Eu(3+)-CeO2-ZrO2 calcined at 1000 as compared to sample calcined at 750 °C is demonstrated. Based on the comparison of luminescence properties of 10% Eu(3+) impregnated on preformed nanosized CeO2-ZrO2 and CeO2, we also show that the presence of zirconium does not only preserve the ability of cerium oxide to "dissolve" lanthanide oxide, but also determines an important stabilization of defects (oxygen vacancies) generated upon Eu(3+) doping.

Photomineralization and photomethanification of dissolved organic matter in Saguenay River surface water

NASA Astrophysics Data System (ADS)

Zhang, Y.; Xie, H.

2015-08-01

Rates and apparent quantum yields of photomineralization (AQYDOC) and photomethanification (AQYCH4) of chromophoric dissolved organic matter (CDOM) in Saguenay River surface water were determined at three widely differing dissolved oxygen concentrations ([O2]) (suboxic, air-saturation, and oxygenated) using simulated-solar radiation. Photomineralization increased linearly with CDOM absorbance photobleaching for all three O2 treatments. Whereas the rate of photochemical dissolved organic carbon (DOC) loss increased with increasing [O2], the ratio of fractional DOC loss to fractional absorbance loss showed an inverse trend. CDOM photodegradation led to a nearly complete mineralization under suboxic conditions but to only a partial mineralization under oxic conditions. AQYDOC determined under oxygenated, suboxic, and air-saturated conditions increased, decreased, and remained largely constant with photobleaching, respectively; AQYDOC obtained under air-saturation with short-term irradiations could thus be applied to longer exposures. AQYDOC decreased successively from ultraviolet B (UVB) to ultraviolet A (UVA) to visible (VIS), which, alongside the solar irradiance spectrum, points to VIS and UVA being the primary drivers for photomineralization in the water column. The photomineralization rate in the Saguenay River was estimated to be 2.31 × 108 mol C yr-1, accounting for only 1 % of the annual DOC input into this system. Photoproduction of CH4 occurred under both suboxic and oxic conditions and increased with decreasing [O2], with the rate under suboxic conditions ~ 7-8 times that under oxic conditions. Photoproduction of CH4 under oxic conditions increased linearly with photomineralization and photobleaching. Under air-saturation, 0.00057 % of the photochemical DOC loss was diverted to CH4, giving a photochemical CH4 production rate of 4.36 × 10-6 mol m-2 yr-1 in the Saguenay River and, by extrapolation, of (1.9-8.1) × 108 mol yr-1 in the global ocean. AQYCH4 changed little with photobleaching under air-saturation but increased exponentially under suboxic conditions. Spectrally, AQYCH4 decreased sequentially from UVB to UVA to VIS, with UVB being more efficient under suboxic conditions than under oxic conditions. On a depth-integrated basis, VIS prevailed over UVB in controlling CH4 photoproduction under air-saturation while the opposite held true under O2-deficiency. An addition of micromolar levels of dissolved dimethyl sulfide (DMS) substantially increased CH4 photoproduction, particularly under O2-deficiency; DMS at nanomolar ambient concentrations in surface oceans is, however, unlikely a significant CH4 precursor. Results from this study suggest that CDOM-based CH4 photoproduction only marginally contributes to the CH4 supersaturation in modern surface oceans and to both the modern and Archean atmospheric CH4 budgets, but that the photochemical term can be comparable to microbial CH4 oxidation in modern oxic oceans. Our results also suggest that anoxic microniches in particulate organic matter and phytoplankton cells containing elevated concentrations of precursors of the methyl radical such as DMS may provide potential hotspots for CH4 photoproduction.

Photomineralization and photomethanification of dissolved organic matter in Saguenay River surface water

NASA Astrophysics Data System (ADS)

Zhang, Y.; Xie, H.

2015-11-01

Rates and apparent quantum yields of photomineralization (AQYDOC) and photomethanification (AQYCH4) of chromophoric dissolved organic matter (CDOM) in Saguenay River surface water were determined at three widely differing dissolved oxygen concentrations ([O2]) (suboxic, air saturation, and oxygenated) using simulated-solar radiation. Photomineralization increased linearly with CDOM absorbance photobleaching for all three O2 treatments. Whereas the rate of photochemical dissolved organic carbon (DOC) loss increased with increasing [O2], the ratio of fractional DOC loss to fractional absorbance loss showed an inverse trend. CDOM photodegradation led to a higher degree of mineralization under suboxic conditions than under oxic conditions. AQYDOC determined under oxygenated, suboxic, and air-saturated conditions increased, decreased, and remained largely constant with photobleaching, respectively; AQYDOC obtained under air saturation with short-term irradiations could thus be applied to longer exposures. AQYDOC decreased successively from ultraviolet B (UVB) to ultraviolet A (UVA) to visible (VIS), which, alongside the solar irradiance spectrum, points to VIS and UVA being the primary drivers for photomineralization in the water column. The photomineralization rate in the Saguenay River was estimated to be 2.31 × 108 mol C yr-1, accounting for only 1 % of the annual DOC input into this system. Photoproduction of CH4 occurred under both suboxic and oxic conditions and increased with decreasing [O2], with the rate under suboxic conditions ~ 7-8 times that under oxic conditions. Photoproduction of CH4 under oxic conditions increased linearly with photomineralization and photobleaching. Under air saturation, 0.00057 % of the photochemical DOC loss was diverted to CH4, giving a photochemical CH4 production rate of 4.36 × 10-6 mol m-2 yr-1 in the Saguenay River and, by extrapolation, of (1.9-8.1) × 108 mol yr-1 in the global ocean. AQYCH4 changed little with photobleaching under air saturation but increased exponentially under suboxic conditions. Spectrally, AQYCH4 decreased sequentially from UVB to UVA to VIS, with UVB being more efficient under suboxic conditions than under oxic conditions. On a depth-integrated basis, VIS prevailed over UVB in controlling CH4 photoproduction under air saturation while the opposite held true under O2-deficiency. An addition of micromolar levels of dissolved dimethyl sulfide (DMS) substantially increased CH4 photoproduction, particularly under O2-deficiency; DMS at nanomolar ambient concentrations in surface oceans is, however, unlikely a significant CH4 precursor. Results from this study suggest that CDOM-based CH4 photoproduction only marginally contributes to the CH4 supersaturation in modern surface oceans and to both the modern and Archean atmospheric CH4 budgets, but that the photochemical term can be comparable to microbial CH4 oxidation in modern oxic oceans. Our results also suggest that anoxic microniches in particulate organic matter and phytoplankton cells containing elevated concentrations of precursors of the methyl radical such as DMS may provide potential hotspots for CH4 photoproduction.

Size effects in MgO cube dissolution.

PubMed

Baumann, Stefan O; Schneider, Johannes; Sternig, Andreas; Thomele, Daniel; Stankic, Slavica; Berger, Thomas; Grönbeck, Henrik; Diwald, Oliver

2015-03-10

Stability parameters and dissolution behavior of engineered nanomaterials in aqueous systems are critical to assess their functionality and fate under environmental conditions. Using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we investigated the stability of cubic MgO particles in water. MgO dissolution proceeding via water dissociation at the oxide surface, disintegration of Mg(2+)-O(2-) surface elements, and their subsequent solvation ultimately leads to precipitation of Mg(OH)2 nanosheets. At a pH ≥ 10, MgO nanocubes with a size distribution below 10 nm quantitatively dissolve within few minutes and convert into Mg(OH)2 nanosheets. This effect is different from MgO cubes originating from magnesium combustion in air. With a size distribution in the range 10 nm ≤ d ≤ 1000 nm they dissolve with a significantly smaller dissolution rate in water. On these particles water induced etching generates (110) faces which, above a certain face area, dissolve at a rate equal to that of (100) planes.1 The delayed solubility of microcrystalline MgO is attributed to surface hydroxide induced self-inhibition effects occurring at the (100) and (110) microplanes. The present work underlines the importance of morphology evolution and surface faceting of engineered nanomaterials particles during their dissolution.

Comparative effects of zinc oxide nanoparticles and dissolved zinc on zebrafish embryos and eleuthero-embryos: importance of zinc ions.

PubMed

Brun, Nadja Rebecca; Lenz, Markus; Wehrli, Bernhard; Fent, Karl

2014-04-01

The increasing use of zinc oxide nanoparticles (nZnO) and their associated environmental occurrence make it necessary to assess their potential effects on aquatic organisms. Upon water contact, nZnO dissolve partially to zinc (Zn(II)). To date it is not yet completely understood, whether effects of nZnO are solely or partly due to dissolved Zn(II). Here we compare potential effects of 0.2, 1 and 5mg/L nZnO and corresponding concentrations of released Zn(II) by water soluble ZnCl2 to two development stages of zebrafish, embryos and eleuthero-embryos, by analysing expressional changes by RT-qPCR. Another objective was to assess uptake and tissue distribution of Zn(II). Laser ablation-ICP-MS analysis demonstrated that uptake and tissue distribution of Zn(II) were identical for nZnO and ZnCl2 in eleuthero-embryos. Zn(II) was found particularly in the retina/pigment layer of eyes and brain. Both nZnO and dissolved Zn(II) derived from ZnCl2 had similar inhibiting effects on hatching, and they induced similar expressional changes of target genes. At 72hours post fertilization (hpf), both nZnO and Zn(II) delayed hatching at all doses, and inhibited hatching at 1 and 5 mg/L at 96 hpf. Both nZnO and Zn(II) lead to induction of metallothionein (mt2) in both embryos and eleuthero-embryos at all concentrations. Transcripts of oxidative stress related genes cat and Cu/Zn sod were also altered. Moreover, we show for the first time that nZnO exposure results in transcriptional changes of pro-inflammatory cytokines IL-1β and TNFα. Overall, transcriptional alterations were higher in embryos than eleuthero-embryos. The similarities of the effects lead to the conclusion that effects of nZnO are mainly related to the release of Zn(II). Copyright © 2014 Elsevier B.V. All rights reserved.

Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers

USGS Publications Warehouse

Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Snyder, D.M.; McCleskey, R. Blaine; Amils, R.; Poulson, S.R.

2008-01-01

A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Ri??o Tinto, Ri??o Odiel, and Ri??o Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66????M at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3??nmol L- 1 s- 1) and maximum rates of Fe(III) photoreduction (1.7 to 4.3??nmol L- 1 s- 1). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Ri??o Tinto in about 30??days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans. Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research. ?? 2008 Elsevier B.V. All rights reserved.

Assessment of online monitoring strategies for measuring N2O emissions from full-scale wastewater treatment systems.

PubMed

Marques, Ricardo; Rodriguez-Caballero, A; Oehmen, Adrian; Pijuan, Maite

2016-08-01

Clark-Type nitrous oxide (N2O) sensors are routinely used to measure dissolved N2O concentrations in wastewater treatment plants (WWTPs), but have never before been applied to assess gas-phase N2O emissions in full-scale WWTPs. In this study, a full-scale N2O gas sensor was tested and validated for online gas measurements, and assessed with respect to its linearity, temperature dependence, signal saturation and drift prior to full-scale application. The sensor was linear at the concentrations tested (0-422.3, 0-50 and 0-10 ppmv N2O) and had a linear response up to 2750 ppmv N2O. An exponential correlation between temperature and sensor signal was described and predicted using a double exponential equation while the drift did not have a significant influence on the signal. The N2O gas sensor was used for online N2O monitoring in a full-scale sequencing batch reactor (SBR) treating domestic wastewater and results were compared with those obtained by a commercial online gas analyser. Emissions were successfully described by the sensor, being even more accurate than the values given by the commercial analyser at N2O concentrations above 500 ppmv. Data from this gas N2O sensor was also used to validate two models to predict N2O emissions from dissolved N2O measurements, one based on oxygen transfer rate and the other based on superficial velocity of the gas bubble. Using the first model, predictions for N2O emissions agreed by 98.7% with the measured by the gas sensor, while 87.0% similarity was obtained with the second model. This is the first study showing a reliable estimation of gas emissions based on dissolved N2O online data in a full-scale wastewater treatment facility. Copyright © 2016 Elsevier Ltd. All rights reserved.

TH-AB-209-05: Validating Hemoglobin Saturation and Dissolved Oxygen in Tumors Using Photoacoustic Computed Tomographic Spectroscopic Imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burnett, J; Sick, J; Liu, B

Purpose: Photoacoustic computed tomographic spectroscopy (PCT-S) provides intra-tumor measurements of oxygenation with high spatial resolution (0.2mm) and temporal fidelity (1–2 minutes) without the need for exogenous agents or ionizing radiation, thus providing a unique in vivo assay to measure SaO{sub 2} and investigate acute and chronic forms of hypoxia. The goal of this study is to validate in vivo SaO{sub 2} levels within tail artery of mice and the relationship between SaO{sub 2} and pO{sub 2} within subcutaneous breast tumors using PCT-S imaging, pulse oximetry and an OxyLite probe. Methods: A closed circuit phantom was fabricated to control blood oxygenationmore » levels, where SaO{sub 2} was measured using a co-oximeter and pO{sub 2} using an Oxylite probe. Next, SaO{sub 2} levels within the tail arteries of mice (n=3) were measured using PCT-S and pulse oximetry while breathing high-to-low oxygen levels (6-cycles). Finally, PCT-S was used to measure SaO{sub 2} levels in MCF-7, MCF-7-VEGF165, and MDA-MB-231 xenograft breast tumors and compared to Oxylite pO{sub 2} levels values. Results: SaO{sub 2} and pO{sub 2} data obtained from the calibration phantom was fit to Hill’s equation: aO{sub 2} levels between 88 and 52% demonstrated a linear relationship (r2=0.96) and a 3.2% uncertainty between PCT-S values relative to pulse oximetry. Scatter plots of localized PCT-S measured SaO2 and Oxylite pO{sub 2} levels in MCF-7/MCF-7-VEGF165 and MDA-MD-231 breast tumors were fit to Hill’s equation: P50=17.2 and 20.7mmHg, and n=1.76 and 1.63. These results are consistent with sigmoidal form of Hill’s equation, where the lower P{sub 50} value is indicative of an acidic tumor microenvironment. Conclusion: The results demonstrate photoacoustic imaging can be used to measure SaO{sub 2} cycling and intra-tumor oxygenation, and provides a powerful in vivo assay to investigate the role of hypoxia in radiation, anti-angiogenic, and immunotherapies.« less

Synergistic effect of the presence of suspended and dissolved matter on the removal of cyanide from coking wastewater by TiO2 photocatalysis.

PubMed

Pueyo, Noelia; Miguel, Natividad; Mosteo, Rosa; Ovelleiro, José L; Ormad, María P

2017-01-28

This study assesses the influence of the presence of suspended and dissolved matter on the efficiency of TiO 2 photocatalysis for the removal of cyanide from coking wastewater. Photocatalytic processes were carried out at basic pH (pH 9) with titanium dioxide (1 g/L), artificial radiation (290-800 nm) and during different time periods (20-100 min). The first assays applied in aqueous solutions achieved promising results in terms of removing cyanide. The maximum cyanide removal obtained in coking wastewater was 89% after 80 min of irradiation in the presence of suspended and dissolved matter. The presence of suspended matter composed of coal improves the efficiency of the photocatalytic process due to the synergistic effect between carbon and TiO 2 . The absence of dissolved matter also improves the process due to the minimization of the hydroxyl radical scavenging effect produced by carbonate and bicarbonate ions. On the other hand, the presence of certain species in the real matrix such as silicon increases the activity of the titanium dioxide catalyst. In consequence, the improvement achieved by the photocatalytic process for the removal of cyanide in the absence of dissolved matter is counteracted.

Effects of aeration and internal recycle flow on nitrous oxide emissions from a modified Ludzak-Ettinger process fed with glycerol.

PubMed

Song, Kang; Suenaga, Toshikazu; Harper, Willie F; Hori, Tomoyuki; Riya, Shohei; Hosomi, Masaaki; Terada, Akihiko

2015-12-01

Nitrous oxide (N2O) is emitted from a modified Ludzak-Ettinger (MLE) process, as a primary activated sludge system, which requires mitigation. The effects of aeration rates and internal recycle flow (IRF) ratios on N2O emission were investigated in an MLE process fed with glycerol. Reducing the aeration rate from 1.5 to 0.5 L/min increased gaseous the N2O concentration from the aerobic tank and the dissolved N2O concentration in the anoxic tank by 54.4 and 53.4 %, respectively. During the period of higher aeration, the N2O-N conversion ratio was 0.9 % and the potential N2O reducers were predominantly Rhodobacter, which accounted for 21.8 % of the total population. Increasing the IRF ratio from 3.6 to 7.2 decreased the N2O emission rate from the aerobic tank and the dissolved N2O concentration in the anoxic tank by 56 and 48 %, respectively. This study suggests effective N2O mitigation strategies for MLE systems.

Pressure, O2, and CO2, in aquatic Closed Ecological Systems

NASA Astrophysics Data System (ADS)

Taub, Frieda B.; McLaskey, Anna K.

2013-03-01

Pressure increased during net photosynthetic O2 production in the light and decreased during respiratory O2 uptake during the dark in aquatic Closed Ecological Systems (CESs) with small head gas volumes. Because most CO2 will be in the liquid phase as bicarbonate and carbonate anions, and CO2 is more soluble than O2, volumes of gaseous CO2 and gaseous O2 will not change in a compensatory manner, leading to the development of pressure. Pressure increases were greatest with nutrient rich medium with NaHCO3 as the carbon source. With more dilute media, pressure was greatest with NaHCO3, and less with cellulose or no-added carbon. Without adequate turbulence, pressure measurements lagged dissolved O2 concentrations by several hours and dark respiration would have been especially underestimated in our systems (250-1000 ml). With adequate turbulence (rotary shaker), pressure measurements and dissolved O2 concentrations generally agreed during lights on/off cycles, but O2 measurements provided more detail. At 20 °C, 29.9 times as much O2 will distribute into the gas phase as in the liquid, per unit volume, as a result of the limited solubility of O2 in water and according to Henry's Law. Thus even a small head gas volume can contain more O2 than a larger volume of water. When both dissolved and gaseous O2 and CO2 are summed, the changes in Total O2 and CO2 are in relatively close agreement when NaHCO3 is the carbon source. These findings disprove an assumption made in some of Taub's earlier research that aquatic CESs would remain at approximately atmospheric pressure because approximately equal molar quantities of O2 and CO2 would exchange during photosynthesis and respiration; this assumption neglected the distribution of O2 between water and gas phases. High pressures can occur when NaHCO3 is the carbon source in nutrient rich media and if head-gas volumes are small relative to the liquid volume; e.g., one "worse case" condition developed 800 mm Hg above atmospheric pressure and broke the glass container. Plastic screw cap closures are likely to leak at high pressures and should not be assumed to seal unless tested at appropriate pressures. Pressure can be reduced by having larger head-gas volumes and using less concentrated nutrient solutions. It is important that pressure changes be considered for both safety and closure, and if total O2 is used as the measure of net photosynthesis and respiration, the O2 in the gas phase must be added to the dissolved O2.

Nitrous oxide emissions and dissolved oxygen profiling in a full-scale nitrifying activated sludge treatment plant.

PubMed

Aboobakar, Amina; Cartmell, Elise; Stephenson, Tom; Jones, Mark; Vale, Peter; Dotro, Gabriela

2013-02-01

This paper reports findings from online, continuous monitoring of dissolved and gaseous nitrous oxide (N₂O), combined with dissolved oxygen (DO) and ammonia loading, in a full-scale nitrifying activated sludge plant. The study was conducted over eight weeks, at a 210,000 population equivalent sewage treatment works in the UK. Results showed diurnal variability in the gaseous and dissolved N₂O emissions, with hourly averages ranging from 0 to 0.00009 kgN₂O-N/h for dissolved and 0.00077-0.0027 kgN₂O-N/h for gaseous nitrous oxide emissions respectively, per ammonia loading, depending on the time of day. Similarly, the spatial variability was high, with the highest emissions recorded immediately after the anoxic zone and in the final pass of the aeration lane, where ammonia concentrations were typically below 0.5 mg/L. Emissions were shown to be negatively correlated to dissolved oxygen, which fluctuated between 0.5 and 2.5 mgO₂/L, at the control set point of 1.5 mgO₂/L. The resulting dynamic DO conditions are known to favour N₂O production, both by autotrophic and heterotrophic processes in mixed cultures. Average mass emissions from the lane were greater in the gaseous (0.036% of the influent total nitrogen) than in the dissolved (0.01% of the influent total nitrogen) phase, and followed the same diurnal and spatial patterns. Nitrous oxide emissions corresponded to over 34,000 carbon dioxide equivalents/year, adding 13% to the carbon footprint associated with the energy requirements of the monitored lane. A clearer understanding of emissions obtained from real-time data can help towards finding the right balance between improving operational efficiency and saving energy, without increasing N₂O emissions. Copyright © 2012 Elsevier Ltd. All rights reserved.

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

NASA Astrophysics Data System (ADS)

Tiraboschi, Carla; Tumiati, Simone; Sverjensky, Dimitri; Pettke, Thomas; Ulmer, Peter; Poli, Stefano

2018-01-01

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni-NiO-H2O (ΔFMQ = - 0.21 to - 1.01), employing a double-capsule setting. Fluids, binary H2O-CO2 mixtures at the P, T, and fO2 conditions investigated, were generated from graphite, oxalic acid anhydrous (H2C2O4) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO2-bearing fluids. The experimental data show that forsterite + enstatite solubility in H2O-CO2 fluids is higher compared to pure water, both in terms of dissolved silica ( mSiO2 = 1.24 mol/kgH2O versus mSiO2 = 0.22 mol/kgH2O at P = 1 GPa, T = 800 °C) and magnesia ( mMgO = 1.08 mol/kgH2O versus mMgO = 0.28 mol/kgH2O) probably due to the formation of organic C-Mg-Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H2O-CO2 fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO2 ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO2 ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P- T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.

Modeling Closed Equilibrium Systems of H2O-Dissolved CO2-Solid CaCO3.

PubMed

Tenno, Toomas; Uiga, Kalev; Mashirin, Alexsey; Zekker, Ivar; Rikmann, Ergo

2017-04-27

In many places in the world, including North Estonia, the bedrock is limestone, which consists mainly of CaCO 3 . Equilibrium processes in water involving dissolved CO 2 and solid CaCO 3 play a vital role in many biological and technological systems. The solubility of CaCO 3 in water is relatively low. Depending on the concentration of dissolved CO 2 , the solubility of CaCO 3 changes, which determines several important ground- and wastewater parameters, for example, Ca 2+ concentration and pH. The distribution of ions and molecules in the closed system solid H 2 O-dissolved CO 2 -solid CaCO 3 is described in terms of a structural scheme. Mathematical models were developed for the calculation of pH and concentrations of ions and molecules (Ca 2+ , CO 3 2- , HCO 3 - , H 2 CO 3 , CO 2 , H + , and OH - ) in the closed equilibrium system at different initial concentrations of CO 2 in the water phase using an iteration method. The developed models were then experimentally validated.

Contrasting biogeochemical characteristics of the Oubangui River and tributaries (Congo River basin)

PubMed Central

Bouillon, Steven; Yambélé, Athanase; Gillikin, David P.; Teodoru, Cristian; Darchambeau, François; Lambert, Thibault; Borges, Alberto V.

2014-01-01

The Oubangui is a major tributary of the Congo River. We describe the biogeochemistry of contrasting tributaries within its central catchment, with watershed vegetation ranging from wooded savannahs to humid rainforest. Compared to a 2-year monitoring record on the mainstem Oubangui, these tributaries show a wide range of biogeochemical signatures, from highly diluted blackwaters (low turbidity, pH, conductivity, and total alkalinity) in rainforests to those more typical for savannah systems. Spectral analyses of chromophoric dissolved organic matter showed wide temporal variations in the Oubangui compared to spatio-temporal variations in the tributaries, and confirm that different pools of dissolved organic carbon are mobilized during different hydrological stages. δ13C of dissolved inorganic carbon ranged between −28.1‰ and −5.8‰, and was strongly correlated to both partial pressure of CO2 and to the estimated contribution of carbonate weathering to total alkalinity, suggesting an important control of the weathering regime on CO2 fluxes. All tributaries were oversaturated in dissolved greenhouse gases (CH4, N2O, CO2), with highest levels in rivers draining rainforest. The high diversity observed underscores the importance of sampling that covers the variability in subcatchment characteristics, to improve our understanding of biogeochemical cycling in the Congo Basin. PMID:24954525

Effects of copper-oxide nanoparticles, dissolved copper and ultraviolet radiation on copper bioaccumulation, photosynthesis and oxidative stress in the aquatic macrophyte Elodea nuttallii.

PubMed

Regier, Nicole; Cosio, Claudia; von Moos, Nadia; Slaveykova, Vera I

2015-06-01

In this study, the uptake and sub-toxic effects of CuO nanoparticles (CuO-NPs), dissolved Cu(II) alone or in combination with UV radiation on the aquatic macrophyte Elodea nuttallii were studied. Emphasis was on Cu accumulation, growth, photosynthesis and the oxidative stress related enzymes peroxidase (POD) and superoxide dismutase (SOD). The results showed stronger Cu accumulation in plants exposed to 10 mg L(-1) CuO-NPs, corresponding to 1.4-2 mg L(-1) dissolved Cu(II), than to 256 μg L(-1) Cu(II). However, the ratio between the accumulated Cu and dissolved Cu in CuO treatments was lower than in Cu(II) treatments. Additional UV exposure increased accumulation in both treatments, with the effect being stronger for Cu accumulation from CuO-NPs than for dissolved Cu(II). Photosynthetic capacity was strongly reduced by UV treatment, whereas remained unaffected by Cu(II) or CuO-NP treatments. Similarly, the increase of SOD activity was more pronounced in the UV treatments. On the other hand, POD activity enhancement was strongest in the plants exposed to CuO-NPs for 24 h. Expression of the copper transporter COPT1 as revealed by RT-qPCR was inhibited by Cu(II) and CuO-NP treatment, limiting the uptake of excess Cu into the cells. Overall, the combined exposure of E. nuttallii to UV radiation with CuO-NPs or Cu(II) has a higher impact than exposure to CuO-NPs or Cu(II) alone. The results imply that heavy pollution of natural water with CuO-NPs or dissolved Cu might have stronger effects in combination with natural UV irradiation on organisms in situ. Copyright © 2015 Elsevier Ltd. All rights reserved.

The toxicity of zinc oxide nanoparticles to Lemna minor (L.) is predominantly caused by dissolved Zn.

PubMed

Chen, Xiaolin; O'Halloran, John; Jansen, Marcel A K

2016-05-01

Nano-ZnO particles have been reported to be toxic to many aquatic organisms, although it is debated whether this is caused by nanoparticles per sé, or rather dissolved Zn. This study investigated the role of dissolved Zn in nano-ZnO toxicity to Lemna minor. The technical approach was based on modulating nano-ZnO dissolution by either modifying the pH of the growth medium and/or surface coating of nano-ZnO, and measuring resulting impacts on L. minor growth and physiology. Results show rapid and total dissolution of nano-ZnO in the medium (pH 4.5). Quantitatively similar toxic effects were found when L. minor was exposed to nano-ZnO or the "dissolved Zn equivalent of dissolved nano-ZnO". The conclusion that nano-ZnO toxicity is primarily caused by dissolved Zn was further supported by the observation that phytotoxicity was absent on medium with higher pH-values (>7), where dissolution of nano-ZnO almost ceased. Similarly, the reduced toxicity of coated nano-ZnO, which displays a slower Zn dissolution, is also consistent with a major role for dissolved Zn in nano-ZnO toxicity. Copyright © 2016 Elsevier B.V. All rights reserved.

Measurements of the Activity of dissolved H2O in an Andesite Melt

NASA Astrophysics Data System (ADS)

Moore, G. M.; Touran, J. P.; Pu, X.; Kelley, K. A.; Cottrell, E.; Ghiorso, M. S.

2016-12-01

The large effect of dissolved H2O on the physical and chemical nature of silicate melts, and its role in driving volcanism, is well known and underscores the importance of this volatile component. A complete understanding of the chemical behavior of dissolved H2O in silicate melts requires the quantification of its thermodynamic activity as a function of pressure, temperature, and melt composition, particularly at low H2O contents (i.e. at under-saturated conditions). Knowledge of the activity of H2O in silicate melts at H2O-undersaturated conditions will improve our understanding of hydrous phase equilibria, as well as our models of physical melt properties. Measurement of the activity of any silicate melt component, much less that of a volatile component such as H2O, is a difficult experimental task however. By using a modified double capsule design (Matjuschkin et al, 2015) to control oxygen fugacity in piston cylinder experiments, along with high precision X-ray absorption techniques (XANES) to measure iron oxidation state in silicate glasses (Cottrell et al, 2009), we are able to constrain the H2O activity in silicate melts at under-saturated conditions. Preliminary results on an andesite melt with low H2O content (3 wt%) have been shown (Moore et al, 2016) to match predicted H2O activity values calculated using the H2O equation of state of Duan and Zhang (1996) and the H2O solubility model of Ghiorso and Gualda (2015). More recent results on the same andesite melt containing approximately 5 wt% H2O however show a large negative deviation from the predicted values. Reversal experiments involving an oxidized starting material are ongoing, as well as further characterization of the samples to detect the presence of possible contaminants that would induce reduction of the melt beyond that related to the H2O activity (e.g. graphite contamination).

Geochemical studies of clay minerals III. The determination of free silica and free alumina in montmorillonites

USGS Publications Warehouse

Foster, M.D.

1953-01-01

Determination of free silica by the method proposed made possible the derivation of logical formulas for several specimens of montmorillonites for which the formulas could not be derived from the analyses alone. Other montmorillonites, for which logical formulas could be derived from their analyses, were found to contain small amounts of free silica or free alumina. Others were found to contain neither free silica nor free alumina. The method consists of the following steps: (1) digestion of 1 g of the specimen with 0.5 N NaOH solution in a covered platinum crucible or dish on a steam bath for 4 hrs, stirring the mixture at 30-min intervals, (2) filtration of the undissolved material, followed by washing several times with 1% NaOH solution, (3) neutralization of the filtrate with HCl, addition of 5 ml HCl in excess and determination of SiO and Al2O3 in the usual way and (4) calculation of the amount of free SiO2 or free Al2O3 if any and the amount of attack of the clay structure by the treatment from the ratio of SiO2 to Al2O3 dissolved and the ratio of SiO2 to Al2O3 obtained on analysis. Tests with 5% Na2CO3 solution, the reagent formerly used for the solution of free SiO2 in rocks and minerals, showed that solution of opal by this reagent is always fractional, never complete, no matter how small the amount present or how long the period of treatment. Re-treatment of the sample results in 90-95% solution if 10 mg or less of opal is present, but for larger amounts of opal the percentage dissolved decreases as the amount present increases. On the other hand, 75 ml of 0.5 N NaOH completely dissolves as much as 400 mg of opal in 4 hrs digestion in a covered platinum crucible or dish, on a steam bath. However, a weaker solution or a shorter period of digestion does not effect complete solution. The same amount (75 ml) of 0.5 N NaOH also dissolves 90 mg of cristobalite and 57 mg of quartz having a grain size of less than 2 microns. Use of NaOH also permits determination of the amount of alumina dissolved, and estimation of the extent to which the clay structure was attacked by the treatment. ?? 1953.

Response surface modeling for optimization heterocatalytic Fenton oxidation of persistence organic pollution in high total dissolved solid containing wastewater.

PubMed

Sekaran, G; Karthikeyan, S; Boopathy, R; Maharaja, P; Gupta, V K; Anandan, C

2014-01-01

The rice-husk-based mesoporous activated carbon (MAC) used in this study was precarbonized and activated using phosphoric acid. N2 adsorption/desorption isotherm, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy and scanning electron microscopy, transmission electron microscopy, (29)Si-NMR spectroscopy, and diffuse reflectance spectroscopy were used to characterize the MAC. The tannery wastewater carrying high total dissolved solids (TDS) discharged from leather industry lacks biodegradability despite the presence of dissolved protein. This paper demonstrates the application of free electron-rich MAC as heterogeneous catalyst along with Fenton reagent for the oxidation of persistence organic compounds in high TDS wastewater. The heterogeneous Fenton oxidation of the pretreated wastewater at optimum pH (3.5), H2O2 (4 mmol/L), FeSO4[Symbol: see text]7H2O (0.2 mmol/L), and time (4 h) removed chemical oxygen demand, biochemical oxygen demand, total organic carbon and dissolved protein by 86, 91, 83, and 90%, respectively.

Electrochemistry of free chlorine and monochloramine and its relevance to the presence of Pb in drinking water.

PubMed

Rajasekharan, Vishnu V; Clark, Brandi N; Boonsalee, Sansanee; Switzer, Jay A

2007-06-15

The commonly used disinfectants in drinking water are free chlorine (in the form of HOCl/OCl-) and monochloramine (NH2Cl). While free chlorine reacts with natural organic matter in water to produce chlorinated hydrocarbon byproducts, there is also concern that NH2Cl may react with Pbto produce soluble Pb(II) products--leading to elevated Pb levels in drinking water. In this study, electrochemical methods are used to compare the thermodynamics and kinetics of the reduction of these two disinfectants. The standard reduction potential for NH2Cl/Cl- was estimated to be +1.45 V in acidic media and +0.74 V in alkaline media versus NHE using thermodynamic cycles. The kinetics of electroreduction of the two disinfectants was studied using an Au rotating disk electrode. The exchange current densities estimated from Koutecky-Levich plots were 8.2 x 10(-5) and 4.1 x 10(-5) A/cm2, and by low overpotential experiments were 7.5 +/- 0.3 x 10(-5) and 3.7 +/- 0.4 x 10(-5) A/cm2 for free chlorine and NH2Cl, respectively. The rate constantforthe electrochemical reduction of free chlorine at equilibrium is approximately twice as large as that for the reduction of NH2Cl. Equilibrium potential measurements show that free chlorine will oxidize Pb to PbO2 above pH 1.7, whereas NH2Cl will oxidize Pb to PbO2 only above about pH 9.5, if the total dissolved inorganic carbon (DIC) is 18 ppm. Hence, NH2Cl is not capable of producing a passivating PbO2 layer on Pb, and could lead to elevated levels of dissolved Pb in drinking water.

[Distributions and air-sea fluxes of dissolved nitrous oxide in the Yangtze River estuary and its adjacent marine area in spring and summer].

PubMed

Wang, Lan; Zhang, Gui-ling; Sun, Ming-shuang; Ren, Jing-ling

2014-12-01

Distributions and air-sea fluxes of nitrous oxide (N2O) in the seawaters of the Yangtze River estuary and its adjacent marine area were investigated during two cruises in March and July 2012. Dissolved N2O concentrations in surface waters ranged from 9.34 to 49.08 nmol x L(-1) with an average of (13.27 ± 6.40) nmol x L(-1) in spring and ranged from 7.27 to 27.81 nmol x L(-1) with an average of (10.62 ± 5.03) nmol x L(-1) in summer. There was no obvious difference between surface and bottom N2O concentrations. N2O concentrations in both surface and bottom waters decreased along the freshwater plume from the river mouth to the open sea. High values of dissolved N2O were found in turbidity maximum zone, which suggests that maximal turbidity enhances nitrification. Temperature had dual effects on dissolved N2O concentrations. N2O saturations in surface waters ranged from 86.9% to 351.3% with an average of (111.5 ± 41.4)% in spring and ranged from 111.7% to 396.0% with an average of (155.9 ± 68.4)% in summer. N2O were over-saturated at most stations. The sea-to-air fluxes of N2O were estimated to be (3.2 ± 10.9), (5.5 ± 19.3) and (12.2 ±52.3) μmol x (m2 x d)(-1) in spring and (7.3 ± 12.4), (12.7 ± 20.4) and (20.4 ± 35.9) μmol x (m2 x d)(-1) in summer using the LM86, W92 and RC01 relationships, respectively. The annual emissions of N2O from the Yangtze River estuary and its adjacent marine area were estimated to be 0.6 x 10(-2) Tg x a(-1) (LM86), 1.1 x 10(-2) Tg x a(-1) (W92) and 2.0 x 10(-2) Tg x a(-1) (RC01). Although the area of the Yangtze River estuary and its adjacent marine area only accounts for 0.02% of the total area of the world's oceans, their emission of N2O accounts for 0.06% of global oceanic N2O emission, indicating that the Yangtze River estuary and its adjacent marine area is an active area to produce and emit N2O.

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

NASA Technical Reports Server (NTRS)

Freund, Friedemann

1991-01-01

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Effects of land use on the concentration and emission of nitrous oxide in nitrogen-enriched rivers.

PubMed

Yang, Libiao; Lei, Kun

2018-07-01

Nitrous oxide (N 2 O) is a potent greenhouse gas that contributes to climate change and stratospheric ozone destruction. Nitrogen-enriched rivers are significant sources of atmospheric N 2 O. This study conducted a one-year field campaign in seven N-enriched rivers draining urban, rural, and agricultural land to determine the link between the production, concentrations, and emissions of N 2 O and land use. Estimated N 2 O fluxes varied between 1.30 and 1164.38 μg N 2 O-N m -2 h -1 with a mean value of 154.90 μg N 2 O-N m -2 h -1 , indicating that rivers were the net sources of atmospheric N 2 O. Concentrations of N 2 O ranged between 0.23 and 29.21 μg N 2 O-N L -1 with an overall mean value of 3.81 μg N 2 O-N L -1 . Concentrations of ammonium and nitrate in urban and rural rivers were high in the cold season. The concentrations were also high in agricultural rivers in the wet season. N 2 O concentrations and emissions in rural and urban rivers followed a similar pattern to ammonium and a similar pattern to nitrate in agricultural rivers. A strong link between the concentrations and emissions of N 2 O and land use was observed. N 2 O concentrations in and emissions from the rivers draining the urban and rural areas were significantly higher than the rivers draining the agricultural areas (P < 0.01). Stepwise regression analysis indicated that dissolved N 2 O were primarily influenced by NH 4 + in agricultural rivers and by NO 3 - in rural rivers; while dissolved N 2 O in urban rivers was primarily predicted by temperature and reflected the integrated impact of sewage input and river hydrology. Nitrate-N and NO 3- -O isotope data and linear regression of N 2 O and river water variables strongly indicated that dissolved N 2 O was mainly derived from nitrification in agricultural rivers and denitrification in rural and urban rivers. Copyright © 2018 Elsevier Ltd. All rights reserved.

Zirconia ceramics for excess weapons plutonium waste

NASA Astrophysics Data System (ADS)

Gong, W. L.; Lutze, W.; Ewing, R. C.

2000-01-01

We synthesized a zirconia (ZrO 2)-based single-phase ceramic containing simulated excess weapons plutonium waste. ZrO 2 has large solubility for other metallic oxides. More than 20 binary systems A xO y-ZrO 2 have been reported in the literature, including PuO 2, rare-earth oxides, and oxides of metals contained in weapons plutonium wastes. We show that significant amounts of gadolinium (neutron absorber) and yttrium (additional stabilizer of the cubic modification) can be dissolved in ZrO 2, together with plutonium (simulated by Ce 4+, U 4+ or Th 4+) and impurities (e.g., Ca, Mg, Fe, Si). Sol-gel and powder methods were applied to make homogeneous, single-phase zirconia solid solutions. Pu waste impurities were completely dissolved in the solid solutions. In contrast to other phases, e.g., zirconolite and pyrochlore, zirconia is extremely radiation resistant and does not undergo amorphization. Baddeleyite (ZrO 2) is suggested as the natural analogue to study long-term radiation resistance and chemical durability of zirconia-based waste forms.

ANALYTICAL METHOD FOR THE ABSORPTIOMETRIC DETERMINATION OF BORON IN URANIUM METAL POWDER

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1963-01-01

The U powder is dissolved in HCl and H/sub 2/O/sub 2/. The resulting solution is evaporated to dryness in the presence of H/sub 2/SO/sub 3/. Rosocyanin is formed, separated from the excess curcumin, and dissolved in ethanol for absorptiometric measurement. (auth)

Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

NASA Astrophysics Data System (ADS)

Gonzalez, Julia; Peña, Jasquelin

2016-04-01

Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the labile fraction may lower solution pH into a regime that favours abiotic oxidation of recalcitrant C by MnO2. This project demonstrates that the co-occurrence of mineral particles with metabolically active cells provides a direct link between the C and Mn cycles.

Toxicity of CuO nanoparticles to yeast Saccharomyces cerevisiae BY4741 wild-type and its nine isogenic single-gene deletion mutants.

PubMed

Kasemets, Kaja; Suppi, Sandra; Künnis-Beres, Kai; Kahru, Anne

2013-03-18

A suite of eight tentatively oxidative stress response-deficient Saccharomyces cerevisiae BY4741 single-gene mutants (sod1Δ, sod2Δ, yap1Δ, cta1Δ, ctt1Δ, gsh1Δ, glr1Δ, and ccs1Δ) and one copper-vulnerable mutant (cup2Δ) was used to elucidate weather the toxicity of CuO nanoparticles to S. cerevisiae is mediated by oxidative stress (OS). Specifically, sensitivity profiles of mutants' phenotypes and wild-type (wt) upon exposure to nano-CuO were compared. As controls, CuSO4 (solubility), bulk-CuO (size), H2O2, and menadione (OS) were used. Growth inhibition of wt and mutant strains was studied in rich YPD medium and cell viability in deionized water (DI). Dissolved Cu-ions were quantified by recombinant metal-sensing bacteria and chemical analysis. To wt strain nano-CuO was 32-fold more toxic than bulk-CuO: 24-h IC50 4.8 and 155 mg/L in DI and 643 and >20000 mg/L in YPD, respectively. In toxicant-free YPD medium, all mutants had practically similar growth patterns as wt. However, the mutant strains sod1Δ, sod2Δ, ccs1Δ, and yap1Δ showed up to 12-fold elevated sensitivity toward OS standard chemicals menadione and H2O2 but not to nano-CuO, indicating that CuO nanoparticles exerted toxicity to yeast cells via different mechanisms. The most vulnerable strain to all studied Cu compounds was the copper stress response-deficient strain cup2Δ (∼16-fold difference with wt), indicating that the toxic effect of CuO (nano)particles proceeds via dissolved Cu-ions. The dissolved copper solely explained the toxicity of nano-CuO in DI but not in YPD. Assumingly, in YPD nano-CuO acquired a coating of peptides/proteins and sorbed onto the yeast's outer surface, resulting in their increased solubility in the close vicinity of yeast cells and increased uptake of Cu-ions that was not registered by the assays used for the analysis of dissolved Cu-ions in the test medium. Lastly, as yeast retained its viability in DI even by 24th hour of incubation, the profiling of the acute basal toxicity of chemicals toward yeasts may be conducted in DI.

PHOTOOXIDATION AND ITS EFFECTS ON THE CARBOXYL CONTENT OF DISSOLVED ORGANIC MATTER IN TWO COASTAL RIVERS IN THE SOUTHEASTERN UNITED STATES

EPA Science Inventory

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 (ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study the quantitative relationships were investigated ...

An effective device for gas-liquid oxygen removal in enclosed microalgae culture.

PubMed

Su, Zhenfeng; Kang, Ruijuan; Shi, Shaoyuan; Cong, Wei; Cai, Zhaoling

2010-01-01

A high-performance gas-liquid transmission device (HPTD) was described in this paper. To investigate the HPTD mass transfer characteristics, the overall volumetric mass transfer coefficients, K(A)(La,CO(2)) for the absorption of gaseous CO(2) and K(A)(La,O(2)) for the desorption of dissolved O(2) were determined, respectively, by titration and dissolved oxygen electrode. The mass transfer capability of carbon dioxide was compared with that of dissolved oxygen in the device, and the operating conditions were optimized to suit for the large-scale enclosed micro-algae cultivation. Based on the effectiveness evaluation of the HPTD applied in one enclosed flat plate Spirulina culture system, it was confirmed that the HPTD can satisfy the demand of the enclosed system for carbon supplement and excessive oxygen removal.

Transcriptome analysis of Lactococcus lactis subsp. lactis during milk acidification as affected by dissolved oxygen and the redox potential.

PubMed

Larsen, Nadja; Moslehi-Jenabian, Saloomeh; Werner, Birgit Brøsted; Jensen, Maiken Lund; Garrigues, Christel; Vogensen, Finn Kvist; Jespersen, Lene

2016-06-02

Performance of Lactococcus lactis as a starter culture in dairy fermentations depends on the levels of dissolved oxygen and the redox state of milk. In this study the microarray analysis was used to investigate the global gene expression of L. lactis subsp. lactis DSM20481(T) during milk acidification as affected by oxygen depletion and the decrease of redox potential. Fermentations were carried out at different initial levels of dissolved oxygen (dO2) obtained by milk sparging with oxygen (high dO2, 63%) or nitrogen (low dO2, 6%). Bacterial exposure to high initial oxygen resulted in overexpression of genes involved in detoxification of reactive oxygen species (ROS), oxidation-reduction processes, biosynthesis of trehalose and down-regulation of genes involved in purine nucleotide biosynthesis, indicating that several factors, among them trehalose and GTP, were implicated in bacterial adaptation to oxidative stress. Generally, transcriptional changes were more pronounced during fermentation of oxygen sparged milk. Genes up-regulated in response to oxygen depletion were implicated in biosynthesis and transport of pyrimidine nucleotides, branched chain amino acids and in arginine catabolic pathways; whereas genes involved in salvage of nucleotides and cysteine pathways were repressed. Expression pattern of genes involved in pyruvate metabolism indicated shifts towards mixed acid fermentation after oxygen depletion with production of specific end-products, depending on milk treatment. Differential expression of genes, involved in amino acid and pyruvate pathways, suggested that initial oxygen might influence the release of flavor compounds and, thereby, flavor development in dairy fermentations. The knowledge of molecular responses involved in adaptation of L. lactis to the shifts of redox state and pH during milk fermentations is important for the dairy industry to ensure better control of cheese production. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of carbon and nitrogen addition on nitrous oxide and carbon dioxide fluxes from thawing forest soils

NASA Astrophysics Data System (ADS)

Haohao, Wu; Xingkai, Xu; Cuntao, Duan; TuanSheng, Li; Weiguo, Cheng

2017-07-01

Packed soil-core incubation experiments were done to study the effects of carbon (glucose, 6.4 g C m-2) and nitrogen (NH4Cl and KNO3, 4.5 g N m-2) addition on nitrous oxide (N2O) and carbon dioxide (CO2) fluxes during thawing of frozen soils under two forest stands (broadleaf and Korean pine mixed forest and white birch forest) with two moisture levels (55 and 80% water-filled pore space). With increasing soil moisture, the magnitude and longevity of the flush N2O flux from forest soils was enhanced during the early period of thawing, which was accompanied by great NO3--N consumption. Without N addition, the glucose-induced cumulative CO2 fluxes ranged from 9.61 to 13.49 g CO2-C m-2, which was larger than the dose of carbon added as glucose. The single addition of glucose increased microbial biomass carbon but slightly affected soil dissolved organic carbon pool. Thus, the extra carbon released upon addition of glucose can result from the decomposition of soil native organic carbon. The glucose-induced N2O and CO2 fluxes were both significantly correlated to the glucose-induced total N and dissolved organic carbon pools and influenced singly and interactively by soil moisture and KNO3 addition. The interactive effects of glucose and nitrogen inputs on N2O and CO2 fluxes from forest soils after frost depended on N sources, soil moisture, and vegetation types.

Electrochemical, H2O2-Boosted Catalytic Oxidation System

NASA Technical Reports Server (NTRS)

Akse, James R.; Thompson, John O.; Schussel, Leonard J.

2004-01-01

An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

Electrodeposition of crystalline GaAs on liquid gallium electrodes in aqueous electrolytes.

PubMed

Fahrenkrug, Eli; Gu, Junsi; Maldonado, Stephen

2013-01-09

Crystalline GaAs (c-GaAs) has been prepared directly through electroreduction of As(2)O(3) dissolved in an alkaline aqueous solution at a liquid gallium (Ga(l)) electrode at modest temperatures (T ≥ 80 °C). Ga(l) pool electrodes yielded consistent electrochemical behavior, affording repetitive measurements that illustrated the interdependences of applied potential, concentration of dissolved As(2)O(3), and electrodeposition temperature on the quality of the resultant c-GaAs(s). Raman spectra indicated the composition of the resultant film was strongly dependent on both the electrodeposition temperature and dissolved concentration of As(2)O(3) but not to the applied bias. For electrodepositions performed either at room temperature or with high (≥0.01 M) concentrations of dissolved As(2)O(3), Raman spectra of the electrodeposited films were consistent with amorphous As(s). X-ray diffractograms of As(s) films collected after thermal annealing indicated metallurgical alloying occurred only at temperatures in excess of 200 °C. Optical images and Raman spectra separately showed the composition of the as-electrodeposited film in dilute (≤0.001 M) solutions of dissolved As(2)O(3)(aq) was pure c-GaAs(s) at much lower temperatures than 200 °C. Diffractograms and transmission electron microscopy performed on as-prepared films confirmed the identity of c-GaAs(s). The collective results thus provide the first clear demonstration of an electrochemical liquid-liquid-solid (ec-LLS) process involving a liquid metal that serves simultaneously as an electrode, a solvent/medium for crystal growth, and a coreactant for the synthesis of a polycrystalline semiconductor. The presented data serve as impetus for the further development of the ec-LLS process as a controllable, simple, and direct route for technologically important optoelectronic materials such as c-GaAs(s).

Simultaneous determination of dissolved gases and moisture in mineral insulating oils by static headspace gas chromatography with helium photoionization pulsed discharge detection.

PubMed

Jalbert, J; Gilbert, R; Tétreault, P

2001-07-15

This paper presents the development of a static headspace capillary gas chromatographic method (HS-GC) for simultaneously determining dissolved gases (H2, O2, N2, CO, CO2, CH4, C2H6, C2H4, C2H2, C3H8) and moisture from a unique 15-mL mineral oil sample. A headspace sampler device is used to equilibrate the sample species in a two-phase system under controlled temperature and agitation conditions. A portion of the equilibrated species is then automatically split-injected into two chromatographic channels mounted on the same GC for their separation. The hydrocarbons and the lighter gases are separated on the first channel by a GS-Q column coupled with a MolSieve 5-A column via a bypass valve, while the moisture is separated on the second channel using a Stabilwax column. The analytes are detected by using two universal pulsed-discharge helium ionization detectors (PDHID). The performance of the method was established using equilibrated vials containing known amounts of gas mixture, water, and blank oil. The signal is linear over the concentration ranges normally found for samples collected from open-breathing power transformers. Determination sensitivity varies with the nature of the species considered with values as high as 21 500 A x 10(-9) s (microg/ g)(-1) for H2O, 46-216 A x 10(-9) s (microL/L)(-1) for the hydrocarbons and carbon oxides, and as low as 8-21 A x 10(-9) s (microL/L)(-1) for the O2 and N2 permanent gases. The detection limit of the method is between 0.08 and 6 microL/L for the dissolved gases, except for O2, N2, and CO2, where higher values are observed due to air intrusion during sampler operations, and 0.1 microg/g for the dissolved water. Ten consecutive measurements in the low and high levels of the calibration curves have shown a precision better than 12% and 6%, respectively, in all cases. A comparison study between the HS-GC method and the ASTM standard procedures on 31 field samples showed a very good agreement of the results. The advantages of configuring the arrangement with two PDHID over the conventional flame ionization and thermal conductivity detectors were clearly demonstrated.

Ocean deoxygenation in a warming world.

PubMed

Keeling, Ralph E; Körtzinger, Arne; Gruber, Nicolas

2010-01-01

Ocean warming and increased stratification of the upper ocean caused by global climate change will likely lead to declines in dissolved O2 in the ocean interior (ocean deoxygenation) with implications for ocean productivity, nutrient cycling, carbon cycling, and marine habitat. Ocean models predict declines of 1 to 7% in the global ocean O2 inventory over the next century, with declines continuing for a thousand years or more into the future. An important consequence may be an expansion in the area and volume of so-called oxygen minimum zones, where O2 levels are too low to support many macrofauna and profound changes in biogeochemical cycling occur. Significant deoxygenation has occurred over the past 50 years in the North Pacific and tropical oceans, suggesting larger changes are looming. The potential for larger O2 declines in the future suggests the need for an improved observing system for tracking ocean 02 changes.

Use of multiple sensor technologies for quality control of in situ biogeochemical measurements: A SeaCycler case study

NASA Astrophysics Data System (ADS)

Atamanchuk, Dariia; Koelling, Jannes; Lai, Jeremy; Send, Uwe; Wallace, Douglas

2017-04-01

Over the last two decades observing capacity for the global ocean has increased dramatically. Emerging sensor technologies for dissolved gases, nutrients and bio-optical properties in seawater are allowing extension of in situ observations beyond the traditionally measured salinity, temperature and pressure (CTD). However the effort to extend observations using autonomous instruments and platforms carries the risk of losing the level of data quality achievable through conventional water sampling techniques. We will present results from a case study with the SeaCycler profiling winch focusing on quality control of the in-situ measurements. A total of 13 sensors were deployed from May 2016 to early 2017 on SeaCycler's profiling sensor float, including CTD, dissolved oxygen (O2, 3 sensors), carbon dioxide (pCO2, 2 sensors), nutrients, velocity sensors, fluorometer, transmissometer, single channel PAR sensor, and others. We will highlight how multiple measurement technologies (e.g. for O2 and CO2) complement each other and result in a high quality data product. We will also present an initial assessment of the bio-optical data, their implications for seasonal phytoplankton dynamics and comparisons to climatologies and ocean-color data products obtained from the MODIS satellite.

Localized zones of denitrification in a floodplain aquifer in southern Wisconsin, USA

NASA Astrophysics Data System (ADS)

Craig, Laura; Bahr, Jean M.; Roden, Eric E.

2010-12-01

A floodplain aquifer within an agricultural watershed near Madison, Wisconsin (USA), was studied to determine whether denitrification was occurring below the surface organic layer. Groundwater levels and concentrations of O2, Cl-, NO{3/-}, SO{4/2-}, dissolved organic carbon (DOC), and major cations were monitored over a 1-year period along a 230-m transect between an agricultural field and a stream discharge point. Seventeen groundwater samples were analyzed for δ15NNO3 and δ18ONO3 composition. Samples in which NO{3/-} was too low for stable isotope analysis were analyzed for excess dissolved N2. Groundwater NO{3/-} concentrations declined between the agricultural field and the discharge point. Chloride and δ15NNO3/δ18ONO3 data indicated that the drop in NO{3/-} was caused primarily by dilution of shallow NO{3/-}-rich water with deeper, NO{3/-}-depleted groundwater. Two localized zones of denitrification were identified in the upland-wetland transition by their δ15NNO3 and δ18ONO3 signatures, and two in the stream hyporheic zone by the presence of excess dissolved N2. The combined stratigraphic, hydrologic, and geochemical data in these locations correspond to groundwater mixing zones where NO{3/-} is delivered to subsurface layers that support denitrification fueled by dissolved (e.g. DOC or dissolved Fe(II)) and/or solid-phase (e.g. particulate organic carbon, solid-associated Fe(II), or pyrite) electron donors.

A simple recovery process for biodegradable plastics accumulated in cyanobacteria treated with ionic liquids.

PubMed

Kobayashi, Daigo; Fujita, Kyoko; Nakamura, Nobuhumi; Ohno, Hiroyuki

2015-02-01

Here, we proposed a simple recovery process for poly(3-hydroxybutyrate) (PHB) accumulated in cyanobacteria by using ionic liquids (ILs), which dissolve cyanobacteria but not PHB. First, we investigated the effects of IL polarity on hydrogen-bonding receipt ability (β value) and hydrogen-bonding donating ability (α value) and evaluated the subsequent dissolution of cyanobacteria. We found that ILs having α values higher than approximately 0.4 and β values of approximately 0.9 were suitable for dissolution of cyanobacteria. In particular, 1-ethyl-3-methylimidazolium methylphosphonate ([C2mim][MeO(H)PO2]) was found to dissolve cyanobacteria components, but not PHB. Thus, we verified that PHB produced in cyanobacteria could be separated and recovered by simple filtering after dissolution of cyanobacteria in [C2mim][MeO(H)PO2]. Using this technique, more than 98 % of PHB was obtained on the filter as residues separated from cyanobacteria. Furthermore, [C2mim][MeO(H)PO2] maintained the ability to dissolve cyanobacteria after a simple recycling procedure.

Distributions and Relationships of CO2, O2, and Dimethylsulfide in the Changjiang (Yangtze) Estuary and Its Adjacent Waters in Summer

NASA Astrophysics Data System (ADS)

Wu, Xi; Tan, Tingting; Liu, Chunying; Li, Tie; Liu, Xiaoshou; Yang, Guipeng

2018-04-01

The distributions and relationships of O2, CO2, and dimethylsulfide (DMS) in the Changjiang (Yangtze) Estuary and its adjacent waters were investigated in June 2014. In surface water, mean O2 saturation level, partial pressure of CO2 (pCO2), and DMS concentrations (and ranges) were 110% (89%-167%), 374 μatm (91-640 μatm), and 8.53 nmol L-1 (1.10-27.50 nmol L-1), respectively. The sea-to-air fluxes (and ranges) of DMS and CO2 were 8.24 μmol m-2 d-1 (0.26-62.77 μmol m-2 d-1), and -4.7 mmol m-2 d-1 (-110.8-31.7 mmol m-2 d-1), respectively. Dissolved O2 was oversaturated, DMS concentrations were relatively high, and this region served as a sink of atmospheric CO2. The pCO2 was significantly and negatively correlated with the O2 saturation level, while the DMS concentration showed different positive relationships with the O2 saturation level in different water masses. In vertical profiles, a hypoxic zone existed below 20 m at a longitude of 123°E. The stratification of temperature and salinity caused by the Taiwan Warm Current suppressed seawater exchange between upper and lower layers, resulting in the formation of a hypoxic zone. Oxidative decomposition of organic detritus carried by the Changjiang River Diluted Water (CRDW) consumed abundant O2 and produced additional CO2. The DMS concentrations decreased because of low phytoplankton biomass in the hypoxic zone. Strong correlations appeared between the O2 saturation level, pCO2 and DMS concentrations in vertical profiles. Our results strongly suggested that CRDW played an important role in the distributions and relationships of O2, CO2, and DMS.

A Laughing Gas Greenhouse for the Proterozoic?

NASA Astrophysics Data System (ADS)

Roberson, A. L.; Roadt, J.; Halevy, I.; Kasting, J. F.

2010-12-01

An anoxic, sulfidic ‘Canfield ocean’ during the Proterozoic (0.75-2.3 Ga) would have had limited trace metal abundances because of the low solubility of metal sulfides. The limitation on copper, specifically, would have had a significant impact on marine denitrification. Copper is needed for the enzyme that controls the final step of denitrification, from N2O to N2. Today, only about 5-6 percent of denitrification results in release of N2O. If all denitrification stopped at N2O during the Proterozoic, the N2O flux could have been 15-20 times higher than today. Other parts of the nitrogen cycle should have been able to operate at rates comparable to today, as catalysts for these reactions should have existed. The high N2O flux should have created higher atmospheric N2O concentrations; although this effect may have been offset by faster rates of N2O photolysis if O2 concentrations were lower than today. N2O concentrations of 0.3 to 30 ppmv, along with methane levels of 30-100 ppm, could have kept the surface warm during the Proterozoic without necessitating high CO2 levels. The high methane concentrations were a consequence of lack of dissolved O2 and sulfate in the deep ocean, which should have led to a high CH4 flux from marine sediments. A second oxygenation event at the end of the Proterozoic would have resulted in a shift to a more modern ocean and, consequently, more modern concentrations of atmospheric N2O and CH4.

The Fate of ZnO Nanoparticles Administered to Human Bronchial Epithelial Cells

PubMed Central

Gilbert, Benjamin; Fakra, Sirine C.; Xia, Tian; Pokhrel, Suman; Mädler, Lutz; Nel, André E.

2014-01-01

A particular challenge for nanotoxicology is the evaluation of the biological fate and toxicity of nanomaterials that dissolve in aqueous fluids. Zinc oxide nanomaterials are of particular concern because dissolution leads to release of the toxic divalent zinc ion. Although dissolved zinc ions have been implicated in ZnO cytotoxicity, direct identification of the chemical form of zinc taken up by cells exposed to ZnO nanoparticles, and its intracellular fate, has not yet been achieved. We combined high resolution X-ray spectromicroscopy and high elemental sensitivity X-ray microprobe analyses to determine the fate of ZnO and less soluble iron-doped ZnO nanoparticles following exposure to cultures of human bronchial epithelial cells, BEAS-2B. We complemented two-dimensional X-ray imaging methods with atomic force microscopy of cell surfaces to distinguish between nanoparticles that were transported inside the cells from those that adhered to the cell exterior. The data suggest cellular uptake of ZnO nanoparticles is a mechanism of zinc accumulation in cells. Following uptake, ZnO nanoparticles dissolved completely generating intracellular Zn2+ complexed by molecular ligands. These results corroborate a model for ZnO nanoparticle toxicity that is based on nanoparticle uptake followed by intracellular dissolution. PMID:22646753

The sensitivity of tropospheric chemistry to cloud interactions

NASA Technical Reports Server (NTRS)

Jonson, Jan E.; Isaksen, Ivar S. A.

1994-01-01

Clouds, although only occupying a relatively small fraction of the troposphere volume, can have a substantial impact on the chemistry of the troposphere. In newly formed clouds, or in clouds with air rapidly flowing through, the chemistry is expected to be far more active than in aged clouds with stagnant air. Thus, frequent cycling of air through shortlived clouds, i.e. cumulus clouds, is likely to be a much more efficient media for altering the composition of the atmosphere than an extensive cloud cover i.e. frontal cloud systems. The impact of clouds is tested out in a 2-D channel model encircling the globe in a latitudinal belt from 30 to 60 deg N. The model contains a detailed gas phase chemistry. In addition physiochemical interactions between the gas and aqueous phases are included. For species as H2O2, CH2O, O3, and SO2, Henry's law equilibria are assumed, whereas HNO3 and H2SO4 are regarded as completed dissolved in the aqueous phase. Absorption of HO2 and OH is assumed to be mass-transport limited. The chemistry of the aqueous phase is characterized by rapid cycling of odd hydrogen, (H2O2, HO2, and OH). O2(-) (produced through dissociation of HO2) reacting with dissolved O3 is a major source of OH in the aqueous phase. This reaction can be a significant sink for O3 in the troposphere. In the interstitial cloud air, odd hydrogen is depleted, whereas NO(x) remains in the gas phase, thus reducing ozone production due to the reaction between NO and HO2. Our calculations give markedly lower ozone levels when cloud interactions are included. This may in part explain the overpredictions of ozone levels often experienced in models neglecting cloud chemical interactions. In the present study, the existence of clouds, cloud types, and their lifetimes are modeled as pseudo random variables. Such pseudo random sequences are in reality deterministic and may, given the same starting values, be reproduced. The effects of cloud interactions on the overall chemistry of the troposphere are discussed. In particular, tests are performed to determine the sensitivity of cloud frequencies and cloud types.

Meridional fluxes of dissolved organic matter in the North Atlantic Ocean

NASA Technical Reports Server (NTRS)

Walsh, John J.; Carder, Kendall L.; Mueller-Karger, Frank E.

1992-01-01

Biooptical estimates of gelbstoff and a few platinum measurements of dissolved organic carbon (DOCpt) are used to construct a budget of the meridional flux of DOC and dissolved organic nitrogen (DON) across 36 deg 25 min N in the North Atlantic from previous inverse models of water and element transport. Distinct southward subsurface fluxes of dissolved organic matter within subducted shelf water, cabelled slope water, and overturned basin water are inferred. Within two cases of a positive gradient of DOCpt between terrestrial/shelf and offshore stocks, the net equatorward exports of O2 and DOCpt from the northern North Atlantic yield molar ratios of 2.1 to 9.1, compared to the expected Redfield O2/C ratio of 1.3. It is concluded that some shelf export of DOC, with a positive gradient between coastal and oceanic stocks, as well as falling particles, are required to balance carbon, nitrogen, and oxygen budgets of the North Atlantic.

Major and minor oxide and trace element determination in silicate rocks by direct current plasma optical emission echelle spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bankston, D.C.; Humphris, S.E.; Thompson, G.

1979-07-01

A technique for the determination of major concentrations of SiO/sub 2/, Al/sub 2/O/sub 3/, Fe/sub 2/O/sub 3/, MgO, CaO, Na/sub 2/O, and K/sub 2/O, minor levels of TiO/sub 2/, P/sub 2/O/sub 5/, and MnO, and trace concentrations of Ba, Cr, Cu, Ni, Sr, V, and Zn, in semi-microsamples 200 mg) of powdered whole rock, is described. Chemically diverse standard reference rocks are used both for calibration and assessment of accuracy. A lithium metaborate fusion melt of each standard or sample is dissolved in dilute HNO/sub 3/ containing Cs/sup +/ at a level of 0.2% (w/v). The resulting solution is usedmore » to perform all analyses except those for Na/sub 2/O and K/sub 2/O, which are determined in a portion of the original sample solution wherein the Cs/sup +/ concentration has been raised to 0.32% (w/v). Analyses of both portions of each sample solution are performed using an optical emission spectrometer/spectrograph equipped with an echelle monochromator and a dc argon plasma excitation source. Trace element detection limits ranged from 2 ppM for Cu to 15 ppM for Zn. A study of precision based on replicate determinations in three splits of the proposed USGS reference basalt BHVO-1 yielded the following results: (1) For analyses of the major and minor oxide constituents, values of the percent relative standard deviation (RSD) ranged from 1 for CaO, to 21 for P/sub 2/O/sub 5/. 2) For trace element determinations, values of the RSD ranged from 2 for Cu, to 19 for Zn. 2 figures, 11 tables.« less

Hydrogeologic controls on episodic H2 release from precambrian fractured rocks--energy for deep subsurface life on earth and mars.

PubMed

Sherwood Lollar, B; Voglesonger, K; Lin, L-H; Lacrampe-Couloume, G; Telling, J; Abrajano, T A; Onstott, T C; Pratt, L M

2007-12-01

Dissolved H(2) concentrations up to the mM range and H(2) levels up to 9-58% by volume in the free gas phase are reported for groundwaters at sites in the Precambrian shields of Canada and Finland. Along with previously reported dissolved H(2) concentrations up to 7.4 mM for groundwaters from the Witwatersrand Basin, South Africa, these findings indicate that deep Precambrian Shield fracture waters contain some of the highest levels of dissolved H(2) ever reported and represent a potentially important energy-rich environment for subsurface microbial life. The delta (2)H isotope signatures of H(2) gas from Canada, Finland, and South Africa are consistent with a range of H(2)-producing water-rock reactions, depending on the geologic setting, which include both serpentinization and radiolysis. In Canada and Finland, several of the sites are in Archean greenstone belts characterized by ultramafic rocks that have under-gone serpentinization and may be ancient analogues for serpentinite-hosted gases recently reported at the Lost City Hydrothermal Field and other hydrothermal seafloor deposits. The hydrogeologically isolated nature of these fracture-controlled groundwater systems provides a mechanism whereby the products of water-rock interaction accumulate over geologic timescales, which produces correlations between high H(2) levels, abiogenic hydrocarbon signatures, and the high salinities and highly altered delta (18)O and delta (2)H values of these groundwaters. A conceptual model is presented that demonstrates how periodic opening of fractures and resultant mixing control the distribution and supply of H(2) and support a microbial community of H(2)-utilizing sulfate reducers and methanogens.

Conditions for the formation of pure birnessite during the oxidation of Mn(II) cations in aqueous alkaline medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boumaiza, Hella; Laboratoire de Chimie Physique et Microbiologie pour l'Environnement; Département de Génie Biologique et Chimique, Institut National des Sciences Appliquées et de Technologies

Birnessite was synthetized through redox reaction by mixing MnO{sub 4}{sup -}, Mn{sup 2+} and OH{sup -} solutions. The Mn(VII): Mn(II) ratio of 0.33 was chosen and three methods were used consisting in a quick mixing under vigorous stirring of two of the three reagents and then on the dropwise addition of the third one. The obtained solids were characterized by XRD, FTIR and XPS spectroscopies. Their average oxidation states were determined from ICP and CEC measurements while their surface properties were investigated by XPS. This study provides an increased understanding of the importance of dissolved oxygen in the formation ofmore » birnessite and hausmannite and shows the ways to obtain pure birnessite. The role of counter-ion ie. Na{sup +} or K{sup +} was also examined. - Graphical abstract: Pathways of birnessite formation. - Highlights: • Pure birnessite is prepared through a redox reaction. • Hausmannite formation is prevented by controlling dissolved O2. • The employed counterion influences the purity of birnessite. • Initial Mn(OH){sub 2} is oxidized by both MnO{sub 4}{sup -} and dissolved O{sub 2}.« less

Comparing the efficacy of hyper-pure chlorine-dioxide with other oral antiseptics on oral pathogen microorganisms and biofilm in vitro.

PubMed

Herczegh, Anna; Gyurkovics, Milán; Agababyan, Hayk; Ghidán, Agoston; Lohinai, Zsolt

2013-09-01

This study examines the antibacterial properties of sodium hypochlorite (NaOCl), chlorhexidine gluconate (CHX), Listerine®, and high purity chlorine dioxide (Solumium, ClO2) on selected common oral pathogen microorganisms and on dental biofilm in vitro. Antimicrobial activity of oral antiseptics was compared to the gold standard phenol. We investigated Streptococcus mutans, Lactobacillus acidophilus, Enterococcus faecalis, Veillonella alcalescens, Eikenella corrodens, Actinobacillus actinomycetemcomitans and Candida albicans as some important representatives of the oral pathogens. Furthermore, we collected dental plaque from the upper first molars of healthy young students. Massive biofilm was formed in vitro and its reduction was measured after treating it with mouthrinses: CHX, Listerine® or hyper pure ClO2. Their biofilm disrupting effect was measured after dissolving the crystal violet stain from biofilm by photometer. The results have showed that hyper pure ClO2 solution is more effective than other currently used disinfectants in case of aerobic bacteria and Candida yeast. In case of anaerobes its efficiency is similar to CHX solution. The biofilm dissolving effect of hyper pure ClO2 is significantly stronger compared to CHX and Listerine® after 5 min treatment. In conclusion, hyper pure ClO2 has a potent disinfectant efficacy on oral pathogenic microorganisms and a powerful biofilm dissolving effect compared to the current antiseptics, therefore high purity ClO2 may be a new promising preventive and therapeutic adjuvant in home oral care and in dental or oral surgery practice.

Interannual Variations in Global Net Carbon Production in the Absence of Fixed Nitrogen: Implication of New Production Supported by Dinitrogen Fixing Microorganisms

NASA Astrophysics Data System (ADS)

Lee, K.; Ko, Y. H.

2016-12-01

In the ocean without the measurable levels of nitrate, new production, i.e. the amount of carbon transported from the sunlit upper water to deep water, was estimated by summing the seasonal reduction in the total dissolved inorganic carbon (NCT = CT x 35/S) concentration in the surface mixed layer. Total reduction in the mixed layer NCT inventory in each 4o latitude by 5o longitude was calculated using an annual cycle of NCT, which was deduced from global monthly records of partial pressure of CO2 (based on more than 6.5 million data) and total alkalinity fields using thermodynamic models. The estimation of total NCT reduction for each pixel was then corrected for small changes caused by atmospheric nitrogen deposition and net air-sea CO2 exchange. This novel method yields 0.8 ± 0.3 petagrams of global new production per year (Pg C yr, Pg = 1015 grams), which is likely to be mediated exclusively by dinitrogen (N2) fixing microorganisms. These organisms utilize the inexhaustible pool of dissolved N2 and thereby circumvent nitrate limitation, particularly in the oligotrophic tropical and subtropical ocean.

A coupled geochemical and biogeochemical approach to characterize the bioreactivity of dissolved organic matter from a headwater stream

NASA Astrophysics Data System (ADS)

Sleighter, Rachel L.; Cory, Rose M.; Kaplan, Louis A.; Abdulla, Hussain A. N.; Hatcher, Patrick G.

2014-08-01

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% of stream water DOC was biodegraded by microorganisms, including 31-45% of the humic DOC. This bioreactive DOM separated into two different groups: (1) H/C centered at 1.5 with O/C 0.1-0.5 or (2) low H/C of 0.5-1.0 spanning O/C 0.2-0.7 that were positively correlated (Spearman ranking) with chromophoric and fluorescent DOM (CDOM and FDOM, respectively). DOM that was more recalcitrant and resistant to microbial degradation aligned tightly in the center of the van Krevelen space (H/C 1.0-1.5, O/C 0.25-0.6) and negatively correlated (Spearman ranking) with CDOM and FDOM. These findings were supported further by principal component analysis and 2-D correlation analysis of the relative magnitudes of the mass spectral peaks assigned to molecular formulas. This study demonstrates that our approach of processing stream water through bioreactors followed by EEMs and FTICR-MS analyses, in combination with multivariate statistical analysis, allows for precise, robust characterization of compound bioreactivity and associated molecular level composition.

Continuous high-frequency dissolved O2/Ar measurements by equilibrator inlet mass spectrometry.

PubMed

Cassar, Nicolas; Barnett, Bruce A; Bender, Michael L; Kaiser, Jan; Hamme, Roberta C; Tilbrook, Bronte

2009-03-01

The oxygen (O(2)) concentration in the surface ocean is influenced by biological and physical processes. With concurrent measurements of argon (Ar), which has similar solubility properties as oxygen, we can remove the physical contribution to O(2) supersaturation and determine the biological oxygen supersaturation. Biological O(2) supersaturation in the surface ocean reflects the net metabolic balance between photosynthesis and respiration, i.e., the net community productivity (NCP). We present a new method for continuous shipboard measurements of O(2)/Ar by equilibrator inlet mass spectrometry (EIMS). From these measurements and an appropriate gas exchange parametrization, NCP can be estimated at high spatial and temporal resolution. In the EIMS configuration, seawater from the ship's continuous intake flows through a cartridge enclosing a gas-permeable microporous membrane contactor. Gases in the headspace of the cartridge equilibrate with dissolved gases in the flowing seawater. A fused-silica capillary continuously samples headspace gases, and the O(2)/Ar ratio is measured by mass spectrometry. The ion current measurements on the mass spectrometer reflect the partial pressures of dissolved gases in the water flowing through the equilibrator. Calibration of the O(2)/Ar ion current ratio (32/40) is performed automatically every 2 h by sampling ambient air through a second capillary. A conceptual model demonstrates that the ratio of gases reaching the mass spectrometer is dependent on several parameters, such as the differences in molecular diffusivities and solubilities of the gases. Laboratory experiments and field observations performed by EIMS are discussed. We also present preliminary evidence that other gas measurements, such as N(2)/Ar and pCO(2) measurements, may potentially be performed with EIMS. Finally, we compare the characteristics of the EIMS with the previously described membrane inlet mass spectrometry (MIMS) approach.

Reduction of nitrate in aquifer microcosms by carbon additions

USGS Publications Warehouse

Obenhuber, Donald C.; Lowrance , Richard

1991-01-01

Aquifer microcosms were used to examine the effects of NO−3 and C amendments on groundwater from the Claiborne aquifer. Nitrate concentrations of 12.17 mg L−1 in aquifer microcosms were reduced 0.92%/d to 5.84 mg L−1 by the addition of 10 mg C L−1 for 35 d. Nitrate disappearance correlated with increases in number of denitrifiers and dissolved N2O concentration and decreases in dissolved oxygen, suggesting biological denitrification. Nitrate/chloride ratios decreased in microcosms with 10 mg C L−1 added and then increased when the C addition was removed. Carbon additions of 0.4 mg C L−1 had no effect on the microbial or chemical properties of the microcosms. Nitrous oxide levels in wells sampling the Claiborne aquifer showed an increase with depth, indicating N2O production within the aquifer. Microcosms are useful tools to examine biological transformations of chemical contaminants in unconsolidated aquifer material. The remediation of NO−3 contaminated aquifers by organic infusion is possible and appears to be a function of microbial denitrification.

Optical and Structural Characterization of ZnO/TiO2 Bilayer Thin Films Grown by Sol-Gel Spin Coating

NASA Astrophysics Data System (ADS)

Gareso, P. L.; Musfitasari; Juarlin, Eko

2018-03-01

Structural and optical properties of ZnO/TiO2 bilayers thin films have been investigated using x-ray diffraction (X-RD), scanning electron microscopy (SEM), and optical transmittance UV-Vis measurements. ZnO thin films were prepared by dissolving zinc acetate dehydrated into a solvent of ethanol and then added triethanolamin. In the case of TiO2 layers, tetraisoproxide was dissolved into ethanol and then added an acetate acid. The layer of ZnO was deposited first followed by TiO2 layer on a glass substrate using a spin coating technique. The ZnO/TiO2 bilayers were annealed at various temperatures from 300°C until 600°C for 60 minutes. The X-ray diffraction results show that there was an enhancement of the x-ray spectra as annealed temperature increased to 600°C in comparison to the samples that were annealed at 300°C. Based on the optical measurement of UV-Vis, the band gap energy of ZnO/TiO2 bilayer is around 3.2 eV at temperature of 300°C. This value is similar to the band gap energy of ZnO. SEM results show that there is no cluster in the surface of ZnO/TiO2 bilayer.

Application of Oxygen-Enriched Aeration in the Production of Bacitracin by Bacillus licheniformis

PubMed Central

Flickinger, M. C.; Perlman, D.

1979-01-01

The physiological effects of controlling the dissolved oxygen tension at 0.01, 0.02, and 0.05 atm by the use of oxygen-enriched aeration were investigated during growth and bacitracin production by Bacillus licheniformis ATCC 10716. Up to a 2.35-fold increase in the final antibiotic yield and a 4-fold increase in the rate of bacitracin synthesis were observed in response to O2-enriched aeration. The increase in antibiotic production was accompanied by increased respiratory activity and an increase in the specific productivity of the culture from 1.3 to 3.6 g of antibiotic per g of cell mass produced. Oxygen enrichment of the aeration decreased medium carbohydrate uptake and the maximum specific growth rate of B. licheniformis from 0.6 h−1 to as low as 0.15 h−1, depending upon the level of enrichment and the conditions of oxygen transfer rate (impeller speed). The response of this culture to O2 enrichment suggests that this method of controlling the dissolved oxygen tension for antibiotic-producing cultures may simulate conditions that would occur if the carbon source were fed slowly, as is often employed to optimize antibiotic production. Analysis of the biologically active bacitracins produced by B. licheniformis ATCC 10716 suggested that the ratio of biologically active peptides was not changed by O2 enrichment, nor were any new biologically active compounds formed. Images PMID:34361

Molecular dynamics simulations of the surface tension of oxygen-supersaturated water

NASA Astrophysics Data System (ADS)

Jain, S.; Qiao, L.

2017-04-01

In this work, non-reactive molecular dynamic simulations were conducted to determine the surface tension of water as a function of the concentration of the dissolved gaseous molecules (O2), which would in turn help to predict the pressure inside the nanobubbles under supersaturation conditions. Knowing the bubble pressure is a prerequisite for understanding the mechanisms behind the spontaneous combustion of the H2/O2 gases inside the nanobubbles. First, the surface tension of pure water was determined using the planar interface method and the Irving and Kirkwood formula. Next, the surface tension of water containing four different supersaturation concentrations (S) of O2 gas molecules was computed considering the curved interface of a nanobubble. The surface tension of water was found to decrease with an increase in the supersaturation ratio or the concentration of the dissolved O2 gas molecules.

Method for dissolving plutonium oxide with HI and separating plutonium

DOEpatents

Vondra, Benedict L.; Tallent, Othar K.; Mailen, James C.

1979-01-01

PuO.sub.2 -containing solids, particularly residues from incomplete HNO.sub.3 dissolution of irradiated nuclear fuels, are dissolved in aqueous HI. The resulting solution is evaporated to dryness and the solids are dissolved in HNO.sub.3 for further chemical reprocessing. Alternatively, the HI solution containing dissolved Pu values, can be contacted with a cation exchange resin causing the Pu values to load the resin. The Pu values are selectively eluted from the resin with more concentrated HI.

Influence of dissolved organic matter on photogenerated reactive oxygen species and metal-oxide nanoparticle toxicity.

PubMed

Li, Yang; Niu, Junfeng; Shang, Enxiang; Crittenden, John Charles

2016-07-01

The effect of humic acid (HA) or fulvic acid (FA) on reactive oxygen species (ROS) generation by six metal-oxide nanoparticles (NPs) and their toxicities toward Escherichia coli was investigated under UV irradiation. Dissolved organic matter (DOM) decreased OH generation by TiO2, ZnO, and Fe2O3, with FA inhibiting OH generation more than HA. The generated OH in NPs/DOM mixtures was higher than the measured concentrations because DOM consumes OH faster than its molecular probe. None of NPs/FA mixtures produced O2(-). The generated O2(-) concentrations in NPs/HA mixtures (except Fe2O3/HA) were higher than the sum of O2(-) concentrations that produced as NPs and HA were presented by themselves. Synergistic O2(-) generation in NPs/HA mixtures resulted from O2 reduction by electron transferred from photoionized HA to NPs. DOM increased (1)O2 generation by TiO2, CuO, CeO2, and SiO2, and FA promoted (1)O2 generation more than HA. Enhanced (1)O2 generation resulted from DOM sensitization of NPs. HA did not increase (1)O2 generation by ZnO and Fe2O3 primarily because released ions quenched (1)O2 precursor ((3)HA*). Linear correlation was developed between total ROS concentrations generated by NPs/DOM mixtures and bacterial survival rates (R(2) ≥ 0.80). The results implied the necessity of considering DOM when investigating the photoreactivity of NPs. Copyright © 2016 Elsevier Ltd. All rights reserved.

In situ electrochemical and photo-electrochemical generation of the fenton reagent: a potentially important new water treatment technology.

PubMed

Peralta-Hernández, J M; Meas-Vong, Yunny; Rodríguez, Francisco J; Chapman, Thomas W; Maldonado, Manuel I; Godínez, Luis A

2006-05-01

In this work, the design and construction of an annular tube reactor for the electrochemical and photo-electrochemical in situ generation of H2O2 are described. By cathodic reduction of dissolved oxygen and the coupled oxidation of water at a UV-illuminated nanocrystalline-TiO2 semiconductor anode, it was found that the electrochemically generated H2O2 can be employed to readily oxidize the model compound Direct Yellow-52 in dilute acidic solution at high rates in the presence of small quantities of dissolved iron(II). Although, the model organic compound is chemically stable under UV radiation, its electrochemical oxidation rate increases substantially when the semiconductor anode is illuminated as compared to the same processes carried out in the dark.

Illuminating Geochemical Controls of Methane Oxidation Along a Gradient of Permafrost Thaw

NASA Astrophysics Data System (ADS)

Perryman, C. R.; Kashi, N.; McCalley, C. K.; Malhotra, A.; Giesler, R.; Varner, R.

2017-12-01

Increases in annual mean temperature in the subarctic have accelerated the thaw of organic-rich permafrost peatlands, exacerbating methane (CH4) production from microbial decomposition of peat deposits and subsequent CH4 emissions. Methanotrophic bacteria may oxidize/consume upwards of 90% of produced CH4 in some settings, pending substrate availability and environmental conditions. Redox chemistry may also control the rate of CH4 oxidation in thawing permafrost areas, particularly redox potential (Eh) and the availability of oxygen (O2) and other terminal electron receptors. We investigated potential CH4 oxidation rates across a permafrost thaw gradient in Stordalen Mire (68°21'N,18°49'E) near Abisko, Sweden. Methane oxidation rates for sites from thawing and collapsed palsa, semi-wet Sphagnum, and open-water sedge sites were determined through laboratory incubations. Peat cores were extracted from two depths at each site and incubated at in situ temperatures and CH4 concentrations. Headspace samples were collected over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Dissolved O2, Eh, and dissolved CH4 were measured in sites with porewater. Oxidation rates ranged from <0.1 to 19 μg of CH4 per gram of dry biomass per day. Eh remained positive (41.6 to 316.8 mV) with available dissolved O2 (0.3 - 5.2 mg/L) in all measurement locations down to 20cm, indicating in situ aerobic CH4 oxidation is viable across these environments. Potential CH4 oxidation rates increased with increasing dissolved CH4 concentration. Highest potential CH4 oxidation rates were found in open-water sedge sites. Eh and dissolved O2 were lowest at these sites, suggesting that methanotrophs with low-O2 demand may populate sedge areas. Furthermore, potential CH4 oxidation rates were higher at depth than at the surface in thawing palsa, suggesting CH4 oxidation may mitigate CH4 production triggered by warming in these actively thawing environments. Forthcoming elemental analyses of peat and pore water will further elucidate trends and geochemical controls of CH4 oxidation rates in thawing permafrost areas.

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

USGS Publications Warehouse

Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

2007-01-01

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2 O value was then used to estimate the oxygen isotope fractionation effects (??18 OSO42 - s(-) O2) between sulfate and dissolved oxygen in the aerobic experiments which were -10.0???, -10.8???, and -9.8??? for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between ??18OSO4 values in the biological and abiotic experiments, it is suggested that ??18OSO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions. ?? 2007 Elsevier Ltd. All rights reserved.

The interaction of molecular hydrogen with α-radiolytic oxidants on a (U,Pu)O2 surface

NASA Astrophysics Data System (ADS)

Bauhn, Lovisa; Hansson, Niklas; Ekberg, Christian; Fors, Patrik; Delville, Rémi; Spahiu, Kastriot

2018-07-01

In order to assess the impact of α-radiolysis of water on the oxidative dissolution of spent fuel, an un-irradiated, annealed MOX fuel pellet with high content of Pu (∼24 wt%), and a specific α-activity of 4.96 GBq/gMOX, was leached in carbonate-containing solutions of low ionic strength. The high Pu content in the pellet stabilizes the (U,Pu)O2(s) matrix towards oxidative dissolution, whereas the α-decays emitted from the surface are expected to produce ∼3.6 × 10-7 mol H2O2/day, contributing to the oxidative dissolution of the pellet. Two sets of leaching tests were conducted under different redox conditions: Ar gas atmosphere and deuterium gas atmosphere. A relatively slow increase of the U and Pu concentrations was observed in the Ar case, with U concentrations increasing from 1·10-6 M after 1 h to ∼7 × 10-5 M after 58 days. Leaching under an atmosphere starting at 1 MPa deuterium gas was undertaken in order to evaluate any effect of dissolved hydrogen on the radiolytic dissolution of the pellet, as well as to investigate any potential recombination of the α-radiolytic products with dissolved deuterium. For the latter purpose, isotopic analysis of the D/H content was carried out on solution samples taken during the leaching. Despite the continuous production of radiolytic oxidants, the concentrations of U and Pu remained quite constant at the level of ∼3 × 10-8 M during the first 30 days, i.e. as long as the deuterium pressure remained higher than 0.8 MPa. These data rule out any oxidative dissolution of the pellet during the first month. The un-irradiated MOX fuel does not contain metallic ε-particles, hence it is mainly the interaction of radiolytic oxidants and dissolved deuterium with the surface of the mixed actinide oxide that causes the neutralization of the oxidants. This conclusion is supported by the steadily increasing levels of HDO measured in the leachate samples.

Solubility and chemistry of materials encountered by beryllium mine and ore extraction workers: relation to risk.

PubMed

Deubner, David C; Sabey, Philip; Huang, Wenjie; Fernandez, Diego; Rudd, Abigail; Johnson, William P; Storrs, Jason; Larson, Rod

2011-10-01

Beryllium mine and ore extraction mill workers have low rates of beryllium sensitization and chronic beryllium disease relative to the level of beryllium exposure. The objective was to relate these rates to the solubility and composition of the mine and mill materials. Medical surveillance and exposure data were summarized. Dissolution of BeO, ore materials and beryllium hydroxide, Be(OH)(2) was measured in synthetic lung fluid. The ore materials were more soluble than BeO at pH 7.2 and similar at pH 4.5. Be(OH)(2) was more soluble than BeO at both pH. Aluminum dissolved along with beryllium from ore materials. Higher solubility of beryllium ore materials and Be(OH)(2) at pH 7.2 might shorten particle longevity in the lung. The aluminum content of the ore materials might inhibit the cellular immune response to beryllium.

Evaluating the spatial variation of total mercury in young-of-year yellow perch (Perca flavescens), surface water and upland soil for watershed-lake systems within the southern Boreal Shield.

PubMed

Gabriel, Mark C; Kolka, Randy; Wickman, Trent; Nater, Ed; Woodruff, Laurel

2009-06-15

The primary objective of this research is to investigate relationships between mercury in upland soil, lake water and fish tissue and explore the cause for the observed spatial variation of THg in age one yellow perch (Perca flavescens) for ten lakes within the Superior National Forest. Spatial relationships between yellow perch THg tissue concentration and a total of 45 watershed and water chemistry parameters were evaluated for two separate years: 2005 and 2006. Results show agreement with other studies where watershed area, lake water pH, nutrient levels (specifically dissolved NO(3)(-)-N) and dissolved iron are important factors controlling and/or predicting fish THg level. Exceeding all was the strong dependence of yellow perch THg level on soil A-horizon THg and, in particular, soil O-horizon THg concentrations (Spearman rho=0.81). Soil B-horizon THg concentration was significantly correlated (Pearson r=0.75) with lake water THg concentration. Lakes surrounded by a greater percentage of shrub wetlands (peatlands) had higher fish tissue THg levels, thus it is highly possible that these wetlands are main locations for mercury methylation. Stepwise regression was used to develop empirical models for the purpose of predicting the spatial variation in yellow perch THg over the studied region. The 2005 regression model demonstrates it is possible to obtain good prediction (up to 60% variance description) of resident yellow perch THg level using upland soil O-horizon THg as the only independent variable. The 2006 model shows even greater prediction (r(2)=0.73, with an overall 10 ng/g [tissue, wet weight] margin of error), using lake water dissolved iron and watershed area as the only model independent variables. The developed regression models in this study can help with interpreting THg concentrations in low trophic level fish species for untested lakes of the greater Superior National Forest and surrounding Boreal ecosystem.

Quantification of conservative and reactive transport using a single groundwater tracer test in a fractured media

NASA Astrophysics Data System (ADS)

Chatton, Eliot; Labasque, Thierry; Guillou, Aurélie; Béthencourt, Lorine; de La Bernardie, Jérôme; Boisson, Alexandre; Koch, Florian; Aquilina, Luc

2017-04-01

Identification of biogeochemical reactions in aquifers and determining kinetics is important for the prediction of contaminant transport in aquifers and groundwater management. Therefore, experiments accounting for both conservative and reactive transport are essential to understand the biogeochemical reactivity at field scale. This study presents the results of a groundwater tracer test using the combined injection of dissolved conservative and reactive tracers (He, Xe, Ar, Br-, O2 and NO3-) in order to evaluate the transport properties of a fractured media in Brittany, France. Dissolved gas concentrations were continuously monitored in situ with a CF-MIMS (Chatton et al, 2016) allowing a high frequency (1 gas every 2 seconds) multi-tracer analysis (N2, O2, CO2, CH4, N2O, H2, He, Ne, Ar, Kr, Xe) over a large resolution (6 orders of magnitude). Along with dissolved gases, groundwater biogeochemistry was monitored through the sampling of major anions and cations, trace elements and microbiological diversity. The results show breakthrough curves allowing the combined quantification of conservative and reactive transport properties. This ongoing work is an original approach investigating the link between heterogeneity of porous media and biogeochemical reactions at field scale. Eliot Chatton, Thierry Labasque, Jérôme de La Bernardie, Nicolas Guihéneuf, Olivier Bour and Luc Aquilina; Field Continuous Measurement of Dissolved Gases with a CF-MIMS: Applications to the Physics and Biogeochemistry of Groundwater Flow; Environmental Science & Technology, in press, 2016.

Photooxidation and its effects on the carboxyl content of dissolved organic matter in two coastal rivers in the southeastern United States.

PubMed

Xie, Huixiang; Zafiriou, Oliver C; Cai, Wei-Jun; Zepp, Richard G; Wang, Yongchen

2004-08-01

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 --> ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from approximately 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/ regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m.

Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

NASA Astrophysics Data System (ADS)

Roggensack, K.; Allison, C. M.; Clarke, A. B.

2017-12-01

A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that the presence of H2O enhances CO2 solubility at low to moderate H2O abundance. One implication of these results is that volatile-saturated magmas will behave differently depending on H2O abundance. Magmas with low H2O abundance could undergo isobaric degassing through addition of a CO2-rich fluid.

Novel microelectrode-based online system for monitoring N2O gas emissions during wastewater treatment.

PubMed

Marques, Ricardo; Oehmen, Adrian; Pijuan, Maite

2014-11-04

Clark-type nitrous oxide (N2O) microelectrodes are commonly used for measuring dissolved N2O levels, but have not previously been tested for gas-phase applications, where the N2O emitted from wastewater systems can be directly quantified. In this study, N2O microelectrodes were tested and validated for online gas measurements, and assessed with respect to their temperature, gas flow, composition dependence, gas pressure, and humidity. An exponential correlation between temperature and sensor signal was found, whereas gas flow, composition, pressure, and humidity did not have any influence on the signal. Two of the sensors were tested at different N2O concentration ranges (0-422.3, 0-50, 0-10, and 0-2 ppmv N2O) and exhibited a linear response over each range. The N2O emission dynamics from two laboratory scale sequencing batch reactors performing ammonia or nitrite oxidation were also monitored using one of the microsensors and results were compared with two other analytical methods. Results show that N2O emissions were accurately described with these microelectrodes and support their application for assessing gaseous N2O emissions from wastewater treatment systems. Advantages of the sensors as compared to conventional measurement techniques include a wider quantification range of N2O fluxes, and a single measurement system that can assess both liquid and gas-phase N2O dynamics.

Insight into photocatalytic degradation of dissolved organic matter in UVA/TiO₂ systems revealed by fluorescence EEM-PARAFAC.

PubMed

Phong, Diep Dinh; Hur, Jin

2015-12-15

Photocatalytic degradation of dissolved organic matter (DOM) using TiO2 as a catalyst and UVA as a light source was examined under various experimental settings with different TiO2 doses, solution pH, and the light intensities. The changes in UV absorbance and fluorescence with the irradiation time followed a pseudo-first order model much better than those of dissolved organic carbon. In general, the degradation rates were increased by higher TiO2 doses and light intensities. However, the exact photocatalytic responses of DOM to the irradiation were affected by many other factors such as aggregation of TiO2, light scattering, hydroxyl radicals produced, and DOM sorption on TiO2. Fluorescence excitation-emission matrix (EEM) coupled with parallel factor analysis (PARAFAC) revealed that the DOM changes in fluorescence could be described by the combinations of four dissimilar components including one protein-like, two humic-like, and one terrestrial humic-like components, each of which followed well the pseudo-first order model. The photocatalytic degradation rates were higher for protein-like versus humic-like component, whereas the opposite order was displayed for the degradation rates in the absence of TiO2, suggesting different dominant mechanisms operating between the systems with and without TiO2. Our results based on EEM-PARAFAC provided new insights into the underlying mechanisms associated with the photocatalytic degradation of DOM as well as the potential environmental impact of the treated water. This study demonstrated a successful application of EEM-PARAFAC for photocatalytic systems via directly comparing the kinetic rates of the individual DOM components with different compositions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Origin of oxygen in sulfate during pyrite oxidation with water and dissolved oxygen: an in situ horizontal attenuated total reflectance infrared spectroscopy isotope study.

PubMed

Usher, Courtney R; Cleveland, Curtis A; Strongin, Daniel R; Schoonen, Martin A

2004-11-01

FeS2 (pyrite) is known to react with water and dissolved molecular oxygen to form sulfate and iron oxyhydroxides. This process plays a large role in the environmentally damaging phenomenon known as acid mine drainage. An outstanding scientific issue has been whether the oxygen in the sulfate and oxyhydroxide product was derived from water and/or dissolved oxygen. By monitoring the reaction in situ with horizontal attenuated total reflectance infrared spectroscopy, it was found that when using 18O isotopically substituted water, the majority of the infrared absorbance due to sulfate product red-shifted approximately 70 cm(-1) relative to the absorbance of sulfate using H(2)16O as a reactant. Bands corresponding to the iron oxyhydroxide product did not shift. These results indicate water as the primary source of oxygen in the sulfate product, while the oxygen atoms in the iron oxyhydroxide product are obtained from dissolved molecular oxygen.

Effects of increased inspired oxygen concentration on tissue oxygenation: theoretical considerations.

PubMed

Lumb, Andrew B; Nair, Sindhu

2010-03-01

Breathing increased fractional oxygen concentration (FiO2) is recommended for the treatment of tissue ischaemia. The theoretical benefits of increasing FiO2 on tissue oxygenation were evaluated using standard physiological equations. Assuming constant oxygen consumption by tissues throughout the length of a capillary, the oxygen content at 20 arbitrary points along a capillary was calculated. Using mathematical representations of the haemoglobin dissociation curve and an iterative approach to include the dissolved oxygen component of oxygen content, the oxygen partial pressure (PO2) profile along a capillary was estimated. High FiO2 concentrations cause large increases in PO2 at the arteriolar end of capillaries but these large PO2 values, caused by the extra dissolved oxygen, rapidly decline along the capillary. At the venular end of the capillary (the area of tissue most likely to be hypoxic), breathing oxygen causes only a modest improvement in PO2. Increasing FiO2 to treat tissue hypoxia has clear benefits, but a multimodal approach to management is required.

Equilibrator-based measurements of dissolved nitrous oxide in the surface ocean using an integrated cavity output laser absorption spectrometer

NASA Astrophysics Data System (ADS)

Grefe, I.; Kaiser, J.

2014-06-01

Dissolved nitrous oxide (N2O) concentrations are usually determined by gas chromatography (GC). Here we present laboratory tests and initial field measurements using a novel setup comprising a commercially available laser-based analyser for N2O, carbon monoxide and water vapour coupled to a glass-bed equilibrator. This approach is less labour-intensive and provides higher temporal and spatial resolution than the conventional GC technique. The standard deviation of continuous equilibrator or atmospheric air measurements was 0.2 nmol mol-1 (averaged over 5 min). The short-term repeatability for reference gas measurements within 1 h of each other was 0.2 nmol mol-1 or better. Another indicator of the long-term stability of the analyser is the standard deviation of the calibrated N2O mole fraction in marine air, which was between 0.5 and 0.7 nmol mol-1. The equilibrator measurements were compared with purge-and-trap gas chromatography-mass spectrometry (GC-MS) analyses of N2O concentrations in discrete samples from the Southern Ocean and showed agreement to within the 2% measurement uncertainty of the GC-MS method. The equilibrator response time to concentration changes in water was from 142 to 203 s, depending on the headspace flow rate. The system was tested at sea during a north-to-south transect of the Atlantic Ocean. While the subtropical gyres were slightly undersaturated, the equatorial region was a source of nitrous oxide to the atmosphere, confirming previous findings (Forster et al., 2009). The ability to measure at high temporal and spatial resolution revealed submesoscale variability in dissolved N2O concentrations. Mean sea-to-air fluxes in the tropical and subtropical Atlantic ranged between -1.6 and 0.11 μmol m-2 d-1 and confirm that the subtropical Atlantic is not an important source region for N2O to the atmosphere, compared to global average fluxes of 0.6-2.4 μmol m-2 d-1. The system can be easily modified for autonomous operation on voluntary observing ships (VOS). Future work should include an interlaboratory comparison exercise with other methods of dissolved N2O analyses.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

The influence of dissolved oxygen on winter habitat selection by largemouth bass: an integration of field biotelemetry studies and laboratory experiments.

PubMed

Hasler, C T; Suski, C D; Hanson, K C; Cooke, S J; Tufts, B L

2009-01-01

In this study, field biotelemetry and laboratory physiology approaches were coupled to allow understanding of the behavioral and physiological responses of fish to winter hypoxia. The biotelemetry study compared dissolved oxygen levels measured throughout the winter period with continually tracked locations of nine adult largemouth bass obtained from a whole-lake submerged telemetry array. Fish habitat usage was compared with habitat availability to assess whether fish were selecting for specific dissolved oxygen concentrations. The laboratory study examined behavioral and physiological responses to progressive hypoxia in juvenile largemouth bass acclimated to winter temperatures. Results from the dissolved oxygen measurements made during the biotelemetry study showed high variance in under-ice dissolved oxygen levels. Avoidance of water with dissolved oxygen <2.0 mg/L by telemetered fish was demonstrated, but significant use of water with intermediate dissolved oxygen levels was also found. Results from the lab experiments showed marked changes in behavior (i.e., yawning and vertical movement) at <2.0 mg/L of dissolved oxygen but no change in tissue lactate, an indicator of anaerobic metabolism. Combined results of the biotelemetry and laboratory studies demonstrate that a dissolved oxygen content of 2.0 mg/L may be a critical threshold that induces behavioral responses by largemouth bass during the winter. In addition, the use by fish of areas with intermediate levels of dissolved oxygen suggests that there are multiple environmental factors influencing winter behavior.

CHARACTERIZATION OF TANK 16H ANNULUS SAMPLES PART II: LEACHING RESULTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, M.; Reboul, S.

2012-06-19

The closure of Tank 16H will require removal of material from the annulus of the tank. Samples from Tank 16H annulus were characterized and tested to provide information to evaluate various alternatives for removing the annulus waste. The analysis found all four annulus samples to be composed mainly of Si, Na, and Al and lesser amounts of other elements. The XRD data indicate quartz (SiO{sub 2}) and sodium aluminum nitrate silicate hydrate (Na{sub 8}(Al{sub 6}Si{sub 6}O{sub 24})(NO{sub 3}){sub 2}.4H{sub 2}O) as the predominant crystalline mineral phases in the samples. The XRD data also indicate the presence of crystalline sodium nitratemore » (NaNO{sub 3}), sodium nitrite (NaNO{sub 2}), gibbsite (Al(OH){sub 3}), hydrated sodium bicarbonate (Na{sub 3}H(CO{sub 3}){sub 2}.2H{sub 2}O), and muscovite (KAl{sub 2}(AlSi{sub 3}O{sub 10})(OH){sub 2}). Based on the weight of solids remaining at the end of the test, the water leaching test results indicate 20-35% of the solids dissolved after three contacts with an approximately 3:1 volume of water at 45 C. The chemical analysis of the leachates and the XRD results of the remaining solids indicate sodium salts of nitrate, nitrite, sulfate, and possibly carbonate/bicarbonate make up the majority of the dissolved material. The majority of these salts were dissolved in the first water contact and simply diluted with each subsequent water contact. The water leaching removed large amounts of the uranium in two of the samples and approximately 1/3 of the {sup 99}Tc from all four samples. Most of the other radionuclides analyzed showed low solubility in the water leaching test. The oxalic acid leaching test result indicate approximately 34-47% of the solids in the four annulus samples will dissolve after three contacts with an approximately 3:1 volume of acid to solids at 45 C. The same sodium salts found in the water leaching test comprise the majority of dissolved material in the oxalic acid leaching test. However, the oxalic acid was somewhat more effective in dissolving radionuclides than the water leach. In contrast to the water leaching results, most constituents continued to dissolve during subsequent cycles of oxalic acid leaching. The somewhat higher dissolution found in the oxalic acid leaching test versus the water leaching test might be offset by the tendency of the oxalic acid solutions to take on a gel-like consistency. The filtered solids left behind after three oxalic acid contacts were sticky and formed large clumps after drying. These two observations could indicate potential processing difficulties with solutions and solids from oxalic acid leaching. The gel formation might be avoided by using larger volumes of the acid. Further testing would be recommended before using oxalic acid to dissolve the Tank 16H annulus waste to ensure no processing difficulties are encountered in the full scale process.« less

The role of hemoglobin oxygen affinity in oxygen transport at high altitude.

PubMed

Winslow, Robert M

2007-09-30

Hemoglobin is involved in the regulation of O(2) transport in two ways: a long-term adjustment in red cell mass is mediated by erythropoietin (EPO), a response to renal oxgyenation. Short-term, rapid-response adjustments are mediated by ventilation, cardiac output, hemoglobin oxygen affinity (P50), barriers to O(2) diffusion, and the control of local microvascular tissue perfusion. The distribution of O(2) between dissolved (PO2) and hemoglobin-bound (saturation) is the familiar oxygen equilibrium curve, whose position is noted as P50. Human hemoglobin is not genetically adapted for function at high altitude. However, more specialized species native to high altitudes (guinea pig and bar-headed goose, for example) seem to have a lower P50 than their sea level counterparts, an adaptation that presumably promotes O(2) uptake from a hypoxic environment. Humans, native to very high altitude either in the Andes or Himalayan mountains, also can increase O(2) affinity, not because of a fundamental difference in hemoglobin structure or function, but because of extreme hyperventilation and alkalosis.

A comparison of genotoxicity change in reclaimed wastewater from different disinfection processes.

PubMed

Chai, Qiwan; Hu, Allen; Qian, Yukun; Ao, Xiuwei; Liu, Wenjun; Yang, Hongwei; Xie, Yuefeng F

2018-01-01

Effluents before disinfection from four wastewater reclamation plants were treated with chlorine (Cl 2 ), ozone (O 3 ), chlorine dioxide (ClO 2 ), medium-pressure ultraviolet (MPUV) and four different combinations of the above, to evaluate the effect of disinfection processes on the genotoxicity removal by the SOS/umu test. Results showed that the genotoxicity increased after MPUV irradiation (10-100 mJ/cm 2 ), but declined when adopting other disinfection processes. The effectiveness of genotoxicity reduction by five chemical disinfectants was identified as: O 3  > pre-ozonation with Cl 2  ≈ ClO 2  > combination of ClO 2 and Cl 2  > Cl 2 . The sequential combination of MPUV, Cl 2 and O 3 reduced the genotoxicity to a level similar to the source water. The influence of differential disinfection process varied on iodinated wastewater, which is closely related to the competitive reactions between disinfectants, iodine and dissolved organic matters. The removal of genotoxic pollutants and the formation of genotoxic disinfection by-products are the two major factors that lead to the change in genotoxicity during disinfection. Copyright © 2017 Elsevier Ltd. All rights reserved.

Consequences of land use cover change and precipitation regimes on water quality in a tropical landscape: the case of São Paulo, Brazil

NASA Astrophysics Data System (ADS)

Ribeiro Piffer, P.; Reverberi Tambosi, L.; Uriarte, M.

2017-12-01

One of the most pressing challenges faced by modern societies is ensuring a sufficient supply of water considering the ever-growing conflict between environmental conservation and expansion of agricultural and urban frontiers worldwide. Land use cover change have marked effects on natural landscapes, putting key watershed ecosystem services in jeopardy. We investigated the consequences of land use cover change and precipitation regimes on water quality in the state of São Paulo, Brazil, a landscape that underwent major changes in past century. Water quality data collected bi-monthly between 2000 and 2014 from 229 water monitoring stations was analyzed together with 2011 land use cover maps. We focused on six water quality metrics (dissolved oxygen, total nitrogen, total phosphorus, turbidity, total dissolved solids and fecal coliforms) and used generalized linear mixed models to analyze the data. Models were built at two scales, the entire watershed and a 60 meters riparian buffer along the river network. Models accounted for 46-67% of the variance in water quality metrics and, apart from dissolved oxygen, which reflected land cover composition in riparian buffers, all metrics responded to land use at the watershed scale. Highly urbanized areas had low dissolved oxygen and high fecal coliforms, dissolved solids, phosphorus and nitrogen levels in streams. Pasture was associated with increases in turbidity, while sugarcane plantations significantly increased nitrogen concentrations. Watersheds with high forest cover had greater dissolved oxygen and lower turbidity. Silviculture plantations had little impact on water quality. Precipitation decreased dissolved oxygen and was associated with higher levels of turbidity, fecal coliforms and phosphorus. Results indicate that conversion of forest cover to other land uses had negative impacts on water quality in the study area, highlighting the need for landscape restoration to improve watersheds ecosystem services.

Riverine N2O concentrations, exports to estuary and emissions to atmosphere from the Changjiang River in response to increasing nitrogen loads

NASA Astrophysics Data System (ADS)

Yan, Weijin; Yang, Libiao; Wang, Fang; Wang, Jianing; Ma, Pei

2012-12-01

This study investigated the variations of dissolved N2O and emissions over diurnal and seasonal temporal scales in 2009, as well as the time series of riverine N2O export to estuary and emission to atmosphere in response to increasing anthropogenic nitrogen loads in the Changjiang River. For the diurnal study, N2O concentrations ranged from 0.26 to 0.34 and from 0.44 to 0.52 μg N-N2O L-1 in August and October 2009, respectively. The dissolved N2O was supersaturated with a mean value of 197%. Studies on N2O emissions, also taken in August and October, ranged from 2.67 to 11.6 and from 6.72 to 15.2 μg N-N2O m-2 h-1, respectively. For the seasonal study (June through December 2009), N2O concentrations ranged from 0.34 to 0.72 μg N-N2O L-1 and were supersaturated in all the samples (average 212%). N2O emissions ranged from 1.87 to 40.8 μg N-N2O m-2 h-1. Our study found no significant differences in diurnal patterns of N2O saturation but detected significant difference in seasonal patterns of N2O saturation: higher during summer while lower during autumn and winter. We found a significant relationship between dissolved N2O and river nitrate, which can predict the variation of N2O concentrations in the River. The net production of N2 ranged from 0.01 to 0.47 mg N-N2 L-1. These excess N2 values were significantly correlated to the N2O production and are suggestive of denitrification in the river. Applying the Global News model to the river system using measures taken during the 1970 to 2002 period, we estimated N2O emissions to atmosphere increased from 330 to 3650 ton N-N2O yr-1. During that same 1970-2002 period, N2O exports to estuary increased from 91 to 470 ton N-N2O yr-1. Taken together, the findings reported here suggest that both the river N2O concentrations and emissions would increase in response to rising anthropogenic nitrogen loads. Our study showed that the mean emission factor based on the ratio of the total N2O flux to NO3- flux is four times greater than the value of 0.0025 obtained with the methodology recommended by the Intergovernmental Panel on Climate Change. Thus, our findings reflect the open river channel rapid exchange of gases with the atmosphere.

Proper interpretation of dissolved nitrous oxide isotopes, production pathways, and emissions requires a modelling approach.

PubMed

Thuss, Simon J; Venkiteswaran, Jason J; Schiff, Sherry L

2014-01-01

Stable isotopes ([Formula: see text]15N and [Formula: see text]18O) of the greenhouse gas N2O provide information about the sources and processes leading to N2O production and emission from aquatic ecosystems to the atmosphere. In turn, this describes the fate of nitrogen in the aquatic environment since N2O is an obligate intermediate of denitrification and can be a by-product of nitrification. However, due to exchange with the atmosphere, the [Formula: see text] values at typical concentrations in aquatic ecosystems differ significantly from both the source of N2O and the N2O emitted to the atmosphere. A dynamic model, SIDNO, was developed to explore the relationship between the isotopic ratios of N2O, N2O source, and the emitted N2O. If the N2O production rate or isotopic ratios vary, then the N2O concentration and isotopic ratios may vary or be constant, not necessarily concomitantly, depending on the synchronicity of production rate and source isotopic ratios. Thus prima facie interpretation of patterns in dissolved N2O concentrations and isotopic ratios is difficult. The dynamic model may be used to correctly interpret diel field data and allows for the estimation of the gas exchange coefficient, N2O production rate, and the production-weighted [Formula: see text] values of the N2O source in aquatic ecosystems. Combining field data with these modelling efforts allows this critical piece of nitrogen cycling and N2O flux to the atmosphere to be assessed.

Analysis of engineered nanomaterials in the environment

NASA Astrophysics Data System (ADS)

Reed, Robert Bruce

With increasing incorporation of engineered nanoparticles (NPs) into consumer products, there is concern that these materials will be released to the environment with unknown ecological effects. Methods for detection and characterization of these materials at environmentally relevant concentrations are crucial to understanding this potential risk. A relatively new method, single particle inductively coupled plasma mass spectrometry (spICPMS), was applied to analysis of metal oxide NPs such as ZnO, CeO2, and TiO2, as well as silver nanowires and carbon nanotubes. A lack of nanoparticulate "pulses" in spICPMS analysis of nano-ZnO led to a study on ZnO NP solubility in a variety of matrices. Dissolution of nano-ZnO was observed in nanopure water (7.18 - 7.40 mg/L dissolved Zn, as measured by filtration) and Roswell Park Memorial Institute medium (RPMI-1640) (~5 mg/L), but much more dissolution was observed in Dulbecco's Modified Eagle's Medium (DMEM), where the dissolved Zn concentration exceeded 34 mg/L. These results suggest that solution chemistry exerts a strong influence on ZnO NP dissolution and can result in limits on zinc solubility due to precipitation of less soluble solid phases. Detection and sizing of metal-containing NPs was achieved at concentrations predicted for environmental samples (part-per trillion levels) using spICPMS. Sizing of silver nanowires, titanium dioxide and cerium oxide NPs was done by correlating ICP-MS response (pulses) from NPs entering the plasma to mass of metal in dissolved standards. The ratio of NP pulse detections to the total number of readings during analysis was optimized at 2.5% or less to minimize coincident pulses while still allowing definition of a size distribution. Detection of single walled carbon nanotubes (CNTs) was performed using spICPMS. This study focuses on using trace catalytic metal nanoparticles intercalated in the CNT structure as proxies for the nanotubes. The small, variable, amount of trace metal in each CNT makes separation from instrumental background challenging, and multiple approaches to this problem were attempted. To highlight the potential of spICPMS in environmental studies the release of CNTs from polymer nanocomposites into solution was monitored, showcasing the technique's ability to detect changes in released CNT concentrations as a function of CNT loading.

Obtaining accurate amounts of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1987-01-01

A process for obtaining pre-determined, accurate rate amounts of mercury. In one embodiment, predetermined, precise amounts of Hg are separated from HgO and plated onto a cathode wire. The method for doing this involves dissolving a precise amount of HgO which corresponds to a pre-determined amount of Hg desired in an electrolyte solution comprised of glacial acetic acid and H.sub.2 O. The mercuric ions are then electrolytically reduced and plated onto a cathode producing the required pre-determined quantity of Hg. In another embodiment, pre-determined, precise amounts of Hg are obtained from Hg.sub.2 Cl.sub.2. The method for doing this involves dissolving a precise amount of Hg.sub.2 Cl.sub.2 in an electrolyte solution comprised of concentrated HCl and H.sub.2 O. The mercurous ions in solution are then electrolytically reduced and plated onto a cathode wire producing the required, pre-determined quantity of Hg.

Obtaining accurate amounts of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1987-07-07

A process is described for obtaining pre-determined, accurate rate amounts of mercury. In one embodiment, predetermined, precise amounts of Hg are separated from HgO and plated onto a cathode wire. The method for doing this involves dissolving a precise amount of HgO which corresponds to a pre-determined amount of Hg desired in an electrolyte solution comprised of glacial acetic acid and H[sub 2]O. The mercuric ions are then electrolytically reduced and plated onto a cathode producing the required pre-determined quantity of Hg. In another embodiment, pre-determined, precise amounts of Hg are obtained from Hg[sub 2]Cl[sub 2]. The method for doing this involves dissolving a precise amount of Hg[sub 2]Cl[sub 2] in an electrolyte solution comprised of concentrated HCl and H[sub 2]O. The mercurous ions in solution are then electrolytically reduced and plated onto a cathode wire producing the required, pre-determined quantity of Hg. 1 fig.

Visible-light sensitization of TiO2 photocatalysts via wet chemical N-doping for the degradation of dissolved organic compounds in wastewater treatment: a review

NASA Astrophysics Data System (ADS)

Zhang, Wei; Jia, Baoping; Wang, Qiuze; Dionysiou, Dionysois

2015-05-01

Increased pollution of ground and surface water and emerging new micropollutants from a wide variety of industrial, municipal, and agricultural sources has increased demand on the development of innovative new technologies and materials whereby challenges associated with the provision of safe potable water can be addressed. Heterogeneous photocatalysis using visible-light sensitized TiO2 photocatalysts has attracted a lot of attention as it can effectively remove dissolved organic compound in water without generating harmful by-products. On this note, recent progress on visible-light sensitive TiO2 synthesis via wet chemical N-doping method is reviewed. In a typical visible-light sensitive TiO2 preparation via wet chemical methods, the chemical (e.g., N-doping content and states) and morphological properties (e.g., particle size, surface area, and crystal phase) of TiO2 in as-prepared resultants are sensitively dependent on many experimental variables during the synthesis. This has also made it very difficult to provide a universal guidance at this stage with a certainty for each variable of N-doping preparation. Instead of one-factor-at-a-time style investigation, a statistically valid parameter optimization investigation for general optima of photocatalytic activity will be certainly useful. Optimization of the preparation technique is envisaged to be beneficial to many environmental applications, i.e., dissolved organic compounds removal in wastewater treatment.

Effect of dissolved ozone or ferric ions on photodegradation of thiacloprid in presence of different TiO2 catalysts.

PubMed

Cernigoj, Urh; Stangar, Urska Lavrencic; Jirkovský, Jaromír

2010-05-15

Combining TiO(2) photocatalysis with inorganic oxidants (such as O(3) and H(2)O(2)) or transition metal ions (Fe(3+), Cu(2+) and Ag(+)) often leads to a synergic effect. Electron transfer between TiO(2) and the oxidant is usually involved. Accordingly, the degree of synergy could be influenced by TiO(2) surface area. With this in mind, the disappearance of thiacloprid, a neonicotinoid insecticide, was studied applying various photochemical AOPs and different TiO(2) photocatalysts. In photocatalytic ozonation experiments, synergic effect of three different TiO(2) photocatalysts was quantified. Higher surface area resulted in a more pronounced synergic effect but an increasing amount of TiO(2) did not influence the degree of the synergy. This supports the theory that the synergy is a consequence of adsorption of ozone on the TiO(2) surface. No synergy was observed in photocatalytic degradation of thiacloprid in the presence of dissolved iron(III) species performed under varied experimental conditions (concentration, age of iron(III) solution, different TiO(2) films, usage of TiO(2) slurries). This goes against the literature for different organic compounds (i.e., monuron). It indicates different roles of iron(III) in the photodegradation of different organic molecules. Moreover, TiO(2) surface area did not affect photodegradation efficiency in iron(III)-based experiments which could confirm absence of electron transfer between TiO(2) photocatalyst and iron(III). Copyright (c) 2009 Elsevier B.V. All rights reserved.

In vitro genotoxicity of asbestos substitutes induced by coupled stimulation of dissolved high-valence ions and oxide radicals.

PubMed

Huo, Tingting; Dong, Faqin; Deng, Jianjun; Zhang, Qingbi; Ye, Wei; Zhang, Wei; Wang, Pingping; Sun, Dongping

2017-08-01

The wide use of asbestos and its substitutes has given rise to studies on their possible harmful effects on human health and environment. However, their toxic effects remain unclear. The present study was aimed to disclose the coupled effects of dissolved high-valence ions and oxide radicals using the in vitro cytotoxicity and genotoxicity of chrysotile (CA), nano-SiO 2 (NS), ceramic fiber (CF), glass fiber (GF), and rock wool (RW) on Chinese hamster lung cells V79. All samples induced cell mortality correlated well with the chemical SiO 2 content of asbestos substitutes and the amount of dissolved Si. Alkali or alkaline earth metal elements relieved mortality of V79 cells; Al 2 O 3 reinforced toxicity of materials. Asbestos substitutes generated lasting, increasing amount of acellular ·OH which formed at the fiber surface at sites with loose/unsaturated bonds, as well as by catalytic reaction through dissolved iron. Accumulated mechanical and radical stimulation induced the intracellular reactive oxygen species (ROS) elevation, morphology change, and deviating trans-membrane ion flux. The cellular ROS appeared as NS > GF > CF ≈ CA > RW, consistent with cell mortality rather than with acellular ·OH generation. Chromosomal and DNA lesions in V79 cells were not directly associated with the cellular ROS, while influenced by dissolved high-valence irons in the co-culture medium. In conclusion, ions from short-time dissolution of dust samples and the generation of extracellular ·OH presented combined effects in the elevation of intracellular ROS, which further synergistically induced cytotoxicity and genotoxicity.

Nuclear-powered pacemaker fuel cladding study. [Difficulty of dissolving cladding and /sup 238/PuO/sub 2/ for obtaining materials for acts of terrorism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shoup, R.L.

1976-07-01

The fabrication of fuel capsules with refractory metal and alloy clads used in nuclear-powered cardiac pacemakers precludes the expedient dissolution of the clad in inorganic acid solutions. An experiment to measure penetration rates of acids on commonly used fuel pellet clads indicated that it is not impossible, but that it would be very difficult to dissolve the multiple cladding. This work was performed because of a suggestion that a /sup 238/PuO/sub 2/-powered pacemaker could be transformed into a terrorism weapon.

Ecosystem Metabolism and Air-Water Fluxes of Greenhouse Gases in High Arctic Wetland Ponds

NASA Astrophysics Data System (ADS)

Lehnherr, I.; Venkiteswaran, J.; St. Louis, V. L.; Emmerton, C.; Schiff, S. L.

2012-12-01

Freshwater lakes and wetlands can be very productive systems on the Arctic landscape compared to terrestrial tundra ecosystems and provide valuable resources to many organisms, including waterfowl, fish and humans. Rates of ecosystem productivity dictate how much energy flows through food webs, impacting the abundance of higher-level organisms (e.g., fish), as well as the net carbon balance, which determines whether a particular ecosystem is a source or sink of carbon. Climate change is predicted to result in warmer temperatures, increased precipitation and permafrost melting in the Arctic and is already altering northern ecosystems at unprecedented rates; however, it is not known how freshwater systems are responding to these changes. To predict how freshwater systems will respond to complex environmental changes, it is necessary to understand the key processes, such as primary production and ecosystem respiration, that are driving these systems. We sampled wetland ponds (n=8) and lakes (n=2) on northern Ellesmere Island (81° N, Nunavut, Canada) during the open water season for a suite of biogeochemical parameters, including concentrations of dissolved gases (O2, CO2, CH4, N2O) as well as stable-isotope ratios of dissolved inorganic carbon (δ13C-DIC), dissolved oxygen (δ18O-DO), and water (δ18O-H2O). We will present rates of primary production and ecosystem respiration, modeled from the concentration and stable isotope ratios of DIC and DO, as well as air-water gas exchange of greenhouse gases in these high Arctic ponds and lakes. Preliminary results demonstrate that ecosystem metabolism in these ponds was high enough to result in significant deviations in the isotope ratios of DIC and DO from atmospheric equilibrium conditions. In other words ecosystem rates of primary production and respiration were faster than gas exchange even in these small, shallow, well-mixed ponds. Furthermore, primary production was elevated enough at all sites except Lake Hazen, a large cold ultra-oligotrophic lake, to result in a shift in the δ18O of DO towards more depleted values. Two of the ponds also exhibited enriched δ13C-DIC indicative of high rates of DIC uptake and primary production. However most sites appear to be net heterotrophic systems, with the exception of a few net autotrophic ponds. Interestingly, due to the high DIC concentrations in pond waters, δ13C-DIC values are reflective of ecosystem metabolism on a somewhat longer time scale than δ18O-DO values, which might be useful for examining temporal changes in production and respiration. Finally, most ponds were sources of both CO2 and CH4 to the atmosphere, but were surprisingly under-saturated with respect to N2O, demonstrating that they are sinks for atmospheric N2O. Rates of N2O consumption (denitrification) were modeled from concentration-time data and ranged from <0.1 to 1.1 nmol L-1 h-1.

Estimates of atmospheric O2 in the Paleoproterozoic from paleosols

NASA Astrophysics Data System (ADS)

Kanzaki, Yoshiki; Murakami, Takashi

2016-02-01

A weathering model was developed to constrain the partial pressure of atmospheric O2 (PO2) in the Paleoproterozoic from the Fe records in paleosols. The model describes the Fe behavior in a weathering profile by dissolution/precipitation of Fe-bearing minerals, oxidation of dissolved Fe(II) to Fe(III) by oxygen and transport of dissolved Fe by water flow, in steady state. The model calculates the ratio of the precipitated Fe(III)-(oxyhydr)oxides from the dissolved Fe(II) to the dissolved Fe(II) during weathering (ϕ), as a function of PO2 . An advanced kinetic expression for Fe(II) oxidation by O2 was introduced into the model from the literature to calculate accurate ϕ-PO2 relationships. The model's validity is supported by the consistency of the calculated ϕ-PO2 relationships with those in the literature. The model can calculate PO2 for a given paleosol, once a ϕ value and values of the other parameters relevant to weathering, namely, pH of porewater, partial pressure of carbon dioxide (PCO2), water flow, temperature and O2 diffusion into soil, are obtained for the paleosol. The above weathering-relevant parameters were scrutinized for individual Paleoproterozoic paleosols. The values of ϕ, temperature, pH and PCO2 were obtained from the literature on the Paleoproterozoic paleosols. The parameter value of water flow was constrained for each paleosol from the mass balance of Si between water and rock phases and the relationships between water saturation ratio and hydraulic conductivity. The parameter value of O2 diffusion into soil was calculated for each paleosol based on the equation for soil O2 concentration with the O2 transport parameters in the literature. Then, we conducted comprehensive PO2 calculations for individual Paleoproterozoic paleosols which reflect all uncertainties in the weathering-relevant parameters. Consequently, robust estimates of PO2 in the Paleoproterozoic were obtained: 10-7.1-10-5.4 atm at ∼2.46 Ga, 10-5.0-10-2.5 atm at ∼2.15 Ga, 10-5.2-10-1.7 atm at ∼2.08 Ga and more than 10-4.6-10-2.0 atm at ∼1.85 Ga. Comparison of the present PO2 estimates to those in the literature suggests that a drastic rise of oxygen would not have occurred at ∼2.4 Ga, supporting a slightly rapid rise of oxygen at ∼2.4 Ga and a gradual rise of oxygen in the Paleoproterozoic in long term.

PHOTOGENERATION OF SINGLET OXYGEN AND FREE RADICALS IN DISSOLVED ORGANIC MATTER ISOLATED FROM THE MISSISSIPPI AND ATCHAFALAYA RIVER PLUMES

EPA Science Inventory

The photoreactivity to UV light of ultrafiltered dissolved organic matter (DOM) collected during cruises along salinity transects in the Mississippi and Atchafalaya River plumes was examined by measuring photogenerated free radicals and singlet molecular oxygen (1O2) photosensiti...

A robust and reliable optical trace oxygen sensor

NASA Astrophysics Data System (ADS)

McDowell, G. R.; Holmes-Smith, A. S.; Uttamlal, M.; Mitchell, C.; Shannon, P. H.

2017-05-01

In applications of nitrogen (N2) generation, industrial gas manufacturing and food packaging there is a need to ensure oxygen (O2) is absent from the environment, even at the lowest concentration levels. Therefore, there has been an increased growth in the development of trace O2 parts per million (ppm) sensors over the past decade to detect and quantify the concentration of molecular O2 in the environment whether it be dissolved or gaseous O2. The majority of commercially available trace O2 sensors are based on electrochemical, zirconia and paramagnetic technologies. Here, the development of a luminescence-based optical trace O2 sensor is presented. Luminescence-based sensing is now regarded as one of the best techniques for the detection and quantification of O2. This is due to the high detection sensitivity, no O2 is consumed and there are a vast array of luminescent indicators and sensing platforms (polymers) that can be selected to suit the desired application. The sensor will be shown to operate from -30 °C to +60 °C in the 0-1000 ppm and/or 0-1200 μbar partial pressure of oxygen (ppO2) range and is equipped with temperature and pressure compensation. The luminescence non-depleting principle, sensor specifications and miniaturized nature offers an attractive alternative to other sensing technologies and advantages over other luminescence-based O2 ppm sensors.

Hopewell Beneficial CO2 Capture for Production of Fuels, Fertilizer and Energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

UOP; Honeywell Resins & Chemicals; Honeywell Process Solutions

2010-09-30

For Phase 1 of this project, the Hopewell team developed a detailed design for the Small Scale Pilot-Scale Algal CO2 Sequestration System. This pilot consisted of six (6) x 135 gallon cultivation tanks including systems for CO2 delivery and control, algal cultivation, and algal harvesting. A feed tank supplied Hopewell wastewater to the tanks and a receiver tank collected the effluent from the algal cultivation system. The effect of environmental parameters and nutrient loading on CO2 uptake and sequestration into biomass were determined. Additionally the cost of capturing CO2 from an industrial stack emission at both pilot and full-scale wasmore » determined. The engineering estimate evaluated Amine Guard technology for capture of pure CO2 and direct stack gas capture and compression. The study concluded that Amine Guard technology has lower lifecycle cost at commercial scale, although the cost of direct stack gas capture is lower at the pilot scale. Experiments conducted under high concentrations of dissolved CO2 did not demonstrate enhanced algae growth rate. This result suggests that the dissolved CO2 concentration at neutral pH was already above the limiting value. Even though dissolved CO2 did not show a positive effect on biomass growth, controlling its value at a constant set-point during daylight hours can be beneficial in an algae cultivation stage with high algae biomass concentration to maximize the rate of CO2 uptake. The limited enhancement of algal growth by CO2 addition to Hopewell wastewater was due at least in part to the high endogenous CO2 evolution from bacterial degradation of dissolved organic carbon present at high levels in the wastewater. It was found that the high level of bacterial activity was somewhat inhibitory to algal growth in the Hopewell wastewater. The project demonstrated that the Honeywell automation and control system, in combination with the accuracy of the online pH, dissolved O2, dissolved CO2, turbidity, Chlorophyll A and conductivity sensors is suitable for process control of algae cultivation in an open pond systems. This project concluded that the Hopewell wastewater is very suitable for algal cultivation but the potential for significant CO2 sequestration from the plant stack gas emissions was minimal due to the high endogenous CO2 generation in the wastewater from the organic wastewater content. Algae cultivation was found to be promising, however, for nitrogen remediation in the Hopewell wastewater.« less

Aerosolized ZnO nanoparticles induce toxicity in alveolar type II epithelial cells at the air-liquid interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Yumei; Williams, Nolann G.; Tolic, Ana

The majority of in vitro studies characterizing the impact of engineered nanoparticles (NPs) on cells that line the respiratory tract were conducted in cells exposed to NPs in suspension. This approach introduces processes that are unlikely to occur during inhaled NP exposures in vivo, such as the shedding of toxic doses of dissolved ions. ZnO NPs are used extensively and pose significant sources for human exposure. Exposures to airborne ZnO NPs can induce adverse effects, but the relevance of the dissolved Zn2+ to the observed effects in vivo is still unclear. Our goal was to mimic in vivo exposures tomore » airborne NPs and decipher the contribution of the intact NP from the contribution of the dissolved ions to airborne ZnO NP toxicity. We established the exposure of alveolar type II epithelial cells to aerosolized NPs at the air-liquid interface (ALI), and compared the impact of aerosolized ZnO NPs and NPs in suspension at the same cellular doses, measured as the number of particles per cell. By evaluating membrane integrity and cell viability 6 and 24 hours post exposure we found that aerosolized NPs induced toxicity at the ALI at doses that were in the same order of magnitude as doses required to induce toxicity in submersed cultures. In addition, distinct patterns of oxidative stress were observed in the two exposure systems. These observations unravel the ability of airborne ZnO NPs to induce toxicity without the contribution of dissolved Zn2+ and suggest distinct mechanisms at the ALI and in submersed cultures.« less

Atmospheric deposition and ozone levels in Swiss forests: are critical values exceeded?

PubMed

Waldner, Peter; Schaub, Marcus; Graf Pannatier, Elisabeth; Schmitt, Maria; Thimonier, Anne; Walthert, Lorenz

2007-05-01

Air pollution affects forest health through atmospheric deposition of acidic and nitrogen compounds and elevated levels of tropospheric ozone (O3). In 1985, a monitoring network was established across Europe and various research efforts have since been undertaken to define critical values. We measured atmospheric deposition of acidity and nitrogen as well as ambient levels of O3 on 12, 13, and 14 plots, respectively, in the framework of the Swiss Long-Term Forest Ecosystem Research (LWF) in the period from 1995 to 2002. We estimated the critical loads of acidity and of nitrogen, using the steady state mass balance approach, and calculated the critical O3 levels using the AOT40 approach. The deposition of acidity exceeded the critical loads on 2 plots and almost reached them on 4 plots. The median of the measured molar ratio of base nutrient cations to total dissolved aluminium (Bc/Al) in the soil solution was higher than the critical value of 1 for all depths, and also at the plots with an exceedance of the critical load of acidity. For nitrogen, critical loads were exceeded on 8 plots and deposition likely represents a long-term ecological risk on 3 to 10 plots. For O3, exceedance of critical levels was recorded on 12 plots, and led to the development of typical O3-induced visible injury on trees and shrubs, but not for all plots due to (1) the site specific composition of O3 sensitive and tolerant plant species, and (2) the influence of microclimatic site conditions on the stomatal behaviour, i.e., O3 uptake.

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study.

PubMed

Liang, Chenju; Lee, I-Ling

2008-09-10

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.

Nitrous oxide production and mRNA expression analysis of nitrifying and denitrifying bacterial genes under floodwater disappearance and fertilizer application.

PubMed

Riya, Shohei; Takeuchi, Yuki; Zhou, Sheng; Terada, Akihiko; Hosomi, Masaaki

2017-06-01

A pulse of nitrous oxide (N 2 O) emission has been observed following the disappearance of floodwater by drainage. However, its mechanism is not well understood. We conducted a column study to clarify the mechanism for N 2 O production during floodwater disappearance by using a microsensor and determining the bacterial gene expression. An increase in N 2 O flux was observed following floodwater disappearance after the addition of NH 4 + , with a corresponding increase in the concentrations of NO 3 - and dissolved N 2 O in the oxic and anoxic soil layers, respectively. The transcription level of the bacterial amoA mRNA did not change, while that of nirK mRNA increased sharply after an hour of floodwater disappearance. An additional anoxic soil slurry experiment demonstrated that the addition of NO 3 - induced the expression of nirK gene and caused a concomitant increase in N 2 O production. These findings suggest that NO 3 - production in the oxic layers is important as it provides a substrate and induces the synthesis of denitrification enzymes in the anoxic layer during N 2 O production.

Silicate Carbonation in Supercritical CO2 Containing Dissolved H2O: An in situ High Pressure X-Ray Diffraction Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaef, Herbert T.; Miller, Quin RS; Thompson, Christopher J.

2013-06-30

Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring between supercritical CO2 containing water and the silicate minerals forsterite (Mg2SiO4), wollastonite (CaSiO3), and enstatite (MgSiO3). This study utilizes newly developed in situ high pressure x-ray diffraction (HXRD) and in situ infra red (IR) to examine mineralmore » transformation reactions. Forsterite and enstatite were selected as they are important minerals present in igneous and mafic rocks and have been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Wollastonite, classified as a pyroxenoid (similar to a pyroxene), was chosen as a suitably fast reacting proxy for examining silicate carbonation processes associated with a wet scCO2 fluid as related to geologic carbon sequestration. The experiments were conducted under modest pressures (90 to 160 bar), temperatures between 35° to 70° C, and varying concentrations of dissolved water. Under these conditions scCO2 contains up to 3,500 ppm dissolved water.« less

Sustainable oil and grease removal from synthetic stormwater runoff using bench-scale bioretention studies.

PubMed

Hong, Eunyoung; Seagren, Eric A; Davis, Allen P

2006-02-01

One of the principal components of the contaminant load in urban stormwater runoff is oil and grease (O&G) pollution, resulting from vehicle emissions. A mulch layer was used as a contaminant trap to remove O&G (dissolved and particulate-associated naphthalene, dissolved toluene, and dissolved motor oil hydrocarbons) from a synthetic runoff during a bench-scale infiltration study. Approximately 80 to 95% removal of all contaminants from synthetic runoff was found via sorption and filtration. Subsequently, approximately 90% of the sorbed naphthalene, toluene, oil, and particulate-associated naphthalene was biodegraded within approximately 3, 4, 8, and 2 days after the event, respectively, based on decreases in contaminant concentrations coupled with increases of microbial populations. These results indicate the effectiveness and sustainability of placing a thin layer of mulch on the surface of a bioretention facility for reducing O&G pollution from urban stormwater runoff.

Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer

USGS Publications Warehouse

Brown, C.J.; Schoonen, M.A.A.; Candela, J.L.

2000-01-01

Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO4/2- in the aerobic zone, and to the reduction of SO4/2- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55 x 10-4 to 48.6 x 10-4 mmol 1-1 yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO4/2- (1.31 x 10-4 to 15 x 10-4 mmol 1-1 yr-1). The overall increase in SO4/2- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO4/2- loss through microbial reduction is exceeded by SO4/2- gain through diffusion from sediments and through the oxidation of FeS2. Geochemichal and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO4/2- -rich zones have localized SO4/2- -reducing zones in which the formation of iron disulfides been depleted by microbial reduction and resulted in decreases dissolved iron concentrations. These localized zones of SO4/2- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling. (C) 2000 Elsevier Science B.V.Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO42- in the aerobic zone, and to the reduction of SO42- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55??10-4 to 48.6??10-4mmol l-1yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO42- (1.31??10-4 to 15??10-4mmol l-1yr-1). The overall increase in SO42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO42- loss through microbial reduction is exceeded by SO42- gain through diffusion from sediments and through the oxidation of FeS2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO42--rich zones have been depleted by microbial reduction and resulted in localized SO42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.

Improved arterial blood oxygenation following intravenous infusion of cold supersaturated dissolved oxygen solution.

PubMed

Grady, Daniel J; Gentile, Michael A; Riggs, John H; Cheifetz, Ira M

2014-01-01

One of the primary goals of critical care medicine is to support adequate gas exchange without iatrogenic sequelae. An emerging method of delivering supplemental oxygen is intravenously rather than via the traditional inhalation route. The objective of this study was to evaluate the gas-exchange effects of infusing cold intravenous (IV) fluids containing very high partial pressures of dissolved oxygen (>760 mm Hg) in a porcine model. Juvenile swines were anesthetized and mechanically ventilated. Each animal received an infusion of cold (13 °C) Ringer's lactate solution (30 mL/kg/hour), which had been supersaturated with dissolved oxygen gas (39.7 mg/L dissolved oxygen, 992 mm Hg, 30.5 mL/L). Arterial blood gases and physiologic measurements were repeated at 15-minute intervals during a 60-minute IV infusion of the supersaturated dissolved oxygen solution. Each animal served as its own control. Five swines (12.9 ± 0.9 kg) were studied. Following the 60-minute infusion, there were significant increases in PaO2 and SaO2 (P < 0.05) and a significant decrease in PaCO2 (P < 0.05), with a corresponding normalization in arterial blood pH. Additionally, there was a significant decrease in core body temperature (P < 0.05) when compared to the baseline preinfusion state. A cold, supersaturated dissolved oxygen solution may be intravenously administered to improve arterial blood oxygenation and ventilation parameters and induce a mild therapeutic hypothermia in a porcine model.

Improved Arterial Blood Oxygenation Following Intravenous Infusion of Cold Supersaturated Dissolved Oxygen Solution

PubMed Central

Grady, Daniel J; Gentile, Michael A; Riggs, John H; Cheifetz, Ira M

2014-01-01

BACKGROUND One of the primary goals of critical care medicine is to support adequate gas exchange without iatrogenic sequelae. An emerging method of delivering supplemental oxygen is intravenously rather than via the traditional inhalation route. The objective of this study was to evaluate the gas-exchange effects of infusing cold intravenous (IV) fluids containing very high partial pressures of dissolved oxygen (>760 mm Hg) in a porcine model. METHODS Juvenile swines were anesthetized and mechanically ventilated. Each animal received an infusion of cold (13 °C) Ringer’s lactate solution (30 mL/kg/hour), which had been supersaturated with dissolved oxygen gas (39.7 mg/L dissolved oxygen, 992 mm Hg, 30.5 mL/L). Arterial blood gases and physiologic measurements were repeated at 15-minute intervals during a 60-minute IV infusion of the supersaturated dissolved oxygen solution. Each animal served as its own control. RESULTS Five swines (12.9 ± 0.9 kg) were studied. Following the 60-minute infusion, there were significant increases in PaO2 and SaO2 (P < 0.05) and a significant decrease in PaCO2 (P < 0.05), with a corresponding normalization in arterial blood pH. Additionally, there was a significant decrease in core body temperature (P < 0.05) when compared to the baseline preinfusion state. CONCLUSIONS A cold, supersaturated dissolved oxygen solution may be intravenously administered to improve arterial blood oxygenation and ventilation parameters and induce a mild therapeutic hypothermia in a porcine model. PMID:25249764

Sulfate formation catalyzed by coal fly ash, mineral dust and iron(iii) oxide: variable influence of temperature and light.

PubMed

Gankanda, Aruni; Coddens, Ellen M; Zhang, Yaping; Cwiertny, David M; Grassian, Vicki H

2016-12-08

Recent atmospheric field and modeling studies have highlighted a lack of understanding of the processes responsible for high levels of sulfate aerosol in the atmosphere, ultimately arising from a dearth of experimental data on such processes. Here we investigated the effect of temperature and simulated solar radiation on the catalytic oxidation of S(iv) to S(vi) (i.e., sulfite to sulfate) in aqueous suspensions of several metal-containing, atmospherically relevant particles including coal fly ash (FA), Arizona test dust (ATD) and an iron oxide (γ-Fe 2 O 3 ). The effect of temperature and light on S(iv) oxidation was found to be very different for these three samples. For example, in the presence of FA and γ-Fe 2 O 3 the temporal evolution of dissolved Fe(ii) (formed via reductive particle dissolution) correlated with S(iv) oxidation. Accordingly, we propose that S(iv) oxidation in most of these systems initially occurs primarily at the particle surface (i.e., a heterogeneous reaction pathway), although a solution-phase (i.e., homogeneous) catalytic pathway also contributes over later timescales due to the formation and accumulation of dissolved Fe(iii) (generated via oxidation of dissolved Fe(ii) by O 2 ). It is likely that the homogeneous reaction pathway is operative at initial times in the presence of γ-Fe 2 O 3 at 25 °C. In contrast, S(iv) oxidation in the presence of ATD appears to proceed entirely via a heterogeneous reaction, which notably does not lead to any iron dissolution. In fact, the greater overall rate of S(iv) loss in the presence of ATD compared to FA and γ-Fe 2 O 3 suggests that other factors, including greater adsorption of sulfite, transition metal ion (TMI) catalysis by other metal ions (e.g., Ti), or different species of iron in ATD, play a role. Overall these studies suggest that the rate, extent and products of atmospheric S(iv) oxidation can be highly variable and dependent upon the nature of aerosol sources and ambient conditions (e.g., temperature and irradiance). Ultimately, such complexity precludes simple, broadly generalized schemes for this reaction when modeling atmospheric processes involving diverse components of different mineral dust aerosol as well as other metal-containing aerosol.

Composition of steam in the system NaCl-KCl-H2O-quartz at 600°C

USGS Publications Warehouse

Fournier, Robert O.; Thompson, J. Michael

1993-01-01

In the system NaCl-KCl-H2O, with and without ??-quartz present, steam was equilibrated in a large-volume reaction vessel with brine and/or precipitated salt at 600??C and pressures ranging from about 100 to 0.4 MPa. Episodically, steam was extracted for chemical analysis, accompanied by a decrease in pressure within the reaction vessel. In the absence of precipitated salt, within the analytical uncertainty stoichiometric quantities of Cl and total alkali, metals (Na + K) dissolve in steam coexisting with chloriderich brine. In contrast, in the presence of precipitated salt (in our experiments halite with some KCl in solid solution), significant excess chloride as associated hydrogen chloride (HCl0??) dissolves in steam. The HCl0 is generated by the reaction of steam with solid NaCl(s), producing solid NaOH(s) that diffuses into halite, forming a solid solution. In our quasistatic experiments, compared to dynamic flow-through experiments of others, higher initial ratios of H2O/NaCl have apparently resulted in higher model fractions of NaOH(s) in solid solution in halite. This, in turn, resulted in incrementally higher concentrations of associated NaOHo dissolved in steam. Addition of quartz to the system NaCl + KC1 + H2O resulted in an order of magnitude increase in the concentration of HCl0 dissolved in steam, apparently as a consequence of the formation of sodium disilicate by reaction of silica with NaOH(s). The measured dissolved silica in steam saturated with alkali halides at 600??C in the pressure range 7-70 MPa agrees nicely with calculated values of the solubility of ??-quartz obtained using the equation of Fournier and Potter (1982), corrected for dissolved salt by the method of fournier (1983). Na K ratios in steam at 600??C tend to be slightly greater than in coexisting brine. When precipitated halite is present, larger mole fractions of NaOH(s) in solid solution in that halite apparently result in even larger Na K ratios in coexisting steam. Precipitation of more halite as a consequence of repeated depressurization episodes results in decreased Na K ratios in both the brine and coexisting steam phases, indicating that the lower pressures begin to favor K over Na in the vapor. When steam is in contact with precipitated salts in the absence of brine, the Na K ratio in the steam is less than that of the bulk composition of the salt-H2O system. ?? 1993.

Nitrous oxide emissions in the Shanghai river network: implications for the effects of urban sewage and IPCC methodology.

PubMed

Yu, Zhongjie; Deng, Huanguang; Wang, Dongqi; Ye, Mingwu; Tan, Yongjie; Li, Yangjie; Chen, Zhenlou; Xu, Shiyuan

2013-10-01

Global nitrogen (N) enrichment has resulted in increased nitrous oxide (N(2)O) emission that greatly contributes to climate change and stratospheric ozone destruction, but little is known about the N(2)O emissions from urban river networks receiving anthropogenic N inputs. We examined N(2)O saturation and emission in the Shanghai city river network, covering 6300 km(2), over 27 months. The overall mean saturation and emission from 87 locations was 770% and 1.91 mg N(2)O-N m(-2) d(-1), respectively. Nitrous oxide (N(2)O) saturation did not exhibit a clear seasonality, but the temporal pattern was co-regulated by both water temperature and N loadings. Rivers draining through urban and suburban areas receiving more sewage N inputs had higher N(2)O saturation and emission than those in rural areas. Regression analysis indicated that water ammonium (NH(4)(+)) and dissolved oxygen (DO) level had great control on N(2)O production and were better predictors of N(2)O emission in urban watershed. About 0.29 Gg N(2)O-N yr(-1) N(2)O was emitted from the Shanghai river network annually, which was about 131% of IPCC's prediction using default emission values. Given the rapid progress of global urbanization, more study efforts, particularly on nitrification and its N(2)O yielding, are needed to better quantify the role of urban rivers in global riverine N(2)O emission. © 2013 John Wiley & Sons Ltd.

Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

DOE PAGES

Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Walter Anthony, K.; ...

2015-08-04

Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH 4) produced in lakes. Aerobic CH 4 oxidation depends mainly on lake CH 4 and oxygen (O 2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH 4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcelymore » reported in the literature. In the present study, we measured CH 4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH 4 and O 2 concentrations. Here, we found that in the winter, aerobic CH 4 oxidation was mainly controlled by the dissolved O 2 concentration, while in the summer it was controlled primarily by the CH 4 concentration, which was scarce compared to dissolved O 2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH 4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH 4 cycling.« less

Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Walter Anthony, K.

Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH 4) produced in lakes. Aerobic CH 4 oxidation depends mainly on lake CH 4 and oxygen (O 2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH 4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcelymore » reported in the literature. In the present study, we measured CH 4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH 4 and O 2 concentrations. Here, we found that in the winter, aerobic CH 4 oxidation was mainly controlled by the dissolved O 2 concentration, while in the summer it was controlled primarily by the CH 4 concentration, which was scarce compared to dissolved O 2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH 4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH 4 cycling.« less

Effect of process parameters and operational mode on nitrous oxide emissions from a nitritation reactor treating reject wastewater.

PubMed

Pijuan, Maite; Torà, Josep; Rodríguez-Caballero, Adrián; César, Elvira; Carrera, Julián; Pérez, Julio

2014-02-01

Nitrous oxide (N2O) and methane emissions were monitored in a continuous granular airlift nitritation reactor from ammonium-rich wastewater (reject wastewater). N2O emissions were found to be dependent on dissolved oxygen (DO) concentration in the range of 1-4.5 mg O2/L, increasing within this range when reducing the DO values. At higher DO concentrations, N2O emissions remained constant at 2.2% of the N oxidized to nitrite, suggesting two different mechanisms behind N2O production, one dependent and one independent of DO concentration. Changes on ammonium, nitrite, free ammonia and free nitrous acid concentrations did not have an effect on N2O emissions within the concentration range tested. When operating the reactor in a sequencing batch mode under high DO concentration (>5 mg O2/L), N2O emissions increased one order of magnitude reaching values of 19.3 ± 7.5% of the N oxidized. Moreover, CH4 emissions detected were due to the stripping of the soluble CH4 that remained dissolved in the reject wastewater after anaerobic digestion. Finally, an economical and carbon footprint assessment of a theoretical scaled up of the pilot plant was conducted. Copyright © 2013 Elsevier Ltd. All rights reserved.

Study on Wide-gap Gallium-nitride Based Films and Their Quantum-dots Devices

DTIC Science & Technology

2006-09-05

The chemical reaction is give by 2GaN + 6h+ +6OH- --> Ga2O3 + 3H2O + N2 (2.3.1) From the Faraday’s law, the photocurrent should be... Ga2O3 start to growth whiles the light on. The photocurrent decreased gradually due to the oxide thickness increasing. During the light off duration...the oxide dissolved in KOH solution in dark. The chemical reaction is give by 20 Ga2O3 +6OH- --> 2GaO33- + 3H2O (2.3.3) The oxide

Determination of selenium at trace levels in geologic materials by energy-dispersive X-ray fluorescence spectrometry

USGS Publications Warehouse

Wahlberg, J.S.

1981-01-01

Low levels of selenium (0.1-500 ppm) in both organic and inorganic geologic materials can be semiquantitatively measured by isolating Se as a thin film for presentation to an energy-dispersive X-ray fluorescence spectrometer. Suitably pulverized samples are first digested by fusing with a mixture of Na2CO3 and Na2O2. The fusion cake is dissolved in distilled water, buffered with NH4Cl, and filtered to remove Si and the R2O3 group. A carrier solution of Na2TeO4, plus solid KI, hydrazine sulfate and Na2SO3, is added to the filtrate. The solution is then vacuum-filtered through a 0.45-??m pore-size filter disc. The filter, with the thin film of precipitate, is supported between two sheets of Mylar?? film for analysis. Good agreement is shown between data reported in this study and literature values reported by epithermal neutron-activation analysis and spectrofluorimetry. The method can be made quantitative by utilizing a secondary precipitation to assure complete recovery of the Se. The X-ray method offers fast turn-around time and a reasonably high production rate. ?? 1981.

Effects of different forms of plant-derived organic matter on nitrous oxide emissions.

PubMed

Qiu, Qingyan; Wu, Lanfang; Ouyang, Zhu; Li, Binbin; Xu, Yanyan

2016-07-13

To investigate the impact of different forms of plant-derived organic matter on nitrous oxide (N2O) emissions, an incubation experiment with the same rate of total nitrogen (N) application was carried out at 25 °C for 250 days. Soils were incorporated with maize-derived organic matter (i.e., maize residue-derived dissolved organic matter and maize residues with different C/N ratios) and an inorganic N fertilizer (urea). The pattern and magnitude of nitrous oxide (N2O) emissions were affected by the form of N applied. Single application of maize-derived organic matter resulted in a higher N2O emission than single application of the inorganic N fertilizer or combined application of the inorganic N fertilizer and maize-derived organic matter. The positive effect of maize residue-derived dissolved organic matter (DOM) addition on N2O emissions was relatively short-lived and mainly occurred at the early stage following DOM addition. In contrast, the positive effect induced by maize residue addition was more pronounced and lasted for a longer period. Single application of maize residues resulted in a substantial decrease in soil nitric nitrogen (NO3(-)-N), but it did not affect the production of N2O. No significant relationship between N2O emission and NO3(-)-N and ammonium nitrogen (NH4(+)-N) suggested that the availability of soil N was not limiting the production of N2O in our study. The key factors affecting soil N2O emission were the soil dissolved organic carbon (DOC) content and metabolism quotient (qCO2). Both of them could explain 87% of the variation in cumulative N2O emission. The C/N ratio of maize-derived organic matter was a poor predictor of N2O emission when the soil was not limited by easily available C and the available N content met the microbial N demands for nitrification and denitrification. The results suggested that the magnitude of N2O emission was determined by the impact of organic amendments on soil C availability and microbial activity rather than on soil N availability. In agricultural management practices, if the N inputs from organic and inorganic N fertilizers are equivalent, addition of organic N fertilizers that contain high amounts of available C will result in a higher N2O emission.

Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

NASA Astrophysics Data System (ADS)

Lange, R. A.; Waters, L.

2014-12-01

The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels in these 14 rhyolitic magmas, no effect is detected. Therefore, it can be robustly concluded that degassing of substantial amounts of the H2O component (≤ 6.5 wt%), by itself, does not induce oxidation in erupted magmas, particularly those more iron-rich than rhyolites (e.g., arc basalts).

Formic acid acting as an efficient oxygen scavenger in four-electron reduction of oxygen catalyzed by a heterodinuclear iridium-ruthenium complex in water.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2010-09-01

A heterodinuclear iridium-ruthenium complex [Ir(III)(Cp*)(H(2)O)(bpm)Ru(II)(bpy)(2)](SO(4))(2) (Cp* = eta(5)-pentamethyl-cyclopentadienyl, bpm = 2,2'-bipyrimidine, bpy = 2,2'-bipyridine) acts as an effective catalyst for removal of dissolved O(2) by the four-electron reduction of O(2) with formic acid in water at an ambient temperature.

Chemical weathering rate, denudation rate, and atmospheric and soil CO2 consumption of Paraná flood basalts in São Paulo State, Brazil

NASA Astrophysics Data System (ADS)

da Conceição, Fabiano Tomazini; dos Santos, Carolina Mathias; de Souza Sardinha, Diego; Navarro, Guillermo Rafael Beltran; Godoy, Letícia Hirata

2015-03-01

The chemical weathering rate and atmospheric/soil CO2 consumption of Paraná flood basalts in the Preto Stream basin, São Paulo State, Brazil, were evaluated using major elements as natural tracers. Surface and rain water samples were collected in 2006, and analyses were performed to assess pH, temperature, dissolved oxygen (DO), electrical conductivity (EC) and total dissolved solids (TDS), including SO42-, NO3-, PO43 -, HCO3-, Cl-, SiO2, Ca2 +, Mg2 +, Na+ and K+. Fresh rocks and C horizon samples were also collected, taking into account their geological context, abundance and spatial distribution, to analyze major elements and mineralogy. The Preto Stream, downstream from the city of Ribeirão Preto, receives several elements/compounds as a result of anthropogenic activities, with only sulfate yielding negative flux values. The negative flux of SO42 - can be attributed to atmospheric loading that is mainly related to anthropogenic inputs. After corrections were made for atmospheric inputs, the riverine transport of dissolved material was found to be 30 t km- 2 y- 1, with the majority of the dissolved material transported during the summer (wet) months. The chemical weathering rate and atmospheric/soil CO2 consumption were 6 m/Ma and 0.4 · 106 mol km- 2 y- 1, respectively. The chemical weathering rate falls within the lower range of Paraná flood basalt denudation rates between 135 and 35 Ma previously inferred from chronological studies. This comparison suggests that rates of basalt weathering in Brazil's present-day tropical climate differ by at most one order of magnitude from those prevalent at the time of hothouse Earth. The main weathering process is the monosiallitization of anorthoclase, augite, anorthite and microcline. Magnetite is not weathered and thus remains in the soil profile.

Reservoir N2O data

EPA Pesticide Factsheets

Dissolved oxygen, dissolved nitrous oxide, and water temperature in reservoirs.This dataset is associated with the following publication:Beaulieu , J., C. Nietch , and J. Young. Source or sink: Insight on controls of nitrous oxide biogeochemistry from a 20 reservoir survey. Journal of Geophysical Research - Biogeosciences. American Geophysical Union, Washington, DC, USA, 120(10): 1995-2010, (2015).

The Quench Control of Water Estimates in Convergent Margin Magmas

NASA Astrophysics Data System (ADS)

Gavrilenko, M.; Krawczynski, M.; Ruprecht, P.

2017-12-01

Mineral-hosted glassy melt inclusions (MIs) have been used to quantify magma volatile contents for several decades. Despite the growing number of volatile studies utilizing MIs, it has not been tested whether there is a physical limit on how much dissolved volatiles a glassy MI can contain. We explored the limits of MIs as hydrous magma recorders in an experimental study, showing that there is a limit of dissolved H2O that glassy MIs cannot exceed. These results show there is potential bias in the glassy MI data set; they can only faithfully record pre-eruptive H2O contents in the upper-most part of the Earth's crust where H2O-solubility is low. The current MI database cannot be used to robustly estimate the full range of arc magmas and therefore assess volatile budgets in primitive or evolved compositions. Such magmas may contain much larger amounts of H2O than currently recognized and the diversity of magma evolutionary pathways in subduction zones is likely being significantly underappreciated.

Effects of Carbon and Cover Crop Residues on N2O and N2 Emissions

NASA Astrophysics Data System (ADS)

Burger, M.; Cooperman, Y.; Horwath, W. R.

2016-12-01

In Mediterranean climate, nitrous oxide emissions occurring with the first rainfall after the dry summer season can contribute up to 50% of agricultural systems' total annual emissions, but the drivers of these emissions have not been clearly identified, and there are only few measurements of atmospheric nitrogen (N2) production (denitrification) during these events. In lab incubations, we investigated N2O and N2 production, gross ammonification and nitrification, and microbial N immobilization with wet-up in soil from a vineyard that was previously fallow or where cover crop residue had been incorporated the previous spring. Before the first rainfall, we measured 120 mg dissolved organic carbon (DOC-C) kg-1 soil in the 0-5 cm layer of this vineyard, and after the rain 10 mg DOC-C kg-1, while nitrate levels before the rain were <5 mg N kg-1 in fallow and <10 mg N kg-1 in previously cover cropped soil. The N2O/N2 production was 2, 7, 9, and 86% in fallow, legume-grass mixture, rye, and legume cover cropped soil. The N2O/N2 ratio tended to increase with lower DOC (post-rain) levels in the soil. The results suggest that accumulated carbon in dry surface soil is the main driving factor of N2O and N2 emissions through denitrification with the first rainfall after prolonged dry periods.

Enhanced Indirect Photochemical Transformation of Histidine and Histamine through Association with Chromophoric Dissolved Organic Matter.

PubMed

Chu, Chiheng; Lundeen, Rachel A; Remucal, Christina K; Sander, Michael; McNeill, Kristopher

2015-05-05

Photochemical transformations greatly affect the stability and fate of amino acids (AAs) in sunlit aquatic ecosystems. Whereas the direct phototransformation of dissolved AAs is well investigated, their indirect photolysis in the presence of chromophoric dissolved organic matter (CDOM) is poorly understood. In aquatic systems, CDOM may act both as sorbent for AAs and as photosensitizer, creating microenvironments with high concentrations of photochemically produced reactive intermediates, such as singlet oxygen (1O2). This study provides a systematic investigation of the indirect photochemical transformation of histidine (His) and histamine by 1O2 in solutions containing CDOM as a function of solution pH. Both His and histamine showed pH-dependent enhanced phototransformation in the CDOM systems as compared to systems in which model, low-molecular-weight 1O2 sensitizers were used. Enhanced reactivity resulted from sorption of His and histamine to CDOM and thus exposure to elevated 1O2 concentrations in the CDOM microenvironment. The extent of reactivity enhancement depended on solution pH via its effects on the protonation state of His, histamine, and CDOM. Sorption-enhanced reactivity was independently supported by depressed rate enhancements in the presence of a cosorbate that competitively displaced His and histamine from CDOM. Incorporating sorption and photochemical transformation processes into a reaction rate prediction model improved the description of the abiotic photochemical transformation rates of His in the presence of CDOM.

Aquifer geochemistry at potential aquifer storage and recovery sites in coastal plain aquifers in the New York city area, USA

USGS Publications Warehouse

Brown, C.J.; Misut, P.E.

2010-01-01

The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water.The simulated injection of buffered, oxic city water into a hypothetical ASR well increased the hydraulic head at the well, displaced the ambient groundwater, and formed a spheroid of injected water with lower concentrations of Fe, Mn and major ions in water surrounding the ASR well, than in ambient water. Both the dissolved O2 concentrations and the pH of water near the well generally increased in magnitude during the simulated 5-a injection phase. The resultant oxidation of Fe2+ and attendant precipitation of goethite during injection provided a substrate for sorption of dissolved Fe during the 8-a extraction phase. The baseline scenario with a low (0.001M) concentration of pyrite in aquifer sediments, indicated that nearly 190% more water with acceptably low concentrations of dissolved Fe could be extracted than was injected. Scenarios with larger amounts of pyrite in aquifer sediments generally resulted in less goethite precipitation, increased acidity, and increased concentrations of dissolved Fe in extracted water. In these pyritic scenarios, the lower amounts of goethite precipitated and the lower pH during the extraction phase resulted in decreased sorption of Fe2+ and a decreased amount of extractable water with acceptably low concentrations of dissolved Fe (5.4??10-6M). A linear decrease in recovery efficiency with respect to dissolved Fe concentrations is caused by pyrite dissolution and the associated depletion of dissolved O2 (DO) and increase in acidity. Simulations with more than 0.0037M of pyrite, which is the maximum amount dissolved in the baseline scenario, had just over a 50% recovery efficiency. The precipitation of ferric hydroxide minerals (goethite) at the well screen, and a possible associated decrease in specific capacity of the ASR well, was not apparent during the extraction phase of ASR simulations, but the model does not incorporate the microbial effects and biofouling associated with ferric hydroxide precipitation.The host groundwater chemistry in calcite-poor Cretaceous aquifers of the NYC area consists of low alkalinity and moderate to low pH. The dissolution of goethite in scenarios with unbuffered injectate indicates that corrosion of the well could occur if the injectate is not buffered. Simulations with buffered injectate resulted in greater precipitation of goethite, and lower concentrations of dissolved Fe, in the extracted water. Dissolved Fe concentrations in extracted water were highest in simulations of aquifers (1) in which pyrite and siderite in the aquifer were in equilibrium, and (2) in coastal areas affected by saltwater intrusion, where high dissolved-cation concentrations provide a greater exchange of Fe2+ (FeX2). Results indicate that ASR in pyrite-beari

Isotopic Clues on Factors Controlling Geochemical Fluxes From Large Watersheds in Eastern Canada

NASA Astrophysics Data System (ADS)

Rosa, E.; Helie, J.; Ghaleb, B.; Hillaire-Marcel, C.; Gaillardet, J.

2008-12-01

A monitoring and monthly sampling program of the Nelson, Ottawa, St. Lawrence, La Grande and Great Whale rivers was started in September 2007. It provides information on the seasonality and sources of geochemical fluxes into the Hudson Bay and the North Atlantic from watersheds covering more than 2.6 106 km2 of the eastern Canadian boreal domain. Measurements of pH and alkalinity, analyses of major ions, strontium and dissolved silica, 2H and 18O of water, concentrations and isotopic properties of dissolved organic and inorganic carbon (13C) and uranium (234U/238U) were performed. Lithology more than latitudinal climatic gradients controls the river geochemistry. Rivers draining silicate terrains show lower dissolved U concentrations but greater 234U/238U disequilibria than rivers draining carbonates (average of 1.38 vs. 1.23). Groundwater supplies might exert some control on these U- isotope signatures. No clear seasonality is observed in 234U/238U ratios, but U concentrations are correlated to dissolved organic carbon (DOC) concentrations in most rivers. Rivers draining carbonates present higher total dissolved carbon concentrations and higher 13C-contents in dissolved inorganic carbon (DIC), in response to the dissolution of soil carbonates. DOC/DIC ratios above 2.4 are observed in rivers draining silicates; their lower 13C-DIC content directly reflects the organic matter oxidation in soils. Total dissolved solids are one order of magnitude or more greater in rivers draining carbonates, showing the strong difference in chemical weathering rates according to the geological setting. The stability in chemical fluxes and water isotopic compositions in the La Grande River, which hosts hydroelectric reservoirs covering more than 12 000 km2, indicates that it is the most buffered hydrological system among the investigated watersheds. Seasonal fluctuations are observed elsewhere, with maximum geochemical fluxes during the spring snowmelt. 2H-18O content of river water appears to be the only parameter presenting a strong latitudinal and climatic gradient (independent of lithology).

Geochemical processes controlling selenium in ground water after mining, Powder River Basin, Wyoming, U.S.A.

USGS Publications Warehouse

Naftz, D.L.; Rice, J.A.

1989-01-01

Geochemical data for samples of overburden from three mines in the Powder River Basin indicate a statistically significant (0.01 confidence level) positive correlation (r = 0.74) between Se and organic C. Results of factor analysis with varimax rotation on the major and trace element data from the rock samples indicate large (>50) varimax loadings for Se in two of the three factors. In Factor 1, the association of Se with constituents common to detrital grains indicates that water transporting the detrital particles into the Powder River Basin also carried dissolved Se. The large (>50) varimax loadings of Se and organic C in Factor 2 probably are due to the organic affinities characteristic of Se. Dissolved Se concentrations in water samples collected at one coal mine are directly related to the dissolved organic C concentrations. Hydrophilic acid concentrations in the water samples from the mine ranged from 35 to 43% of the total dissolved organic C, and hydrophobic acid concentrations ranged from 40 to 49% of the total dissolved organic C. The largest dissolved organic C concentrations in water from the same mine (34-302 mg/l), coupled with the large proportion of acidic components, may saturate adsorption sites on geothite and similar minerals that comprise the aquifer material, thus decreasing the extent of selenite (SeO32-) adsorption as a sink for Se as the redox state of ground water decreases. ?? 1989.

Modeling of nitrous oxide production by autotrophic ammonia-oxidizing bacteria with multiple production pathways.

PubMed

Ni, Bing-Jie; Peng, Lai; Law, Yingyu; Guo, Jianhua; Yuan, Zhiguo

2014-04-01

Autotrophic ammonia oxidizing bacteria (AOB) have been recognized as a major contributor to N2O production in wastewater treatment systems. However, so far N2O models have been proposed based on a single N2O production pathway by AOB, and there is still a lack of effective approach for the integration of these models. In this work, an integrated mathematical model that considers multiple production pathways is developed to describe N2O production by AOB. The pathways considered include the nitrifier denitrification pathway (N2O as the final product of AOB denitrification with NO2(-) as the terminal electron acceptor) and the hydroxylamine (NH2OH) pathway (N2O as a byproduct of incomplete oxidation of NH2OH to NO2(-)). In this model, the oxidation and reduction processes are modeled separately, with intracellular electron carriers introduced to link the two types of processes. The model is calibrated and validated using experimental data obtained with two independent nitrifying cultures. The model satisfactorily describes the N2O data from both systems. The model also predicts shifts of the dominating pathway at various dissolved oxygen (DO) and nitrite levels, consistent with previous hypotheses. This unified model is expected to enhance our ability to predict N2O production by AOB in wastewater treatment systems under varying operational conditions.

Synthesis and characterization of stabilized oxygen-releasing CaO2 nanoparticles for bioremediation.

PubMed

Yeh, Chia-Shen; Wang, Reuben; Chang, Wen-Chi; Shih, Yang-Hsin

2018-04-15

Bioremediation is one of the general methods to treat pollutants in soil, sediment, and groundwater. However, the low concentration and restricted dispersion of dissolved oxygen (DO) in these areas have limited the efficiency of remediation especially for microorganisms that require oxygen to grow. Calcium peroxide (CaO 2 ) is one of the oxygen-releasing compounds and has been applied to magnify the remediation efficacy of polluting areas. In this study, CaO 2 nanoparticles (NPs) were synthesized and evaluated by wet chemistry methods as well as dry and wet grinding processes. The characteristics of CaO 2 particles and NPs were analyzed and compared by dynamic light scattering, transmission electron microscopy, scanning electron microscopy, and X-ray powder diffraction. Our results showed that wet-grinded CaO 2 NPs had an average particle size of around 110 nm and were more stable compared to other particles from aggregation and sedimentation tests. In addition, we also observed that CaO 2 NPs had better DO characteristics and patterns; these NPs generated higher DO levels than their non-grinded form. Accordingly, our results suggested that wet-grinding CaO 2 particles to nanoscale could benefit their usage in bioremediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Soil pH effects on the comparative toxicity of dissolved zinc, non-nano and nano ZnO to the earthworm Eisenia fetida.

PubMed

Heggelund, Laura R; Diez-Ortiz, Maria; Lofts, Stephen; Lahive, Elma; Jurkschat, Kerstin; Wojnarowicz, Jacek; Cedergreen, Nina; Spurgeon, David; Svendsen, Claus

2014-08-01

To determine how soil properties influence nanoparticle (NP) fate, bioavailability and toxicity, this study compared the toxicity of nano zinc oxide (ZnO NPs), non-nano ZnO and ionic ZnCl2 to the earthworm Eisenia fetida in a natural soil at three pH levels. NP characterisation indicated that reaction with the soil media greatly controls ZnO properties. Three main conclusions were drawn. First that Zn toxicity, especially for reproduction, was influenced by pH for all Zn forms. This can be linked to the influence of pH on Zn dissolution. Secondly, that ZnO fate, toxicity and bioaccumulation were similar (including relationships with pH) for both ZnO forms, indicating the absence of NP-specific effects. Finally, earthworm Zn concentrations were higher in worms exposed to ZnO compared to ZnCl2, despite the greater toxicity of the ionic form. This observation suggests the importance of considering the relationship between uptake and toxicity in nanotoxicology studies.

Isotope hydrology of voluminous cold springs in fractured rock from an active volcanic region, northeastern California

NASA Astrophysics Data System (ADS)

Roses, Timothy P.; Lee Davisson, M.; Criss, Robert E.

1996-05-01

The more than 1550 km2 (600 mi2) Hat Creek Basin in northeastern California is host to several first magnitude cold springs that emanate from Quaternary basaltic rocks with individual discharge rates ranging from 1.7 to 8.5 m3 s-1 (60-300 ft3 s-1). Stable isotope (δ18O, δD, δ13C) and 14C measurements of surface and groundwater samples were used to identify recharge areas, and to evaluate aquifer residence times and flow paths. Recharge locations were constrained from the regional decrement in meteoric water δ18O values as a function of elevation, determined to be -0.23‰ per 100 m for small springs and creek waters collected along the western Cascade slope of this region. In general, the large-volume springs are lower in (δ18O than surrounding meteoric waters, and are inferred to originate in high-elevation, high-precipitation regions up to 50 km away from their discharge points. Large spring 14C abundances range from 99 to 41 % modern carbon (pmc), and most show evidence of interaction with three distinct carbon isotope reservoirs. These reservoirs are tentatively identified as (1) soil CO2 gas equilibrated under open system conditions with groundwater in the recharge zone [δ13CDIC ≈ -18‰, 14C > 100 pmc], (2) dissolved carbon equilibrated with atmospheric CO2 gas [δ13CDIC ≈ +1‰, 14C > 100 pmc], and (3) dissolved carbon derived from volcanic CO2 gas emissions [δ13CDIC≈0‰, 14C=0 pmc]. Many regional waters show a decrease in 14C abundance with increasing δ13C values, a pattern indicative of interaction with dead carbon originating from volcanic CO2 gas. Several lines of evidence suggest that actual groundwater residence times are too short (⩽ 200 years) to apply radiocarbon dating corrections. In particular, water temperatures measured at springs show that deep groundwater circulation does not occur, which implies an insufficient aquifer volume to account for both the high discharge rates and long residence times suggested by 14C apparent ages. The large springs also exhibit rapid decreases in flow during periods of drought that suggests a high level of aquifer interconnectivity to the recharge area. The estimated amount of volcanic CO2 dissolved in surface and groundwater originating from the Lassen highlands is consistent with the conversion of approximately 10% of the geothermal CO2 flux into dissolved inorganic carbon.

Submarine Flood Basalt Eruptions and Flows of Ontong Java Plateau, Nauru Basin and East Mariana Basin

NASA Astrophysics Data System (ADS)

Michael, P. J.; Trowbridge, S. R.; Zhang, J.; Johnson, A. L.

2016-12-01

The preservation of fresh basalt glasses from the submarine Cretaceous Ontong Java Plateau (OJP), Earth's largest LIP, has allowed correlation of precise lava compositions over 100s of km, as well as determination of eruption depths using dissolved H2O and CO2 contents. Low dissolved H2O in glasses shows that H2O in the mantle source is low [1,2], suggesting mantle temperatures are high. Very high dissolved Cl indicates that magmas interacted extensively with brines. The near total absence of vesicles in OJP glasses contrasts sharply with MORB, and suggests that OJP lavas were saturated or undersaturated with CO2 when they were emplaced, in contrast to MORB that are often oversaturated. The lavas likely remained liquid for a longer period of time so that they degassed to equilibrium levels of dissolved CO2 andlost all bubbles. Very precise major and trace element analyses of glasses, uncomplicated by crystals or alteration, show how lavas within and between widely-spaced drill holes could be related. For example, glasses from Sites 1185B and 1186A, which are about 200 km apart, are compositionally identical within precise limits and must have erupted from the same well-mixed magma chamber. They erupted at about the same depth, but 1186A has a corrected basement depth that is >700m deeper. With a slope of 0.3°, this suggests a flow distance >130km. The eruption depths for glasses from East Mariana and Nauru Basins are similar to those of 1185B and 1186A on OJP, even though their reconstructed basement depths are about 2000 m deeper. It suggests that the plateau lavas flowed into the basins. Similarly, eruption depths in Hole 807C are 3040m for Kwaimbaita lavas but are 1110m [1,2] for Singgalo lavas that directly overlie them. It is unlikely that plateau uplift and subsidence accounts for the observed eruption depths. All of these observations are best explained by very large-volume eruptions whose lavas traveled for long distances, up to 100s of km, into deeper water over gentle slopes (0.1-0.5°). The presence of many glass layers within the cores contrasts with continental flood basalts and suggests the flows were covered by a thick, moving, shifting carapace of solidified lava. They may represent an extreme form of inflated pahoehoe flows. 1 Michael, P.J., 1999 G-Cubed 1 (12), GC000025 2 Roberge J., et al., 2005, Geology 33, 501-504

Dissolution Behaviour of Hazardous Materials from Steel Slag with Wet Grinding Method

NASA Astrophysics Data System (ADS)

Hisyamudin Muhd Nor, Nik; Norhana Selamat, Siti; Hanif Abd Rashid, Muhammad; Fauzi Ahmad, Mohd; Jamian, Saifulnizan; Chee Kiong, Sia; Fahrul Hassan, Mohd; Mohamad, Fariza; Yokoyama, Seiji

2016-06-01

Steel slag is a by-product from steel industry and it contains variety of hazardous materials. In this study, the dissolution behaviour and removal potential of hazardous materials from steel slag with the wet grinding method was investigated. The slag was wet ground in the CO2 atmosphere and the slurry produced was filtered using centrifugal separator to separate the liquid and solid sediments. Then, the concentrations of dissolved metal elements in the liquid sediment were analyzed by ICP-MS. The changes of pH during the grinding were also investigated. It was found that the pHs were decreased immediately after the CO2 gas introduced into the vessel. The pHs were ranging from 6.8 to 7.6 at the end of grinding. The dissolved concentration of Zn and Cr were ranging from 5~45 [mg/dm3] and 0.2~2.5 [mg/dm3] respectively. The ratios of Zn removal for stainless steel oxidizing and reducing slag were very high, but those from normal steel oxidizing and reducing slag were very low. It is assumed that the Zn dissolved as ZnOH+ from Zn(OH)2 that formed due to the reaction between ZnO and water. Dissolution of Cr also occurred but in very low quantity compared to the dissolution of Zn. The dissolution of Cr occurred due to the grinding process and small amount of Cr(OH)3 was formed during the grinding. This small formation of Cr(OH)3 resulted to the low dissolved concentration of Cr in the form of Cr(OH)2+. According to the XRD analysis, the Cr mostly existed in the slags as Cr(IIl) in the form of MgCr2O4 and FeCr2O4.

Tidal pulsing alters nitrous oxide fluxes in a temperate intertidal mudflat.

PubMed

Vieillard, A M; Fulweiler, R W

2014-07-01

Environmental pulses, or sudden, marked changes to the conditions within an ecosystem, can be important drivers of resource availability in many systems. In this study, we investigated the effect of tidal pulsing on the fluxes of nitrous oxide (N2O), a powerful greenhouse gas, from a marine intertidal mudflat on the north shore of Massachusetts, USA. We found these tidal flat sediments to be a sink of N2O at low tide with an average uptake rate of -6.7 +/- 2 micromol x m(-2) x h(-1). Further, this N20 sink increased the longer sediments were tidally exposed. These field measurements, in conjunction with laboratory nutrient additions, revealed that this flux appears to be driven primarily by sediment denitrification. Additionally, N2O uptake was most responsive to dissolved inorganic nitrogen with phosphorus (DIN + DIP) addition, suggesting that the N2O consumption process may be P limited. Furthermore, nutrient addition experiments suggest that dissimilatory nitrate reduction to ammonium (DNRA) releases N20 at the highest levels of nitrate fertilization. Our findings indicate that tidal flats are important sinks of N2O, potentially capable of offsetting the release of this potent greenhouse gas by other, nearby ecosystems.

Evolution of melt-vapor surface tension in silicic volcanic systems: Experiments with hydrous melts

USGS Publications Warehouse

Mangan, M.; Sisson, T.

2005-01-01

We evaluate the melt-vapor surface tension (??) of natural, water-saturated dacite melt at 200 MPa, 950-1055??C, and 4.8-5.7 wt % H2O. We experimentally determine the critical supersaturation pressure for bubble nucleation as a function of dissolved water and then solve for ?? at those conditions using classical nucleation theory. The solutions obtained give dacite melt-vapor surface tensions that vary inversely with dissolved water from 0.042 (??0.003) J m-2 at 5.7 wt% H2O to 0.060 (??0.007) J m-2 at 5.2 wt% H2O to 0.073 (??0.003) J m-2 at 4.8 wt% H2O. Combining our dacite results with data from published hydrous haplogranite and high-silica rhyolite experiments reveals that melt-vapor surface tension also varies inversely with the concentration of mafic melt components (e.g., CaO, FeOtotal, MgO). We develop a thermodynamic context for these observations in which melt-vapor surface tension is represented by a balance of work terms controlled by melt structure. Overall, our results suggest that cooling, crystallization, and vapor exsolution cause systematic changes in ?? that should be considered in dynamic modeling of magmatic processes.

Synthesis of ultrafine powders by microwave heating

DOEpatents

Meek, Thomas T.; Sheinberg, Haskell; Blake, Rodger D.

1988-01-01

A method of synthesizing ultrafine powders using microwaves is described. A water soluble material is dissolved in water and the resulting aqueous solution is exposed to microwaves until the water has been removed. The resulting material is an ultrafine powder. This method can be used to make Al.sub.2 O.sub.3, NiO+Al.sub.2 O.sub.3 and NiO as well as a number of other materials including GaBa.sub.2 Cu.sub.3 O.sub.x.

Tannic acid alleviates bulk and nanoparticle Nd2O3 toxicity in pumpkin: a physiological and molecular response.

PubMed

Chen, Guangcai; Ma, Chuanxin; Mukherjee, Arnab; Musante, Craig; Zhang, Jianfeng; White, Jason C; Dhankher, Om Parkash; Xing, Baoshan

2016-11-01

The effect of dissolved organic matter (DOM) on nanoparticle toxicity to plants is poorly understood. In this study, tannic acid (TA) was selected as a DOM surrogate to explore the mechanisms of neodymium oxide NPs (Nd2O3 NPs) phytotoxicity to pumpkin (Cucurbita maxima). The results from the tested concentrations showed that 100 mg L(-1) Nd2O3 NPs were significantly toxic to pumpkin in term of fresh biomass, and the similar results from the bulk particles and the ionic treatments were also evident. Exposure to 100 mg L(-1) of Nd2O3 NPs and BPs in 1/5 strength Hoagland's solution not only significantly inhibited pumpkin growth, but also decreased the S, Ca, K and Mg levels in plant tissues. However, 60 mg L(-1) TA significantly moderated the observed phytotoxicity, decreased Nd accumulation in the roots, and notably restored S, Ca, K and Mg levels in NPs and BPs treated pumpkin. TA at 60 mg L(-1) increased superoxide dismutase (SOD) activity in both roots (17.5%) and leaves (42.9%), and catalase (CAT) activity (243.1%) in the roots exposed to Nd2O3 NPs. This finding was confirmed by the observed up-regulation of transcript levels of SOD and CAT in Nd2O3 NPs treated pumpkin analyzed by quantitative reverse transcription polymerase chain reaction. These results suggest that TA alleviates Nd2O3 BPs/NPs toxicity through alteration of the particle surface charge, thus reducing the contact and uptake of NPs by pumpkin. In addition, TA promotes antioxidant enzymatic activity by elevating the transcript levels of genes involved in ROS scavenging. Our results shed light on the mechanisms underlying the influence of DOM on the bioavailability and toxicity of NPs to terrestrial plants.

A perspective on underwater photosynthesis in submerged terrestrial wetland plants

PubMed Central

Colmer, Timothy D.; Winkel, Anders; Pedersen, Ole

2011-01-01

Background and aims Wetland plants inhabit flood-prone areas and therefore can experience episodes of complete submergence. Submergence impedes exchange of O2 and CO2 between leaves and the environment, and light availability is also reduced. The present review examines limitations to underwater net photosynthesis (PN) by terrestrial (i.e. usually emergent) wetland plants, as compared with submerged aquatic plants, with focus on leaf traits for enhanced CO2 acquisition. Scope Floodwaters are variable in dissolved O2, CO2, light and temperature, and these parameters influence underwater PN and the growth and survival of submerged plants. Aquatic species possess morphological and anatomical leaf traits that reduce diffusion limitations to CO2 uptake and thus aid PN under water. Many aquatic plants also have carbon-concentrating mechanisms to increase CO2 at Rubisco. Terrestrial wetland plants generally lack the numerous beneficial leaf traits possessed by aquatic plants, so submergence markedly reduces PN. Some terrestrial species, however, produce new leaves with a thinner cuticle and higher specific leaf area, whereas others have leaves with hydrophobic surfaces so that gas films are retained when submerged; both improve CO2 entry. Conclusions Submergence inhibits PN by terrestrial wetland plants, but less so in species that produce new leaves under water or in those with leaf gas films. Leaves with a thinner cuticle, or those with gas films, have improved gas diffusion with floodwaters, so that underwater PN is enhanced. Underwater PN provides sugars and O2 to submerged plants. Floodwaters often contain dissolved CO2 above levels in equilibrium with air, enabling at least some PN by terrestrial species when submerged, although rates remain well below those in air. PMID:22476500

Recovery of Mo for Accelerator Production of Mo-99 Using (y,n) Reaction on Mo-100

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tkac, Peter; Vandegrift, George F.; Nunn, Stephen D.

2013-09-30

Technetium-99m is a widely used radiopharmaceutical. Its parent, Mo-99, is produced worldwide to supply this important isotope. One means to produce Mo-99 is by bombarding a Mo-100 target with an electron beam from a linear accelerator; the γ/n reaction on Mo-100 produces Mo-99. After dissolving Mo-100 enriched disks in hydrogen peroxide, the solution is converted to potassium molybdate (0.2 g-Mo/mL) in 5 M KOH. After milking the Tc-99m in the TechneGen generator over a period of 7-10 days, the molybdenum solution needs to be treated to recover valuable Mo-100 for production of sintered Mo disks. However, during the production ofmore » Mo-99 by (γ, n) reaction on the Mo-100 target, several byproducts are formed. Therefore, recycling Mo will require the conversion of K 2MoO 4 in 5 M KOH solution to MoO 3 powder, and purification from other metals present in the Mo solution. The starting Mo-100 enriched material contains less than 20 mg of potassium in 1 kg of molybdenum (<20 ppm). However, after dissolving the irradiated Mo-100 target in hydrogen peroxide and converting it to K 2MoO 4 in 5 M KOH (0.2 g-Mo/mL), the solution contains about 1.8 kg of potassium per kilogram of molybdenum. The most challenging separation for this recovery step is purifying molybdenum from potassium. One requirement to facilitate the acceptance of the recycled material by the U.S. Food and Drug Administration (FDA) is that the impurities in the recycled material need to be at or below the levels present in the starting material. Therefore, the amount of potassium (K) in purified MoO 3 powder should be below 20 ppm; this will require a decontamination factor for removal of K to be ~1 × 10 5. Such a low K-contamination level will also prevent the production of large amounts of K-42 during irradiation of Mo-100. Based on economic concerns (due to the significant cost of enriched Mo-100) recycling Mo requires the conversion of K 2MoO 4 in a 5 M KOH solution to MoO 3 powder with high Mo recovery yields (>98%).« less

Method for synthesizing thin film electrodes

DOEpatents

Boyle, Timothy J [Albuquerque, NM

2007-03-13

A method for making a thin-film electrode, either an anode or a cathode, by preparing a precursor solution using an alkoxide reactant, depositing multiple thin film layers with each layer approximately 500 1000 .ANG. in thickness, and heating the layers to above 600.degree. C. to achieve a material with electrochemical properties suitable for use in a thin film battery. The preparation of the anode precursor solution uses Sn(OCH.sub.2C(CH.sub.3).sub.3).sub.2 dissolved in a solvent in the presence of HO.sub.2CCH.sub.3 and the cathode precursor solution is formed by dissolving a mixture of (Li(OCH.sub.2C(CH.sub.3).sub.3)).sub.8 and Co(O.sub.2CCH.sub.3).H.sub.2O in at least one polar solvent.

Rates of arsenopyrite oxidation by oxygen and Fe(III) at pH 1.8-12.6 and 15-45 degrees C.

PubMed

Yu, Yunmei; Zhu, Yongxuan; Gao, Zhenmin; Gammons, Christopher H; Li, Denxian

2007-09-15

The oxidation rate of arsenopyrite by dissolved oxygen was measured using a mixed flow reactor at dissolved O2 concentrations of 0.007-0.77 mM, pH 1.8-12.6, and temperatures of 15-45 degrees C. As(III) was the dominant redox species (>75%) in the experimental system, and the As(III)/As(V) ratio of effluent waters did not change with pH. The results were used to derive the following rate law expression (valid between pH 1.8 and 6.4): r = 10((-2211 +/- 57)T) (mO2)(0.45 +/- 0.05), where r is the rate of release of dissolved As in mol m(-2) s(-1) and T is in Kelvin. Activation energies (Ea) for oxidation of arsenopyrite by 02 at pH 1.8 and 5.9 are 43 and 57 kJ/mol, respectively, and they compare to an Ea value of 16 kJ/mol for oxidation by Fe(III) at pH 1.8. Apparent As release rates passed through a minimum in the pH range 7-8, which may have been due to oxidation of Fe2+ to hydrous ferric oxide (HFO) with attenuation of dissolved As onto the freshly precipitated HFO.

Relative contributions of copper oxide nanoparticles and dissolved copper to Cu uptake kinetics of Gulf killifish (Fundulus grandis) embryos

USGS Publications Warehouse

Jiang, Chuanjia; Castellon, Benjamin T.; Matson, Cole W.; Aiken, George R.; Hsu-Kim, Heileen

2017-01-01

The toxicity of soluble metal-based nanomaterials may be due to the uptake of metals in both dissolved and nanoparticulate forms, but the relative contributions of these different forms to overall metal uptake rates under environmental conditions are not quantitatively defined. Here, we investigated the linkage between the dissolution rates of copper(II) oxide (CuO) nanoparticles (NPs) and their bioavailability to Gulf killifish (Fundulus grandis) embryos, with the aim of quantitatively delineating the relative contributions of nanoparticulate and dissolved species for Cu uptake. Gulf killifish embryos were exposed to dissolved Cu and CuO NP mixtures comprising a range of pH values (6.3–7.5) and three types of natural organic matter (NOM) isolates at various concentrations (0.1–10 mg-C L–1), resulting in a wide range of CuO NP dissolution rates that subsequently influenced Cu uptake. First-order dissolution rate constants of CuO NPs increased with increasing NOM concentration and for NOM isolates with higher aromaticity, as indicated by specific ultraviolet absorbance (SUVA), while Cu uptake rate constants of both dissolved Cu and CuO NP decreased with NOM concentration and aromaticity. As a result, the relative contribution of dissolved Cu and nanoparticulate CuO species for the overall Cu uptake rate was insensitive to NOM type or concentration but largely determined by the percentage of CuO that dissolved. These findings highlight SUVA and aromaticity as key NOM properties affecting the dissolution kinetics and bioavailability of soluble metal-based nanomaterials in organic-rich waters. These properties could be used in the incorporation of dissolution kinetics into predictive models for environmental risks of nanomaterials.

Photorespiration and carbon limitation determine productivity in temperate seagrasses.

PubMed

Buapet, Pimchanok; Rasmusson, Lina M; Gullström, Martin; Björk, Mats

2013-01-01

The gross primary productivity of two seagrasses, Zostera marina and Ruppia maritima, and one green macroalga, Ulva intestinalis, was assessed in laboratory and field experiments to determine whether the photorespiratory pathway operates at a substantial level in these macrophytes and to what extent it is enhanced by naturally occurring shifts in dissolved inorganic carbon (DIC) and O2 in dense vegetation. To achieve these conditions in laboratory experiments, seawater was incubated with U. intestinalis in light to obtain a range of higher pH and O2 levels and lower DIC levels. Gross photosynthetic O2 evolution was then measured in this pretreated seawater (pH, 7.8-9.8; high to low DIC:O2 ratio) at both natural and low O2 concentrations (adjusted by N2 bubbling). The presence of photorespiration was indicated by a lower gross O2 evolution rate under natural O2 conditions than when O2 was reduced. In all three macrophytes, gross photosynthetic rates were negatively affected by higher pH and lower DIC. However, while both seagrasses exhibited significant photorespiratory activity at increasing pH values, the macroalga U. intestinalis exhibited no such activity. Rates of seagrass photosynthesis were then assessed in seawater collected from the natural habitats (i.e., shallow bays characterized by high macrophyte cover and by low DIC and high pH during daytime) and compared with open baymouth water conditions (where seawater DIC is in equilibrium with air, normal DIC, and pH). The gross photosynthetic rates of both seagrasses were significantly higher when incubated in the baymouth water, indicating that these grasses can be significantly carbon limited in shallow bays. Photorespiration was also detected in both seagrasses under shallow bay water conditions. Our findings indicate that natural carbon limitations caused by high community photosynthesis can enhance photorespiration and cause a significant decline in seagrass primary production in shallow waters.

Composition characteristics and regularities of dissolving of hydroxyapatite materials obtained in water solutions with varied content of silicate ions

NASA Astrophysics Data System (ADS)

Solonenko, A. P.

2018-01-01

Research aimed at developing new bioactive materials for the repair of defects in bone tissues, do not lose relevance due to the strengthening of the regenerative approach in medicine. From this point of view, materials based on calcium phosphates, including silicate ions, consider as one of the most promising group of substances. Methods of synthesis and properties of hydroxyapatite doped with various amounts of SiO4 4- ions are described in literature. In the present work synthesis of a solid phase in the systems Ca(NO3)2 - (NH4)2HPO4 - Na2SiO3 - NH4OH - H2O (Cca/CP = 1.70) performed with a wide range of sodium silicate additive concentration (y = CSi/CP = 0 ÷ 5). It is established that under the studied conditions at y ≥ 0.3 highly dispersed poorly crystallized apatite containing isomorphic impurities of CO3 2- and SiO4 4- precipitates in a mixture with calcium hydrosilicate and SiO2. It is shown that the resulting composites can gradually dissolve in physiological solution and initiate passive formation of the mineral component of hard tissues.

Evaluating the spatial variation of total mercury in young-of-year yellow perch (Perca flavescens), surface water and upland soil for watershed-lake systems within the southern Boreal Shield

USGS Publications Warehouse

Gabriel, M.C.; Kolka, R.; Wickman, T.; Nater, E.; Woodruff, Laurel G.

2009-01-01

The primary objective of this research is to investigate relationships between mercury in upland soil, lake water and fish tissue and explore the cause for the observed spatial variation of THg in age one yellow perch (Perca flavescens) for ten lakes within the Superior National Forest. Spatial relationships between yellow perch THg tissue concentration and a total of 45 watershed and water chemistry parameters were evaluated for two separate years: 2005 and 2006. Results show agreement with other studies where watershed area, lake water pH, nutrient levels (specifically dissolved NO3−-N) and dissolved iron are important factors controlling and/or predicting fish THg level. Exceeding all was the strong dependence of yellow perch THg level on soil A-horizon THg and, in particular, soil O-horizon THg concentrations (Spearman ρ = 0.81). Soil B-horizon THg concentration was significantly correlated (Pearson r = 0.75) with lake water THg concentration. Lakes surrounded by a greater percentage of shrub wetlands (peatlands) had higher fish tissue THg levels, thus it is highly possible that these wetlands are main locations for mercury methylation. Stepwise regression was used to develop empirical models for the purpose of predicting the spatial variation in yellow perch THg over the studied region. The 2005 regression model demonstrates it is possible to obtain good prediction (up to 60% variance description) of resident yellow perch THg level using upland soil O-horizon THg as the only independent variable. The 2006 model shows even greater prediction (r2 = 0.73, with an overall 10 ng/g [tissue, wet weight] margin of error), using lake water dissolved iron and watershed area as the only model independent variables. The developed regression models in this study can help with interpreting THg concentrations in low trophic level fish species for untested lakes of the greater Superior National Forest and surrounding Boreal ecosystem.

N2O EMISSIONS FROM STREAMS IN THE NEUSE RIVER WATERSHED, NORTH CAROLINA

EPA Science Inventory

The paper presents N₂O emission data from 11 sites in the Neuse River watershed. Emissions were measured using a static surface enclosure technique deployed on eight sites on the main river channel and three tributary sites. Ancillary data collected included dissolved ...

Regional-scale controls on dissolved nitrous oxide in the Upper Mississippi River

USDA-ARS?s Scientific Manuscript database

Bottom-up estimates of riverine nitrous oxide (N2O) emissions developed by the Intergovernmental Panel on Climate Change (IPCC) assume a constant emission factor (EF5r) that predicts N2O production from anthropogenic nitrogen inputs. This relation ignores any direct stream water biochemical charact...

Solubility of platinum-arsenide melt and sperrylite in synthetic basalt at 0.1 MPa and 1200 °C with implications for arsenic speciation and platinum sequestration in mafic igneous systems

NASA Astrophysics Data System (ADS)

Canali, A. C.; Brenan, J. M.; Sullivan, N. A.

2017-11-01

To better understand the Pt-As association in natural magmas, experiments were done at 1200 °C and 0.1 MPa to measure the solubility of Pt and Pt-arsenide phases (melt and sperrylite, PtAs2), as well as to determine the oxidation state, and identify evidence for Pt-As complexing, in molten silicate. Samples consisting of synthetic basalt contained in chromite crucibles were subject to three experimental procedures. In the first, platinum solubility in the synthetic basalt was determined without added arsenic by equilibrating the sample with a platinum source (embedded wire or bead) in a gas-mixing furnace. In the second, the sample plus a Pt-arsenide source was equilibrated in a vacuum-sealed fused quartz tube containing a solid-oxide oxygen buffer. The third approach involved two steps: first equilibrating the sample in a gas-mixing furnace, then with added arsenide melt in a sealed quartz tube. Oxygen fugacity was estimated in the latter step using chromite/melt partitioning of vanadium. Method two experiments done at high initial arsenic activity (PtAs melt + PtAs2), showed significant loss of arsenic from the sample, the result of vapour transfer to newly-formed arsenide phases in the buffer. Method three experiments showed no loss of arsenic, yielding a uniform final distribution in the sample. Analyses of run-product glasses from experiments which did not show arsenic loss reveal significant increase in arsenic concentrations with fO2, varying from ∼10 ppm (FMQ-3.25) to >10,000 ppm (FMQ + 5.5). Despite very high arsenic loadings (>1000 ppm), the solubility of Pt is similar in arsenic-bearing and arsenic-free glasses. The variation in arsenic solubility with fO2 shows a linear relationship, that when corrected for the change in the activity of dissolved arsenic with the melt ferric/ferrous ratio, yields a solubility-fO2 relationship consistent with As3+ as the dissolved species. This result is confirmed by X-ray absorption near edge structure (XANES) determination on run-product glasses. Levels of arsenic required for Pt-arsenide saturation are 50-500 ppm over the fO2 range of most terrestrial basalts (FMQ to FMQ-2), >100× higher than the arsenic concentrations typical of such magmas, indicating significant enrichment of arsenic is required if Pt-arsenide saturation is to occur. In contrast, the level of dissolved Pt required to saturate in sperrylite is >8× lower than for pure Pt, suggesting that arsenic enrichment could lead to Pt removal at concentrations much less than required for pure metal saturation.

Fractionation for further conversion: from raw corn stover to lactic acid

NASA Astrophysics Data System (ADS)

He, Ting; Jiang, Zhicheng; Wu, Ping; Yi, Jian; Li, Jianmei; Hu, Changwei

2016-12-01

Fractionation is considered to be one promising strategy to utilize raw biomass to its fullest and produce chemicals with high selectivity. Herein, ethanol/H2O (1/1, v/v) co-solvent with 0.050 M oxalic acid is used to simultaneously fractionate 88.0 wt% of hemicellulose and 89.2 wt% of lignin in corn stover, while cellulose is not obviously degraded. H2O dissolves hemicellulose, G unit and those with β-O-4 linkage of lignin; whereas ethanol extracts G and S units as well as the skeleton with β-5 and β-β linkages of lignin. Oxalic acid effectively catalyzes the hydrolysis of hemicellulose and breaks the intermolecular linkages between hemicellulose and lignin, therefore further promotes the release of lignin. The dissolved hemicelluloses derivatives are reprocessed to produce lactic acid obtaining a high yield of 79.6 wt% with 90% selectivity by the catalysis of MgO. The remained cellulose and recovered lignin can be used further as feedstock to produce chemicals.

Fractionation for further conversion: from raw corn stover to lactic acid

PubMed Central

He, Ting; Jiang, Zhicheng; Wu, Ping; Yi, Jian; Li, Jianmei; Hu, Changwei

2016-01-01

Fractionation is considered to be one promising strategy to utilize raw biomass to its fullest and produce chemicals with high selectivity. Herein, ethanol/H2O (1/1, v/v) co-solvent with 0.050 M oxalic acid is used to simultaneously fractionate 88.0 wt% of hemicellulose and 89.2 wt% of lignin in corn stover, while cellulose is not obviously degraded. H2O dissolves hemicellulose, G unit and those with β-O-4 linkage of lignin; whereas ethanol extracts G and S units as well as the skeleton with β-5 and β-β linkages of lignin. Oxalic acid effectively catalyzes the hydrolysis of hemicellulose and breaks the intermolecular linkages between hemicellulose and lignin, therefore further promotes the release of lignin. The dissolved hemicelluloses derivatives are reprocessed to produce lactic acid obtaining a high yield of 79.6 wt% with 90% selectivity by the catalysis of MgO. The remained cellulose and recovered lignin can be used further as feedstock to produce chemicals. PMID:27917955

High temperature reaction between sea salt deposit and (U,Zr)O2 simulated corium debris

NASA Astrophysics Data System (ADS)

Takano, Masahide; Nishi, Tsuyoshi

2013-11-01

In order to clarify the possible impacts of seawater injection on the chemical and physical state of the corium debris formed in the severe accident at Fukushima Daiichi Nuclear Power Plants, the high temperature reaction between sea salt deposit and (U,Zr)O2 simulated corium debris (sim-debris) was examined in the temperature range from 1088 to 1668 K. A dense layer of calcium and sodium uranate formed on the surface of a sim-debris pellet at 1275 K under airflow, with the thickness of over 50 μm. When the oxygen partial pressure is low, calcium is likely to dissolve into the cubic sim-debris phase to form solid solution (Ca,U,Zr)O2+x. The diffusion depth was 5-6 μm from the surface, subjected to 1275 K for 12 h. The crystalline MgO remains affixed on the surface as the main residue of salt components. A part of it can also dissolve into the sim-debris.

Perfluorocarbon emulsion therapy attenuates pneumococcal infection in sickle cell mice.

PubMed

Helmi, Nawal; Andrew, Peter W; Pandya, Hitesh C

2015-05-15

Impaired immunity and tissue hypoxia-ischemia are strongly linked with Streptococcus pneumoniae pathogenesis in patients with sickle cell anemia. Perfluorocarbon emulsions (PFCEs) have high O2-dissolving capacity and can alleviate tissue hypoxia. Here, we evaluate the effects of intravenous PFCE therapy in transgenic sickle cell (HbSS) mice infected with S. pneumoniae. HbSS and C57BL/6 (control) mice intravenously infected with S. pneumoniae were treated intravenously with PFCE or phosphate-buffered saline (PBS) and then managed in either air/O2 (FiO2 proportion, 50%; hereafter referred to as the PFCE-O2 and PBS-O2 groups) or air only (hereafter, the PFCE-air and PBS-air groups) gas mixtures. Lungs were processed for leukocyte and bacterial counts and cytokine measurements. HbSS mice developed severe pneumococcal infection significantly faster than C57BL/6 mice (Kaplan-Maier analysis, P < .05). PFCE-O2-treated HbSS mice had significantly better survival at 72 hours than HBSS mice treated with PFCE-air, PBS-O2, or PBS-air (P < .05). PFCE-O2-treated HbSS mice also had significantly lower pulmonary leukocyte counts, lower interleukin 1β and interferon γ levels, and higher interleukin 10 levels than PFCE-air-treated HbSS mice. Clearance of S. pneumoniae from lungs of HbSS mice or C57BL/6 mice was not altered by PFCE treatment. Improved survival of PFCE-O₂-treated HbSS mice infected with S. pneumoniae is associated with altered pulmonary inflammation but not enhanced bacterial clearance. © The Author 2014. Published by Oxford University Press on behalf of the Infectious Diseases Society of America. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Microwave-assisted template-free synthesis of butterfly-like CuO through Cu2Cl(OH)3 precursor and the electrochemical sensing property

NASA Astrophysics Data System (ADS)

Xie, Hanjie; Zhu, Lianjie; Zheng, Wenjun; Zhang, Jing; Gao, Fubo; Wang, Yan

2016-11-01

An energy-efficient and environmentally friendly microwave-assisted method was adopted for synthesis of butterfly-like CuO assembled by nanosheets through a Cu2Cl(OH)3 precursor, using no template. Formation mechanism of the butterfly-like CuO was explored and discussed systematically for the first time on the basis of both experimental results and crystal structure transformations in atomic level. The electrochemical sensing properties of the butterfly-like CuO modified electrode to ascorbic acid (AA) were studied for the first time. The results reveal that Cu(OH)2 nanowires were formed once the Cu2+ ions, located in between two CuO4 parallelogram chains of a Cu2Cl(OH)3 precursor, dissolve into the solution as Cu(OH)42- complex ions after ion exchange reactions and simultaneous assemble along a axis. Upon microwave irradiation, the adjacent CuO4 parallelogram chains of the Cu(OH)2 nanowires dehydrate and assemble along c axis, forming CuO nanosheets with (002) as the main exposed facet, which were further assembled to butterfly-like CuO under the action of microwave field, suggesting that microwave field functions like a 'directing agent'. The butterfly-like CuO modified electrode shows good electrochemical sensing properties to AA with a low detecting limit, short response time and wide linear response range.

The effect of probe choice and solution conditions on the apparent photoreactivity of dissolved organic matter.

PubMed

Maizel, Andrew C; Remucal, Christina K

2017-08-16

Excited triplet states of dissolved organic matter ( 3 DOM) are quantified directly with the species-specific probes trans,trans-hexadienoic acid (HDA) and 2,4,6-trimethylphenol (TMP), and indirectly with the singlet oxygen ( 1 O 2 ) probe furfuryl alcohol (FFA). Although previous work suggests that these probe compounds may be sensitive to solution conditions, including dissolved organic carbon concentration ([DOC]) and pH, and may quantify different 3 DOM subpopulations, the probes have not been systematically compared. Therefore, we quantify the apparent photoreactivity of diverse environmental waters using HDA, TMP, and FFA. By conducting experiments under ambient [DOC] and pH, with standardized [DOC] and pH, and with solid phase extraction isolates, we demonstrate that much of the apparent dissimilarity in photochemical measurements is attributable to solution conditions, rather than intrinsic differences in 3 DOM production. In general, apparent quantum yields (Φ 1 O 2 ≥ Φ 3 DOM,TMP ≫ Φ 3 DOM,HDA ) and pseudo-steady state concentrations ([ 1 O 2 ] ss > [ 3 DOM] ss,TMP > [ 3 DOM] ss,HDA ) show consistent relationships in all waters under standardized conditions. However, intrinsic differences in 3 DOM photoreactivity are apparent between DOM from diverse sources, as seen in the higher Φ 1 O 2 and lower Φ 3 DOM,TMP of wastewater effluents compared with oligotrophic lakes. Additionally, while conflicting trends in photoreactivity are observed under ambient conditions, all probes observe quantum yields increasing from surface wetlands to terrestrially influenced waters to oligotrophic lakes under standardized conditions. This work elucidates how probe selection and solution conditions influence the apparent photoreactivity of environmental waters and confirms that 3 DOM or 1 O 2 probes cannot be used interchangeably in waters that vary in [DOC], pH, or DOM source.

Chemical transformations during aging of zerovalent iron nanoparticles in the presence of common groundwater dissolved constituents.

PubMed

Reinsch, Brian C; Forsberg, Brady; Penn, R Lee; Kim, Christopher S; Lowry, Gregory V

2010-05-01

Nanoscale zerovalent iron (NZVI) that was aged in simulated groundwater was evaluated for alterations in composition and speciation over 6 months to understand the possible transformations NZVI could undergo in natural waters. NZVI was exposed to 10 mN of various common groundwater anions (Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), and HCO(3)(-)) or to dissolved oxygen (saturated, approximately 9 mg/L). Fresh and exposed NZVI samples, along with Fe-oxide model compounds, were then analyzed using synchrotron radiation X-ray absorption spectroscopy (XAS) to yield both relative oxidation state, using the X-ray absorption near edge structure (XANES), and quantitative speciation information regarding the types and proportions of mineral species present, from analysis of the extended X-ray absorption fine structure (EXAFS). Over 1 month of aging the dissolved anions inhibited the oxidation of the NZVI to varying degrees. Aging for 6 months, however, resulted in average oxidation states that were similar to each other regardless of the anion used, except for nitrate. Nitrate passivated the NZVI surface such that even after 6 months of aging the particles retained nearly the same mineral and Fe(0) content as fresh NZVI. Linear least-squares combination fitting (LCF) of the EXAFS spectra for 1 month-aged samples indicated that the oxidized particles remain predominantly a binary phase system containing Fe(0) and Fe(3)O(4), while the 6 month aged samples contained additional mineral phases such as vivianite (Fe(3)(PO(4))(2).8H(2)O) and iron sulfate species, possibly schwertmannite (Fe(3+)(16)O(16)(OH,SO(4))(12-13).10-12H(2)O). The presence of these additional mineral species was confirmed using synchrotron-based X-ray diffraction (XRD). NZVI exposed to water saturated with dissolved oxygen showed a rapid (<24 h) loss of Fe(0) and evolved both magnetite and maghemite (gamma-Fe(2)O(3)) within the oxide layer. These findings have implications toward the eventual fate, transport, and toxicity of NZVI used for groundwater remediation.

A Multi-Pumping Flow System for In Situ Measurements of Dissolved Manganese in Aquatic Systems

PubMed Central

Meyer, David; Prien, Ralf D.; Dellwig, Olaf; Waniek, Joanna J.; Schuffenhauer, Ingo; Donath, Jan; Krüger, Siegfried; Pallentin, Malte; Schulz-Bull, Detlef E.

2016-01-01

A METals In Situ analyzer (METIS) has been used to determine dissolved manganese (II) concentrations in the subhalocline waters of the Gotland Deep (central Baltic Sea). High-resolution in situ measurements of total dissolved Mn were obtained in near real-time by spectrophotometry using 1-(2-pyridylazo)-2-naphthol (PAN). PAN is a complexing agent of dissolved Mn and forms a wine-red complex with a maximum absorbance at a wavelength of 562 nm. Results are presented together with ancillary temperature, salinity, and dissolved O2 data. Lab calibration of the analyzer was performed in a pressure testing tank. A detection limit of 77 nM was obtained. For validation purposes, discrete water samples were taken by using a pump-CTD system. Dissolved Mn in these samples was determined by an independent laboratory based method (inductively coupled plasma–optical emission spectrometry, ICP-OES). Mn measurements from both METIS and ICP-OES analysis were in good agreement. The results showed that the in situ analysis of dissolved Mn is a powerful technique reducing dependencies on heavy and expensive equipment (pump-CTD system, ICP-OES) and is also cost and time effective. PMID:27916898

Biogeochemical controls on diel cycling of stable isotopes of dissolved 02 and dissolved inorganic carbon in the Big Hole River, Montana

USGS Publications Warehouse

Parker, Stephen R.; Poulson, Simon R.; Gammons, Christopher H.; DeGrandpre, Michael D.

2005-01-01

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in δ18O of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13‰) cycles in δ18O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in δ18O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O2 and C budgets in rivers and may also be applicable to lake and groundwater systems.

Cyanobacterial and microcystins dynamics following the application of hydrogen peroxide to waste stabilisation ponds

NASA Astrophysics Data System (ADS)

Barrington, D. J.; Ghadouani, A.; Ivey, G. N.

2013-02-01

Cyanobacteria and cyanotoxins are a risk to human and ecological health, and a hindrance to biological wastewater treatment. This study investigated the use of hydrogen peroxide (H2O2) for the removal of cyanobacteria and cyanotoxins from within waste stabilization ponds (WSPs). The daily dynamics of cyanobacteria and microcystins (a commonly occurring cyanotoxin) were examined following the addition of H2O2 to wastewater within both the laboratory and at the full-scale within a WSP. Hydrogen peroxide treatment at concentrations ≥ 10-4 g H2O2 μg-1 of total phytoplankton chlorophyll a led to the death of cyanobacteria, in turn releasing intracellular microcystins to the dissolved state. In the full-scale trial, dissolved microcystins were then degraded to negligible concentrations by H2O2 and environmental processes within five days. A shift in the phytoplankton assemblage towards beneficial chlorophyta species was also observed within days of H2O2 addition. However, within weeks, the chlorophyta population was significantly reduced by the re-establishment of toxic cyanobacterial species. This re-establishment was likely due to the inflow of cyanobacteria from ponds earlier in the treatment train, suggesting that whilst H2O2 may be a suitable short-term management technique, it must be coupled with control over inflows if it is to improve WSP performance in the longer term.

The Effects of Elevated pCO2, Hypoxia and Temperature on ...

EPA Pesticide Factsheets

Estuarine fish are acclimated to living in an environment with rapid and frequent changes in temperature, salinity, pH, and dissolved oxygen (DO) levels; the physiology of these organisms is well suited to cope with extreme thermal, hypercapnic, and hypoxic stress. While the adverse effects of low dissolved oxygen levels on estuarine fish has been well-documented, the interaction between low DO and elevated pCO2 is not well understood. There is some evidence that low DO and elevated pCO2 interact antagonistically, however little information exists on how projected changes of pCO2 levels in near-shore waters may affect estuarine species, and how these changes may specifically interact with dissolved oxygen and temperature. We explored the survivability of 7-day post fertilization sheepshead minnow, Cyprinodon variegatus, using short term exposure to the combined effects of elevated pCO2 (~1300 µatm; IPCC RCP 8.5) and low dissolved oxygen levels (~2 mg/L). Additionally, we determined if the susceptibility of these fish to elevated pCO2 and low DO was influenced by increases in temperature from 27.5°C to 35°C. Results from this study and future studies will be used to identify estuarine species and lifestages sensitive to the combined effects of elevated pCO2 and low dissolved oxygen. This project was created in order to better understand the interactive effects of projected pCO2 levels and hypoxia in estuarine organisms. This work is currently focused on the se

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

USGS Publications Warehouse

Church, C.D.; Wilkin, R.T.; Alpers, Charles N.; Rye, R.O.; Blaine, R.B.

2007-01-01

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

PubMed Central

Church, Clinton D; Wilkin, Richard T; Alpers, Charles N; Rye, Robert O; McCleskey, R Blaine

2007-01-01

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. PMID:17956615

Experimental Study on the Behavior of TiN and Ti2O3 Inclusions in Contact with CaO‐Al2O3‐SiO2‐MgO Slags

PubMed Central

Bernhard, C.

2017-01-01

TiN and Ti2O3 are the predominant inclusion types in Ti-alloyed ferritic chromium stainless steels. In order to ensure the required steel cleanness level, an effective removal of such inclusions in the slag during secondary metallurgy is essential. This inclusion removal predominantly takes place via dissolution of the inclusion in the slag. The dissolution behavior of TiN and Ti2O3 in CaO-SiO2-Al2O3-MgO slags as well as their agglomeration behavior in the liquid steel is investigated using High Temperature Laser Scanning Confocal Microscopy and Tammann Furnace experiments. Thermodynamic calculations are performed using FactSage 7.0. The behavior of TiN is observed to be completely different to that of oxides. Ti2O3 dissolves quickly in slags, and its dissolution behavior is comparable to that of other already well examined oxides. In contrast, TiN shows a very intense gas reaction which is attributed to the release of nitrogen during contact with slag. Slags with higher SiO2 content show a significantly higher ability for the dissolution of TiN as compared to Al2O3-rich slags. The gas reaction is found to also significantly influence the final steel cleanness. Despite the easy absorption of TiN in the slag, the formed nitrogen supports the formation of pinholes in the steel. PMID:29109805

Sonochemiluminescence of lucigenin: Evidence of superoxide radical anion formation by ultrasonic irradiation

NASA Astrophysics Data System (ADS)

Matsuoka, Masanori; Takahashi, Fumiki; Asakura, Yoshiyuki; Jin, Jiye

2016-07-01

The sonochemiluminescence (SCL) behavior of lucigenin (Luc2+) has been studied in aqueous solutions irradiated with 500 kHz ultrasound. Compared with the SCL of a luminol system, a tremendously increased SCL intensity is observed from 50 µM Luc2+ aqueous solution (pH =11) when small amounts of coreactants such as 2-propanol coexist. It is shown that SCL intensity strongly depends on the presence of dissolved gases such as air, O2, N2, and Ar. The highest SCL intensity is obtained in an O2-saturated solution, indicating that molecular oxygen is required to generate SCL. Since SCL intensity is quenched completely in the presence of superoxide dismutase (SOD), an enzyme that can catalyze the disproportionation of O2 •-, the generation of O2 •- in the ultrasonic reaction field is important in the SCL of Luc2+. In this work, the evidence of O2 •- production is examined by a spectrofluorometric method using 2-(2-pyridyl)benzothiazoline as the fluorescent probe. The results indicate that the yield of O2 •- is markedly increased in the O2-saturated solutions when a small amount of 2-propanol coexists, which is consistent with the results of SCL measurements. 2-Propanol in the interfacial region of a cavitation bubble reacts with a hydroxyl radical (•OH) to form a 2-propanol radical, CH3C•(OH)CH3, which can subsequently react with dissolved oxygen to generate O2 •-. The most likely pathways for SCL as well as the spatial distribution of SCL in a microreactor are discussed in this study.

The self-setting properties and in vitro bioactivity of tricalcium silicate.

PubMed

Zhao, Wenyuan; Wang, Junying; Zhai, Wanyin; Wang, Zheng; Chang, Jiang

2005-11-01

In this study, tricalcium silicate (Ca(3)SiO(5)), as a new promising injectable bioactive material, was employed to investigate its physical and chemical properties for an injectable bioactive cement filler. The workable Ca(3)SiO(5) pastes with a liquid to powder (L/P) ratio of 0.8--.2 mlg(-1)could be injected for 15--60 min (nozzle diameter 2.0mm). The setting process yielded cellular structures with compressive strength of 6.4--20.2 MPa after 2--28 days. The in vitro bioactivity of Ca(3)SiO(5) paste was investigated by soaking in simulated body fluid (SBF) for various periods. The result showed that the Ca(3)SiO(5) paste could induce hydroxyapatite (HA) formation and dissolve slowly in SBF. The result of indirect cytotoxicity evaluation indicated that Ca(3)SiO(5) paste had a stimulatory effect on cell growth in a certain concentration range. The exothermic process showed that Ca(3)SiO(5) had lower heat evolution rate during the hydration as compared to calcium phosphate cement (CPC). Our results indicated that Ca(3)SiO(5) paste was bioactive and dissolvable, and it is a progressive candidate for further investigation as injectable tissue repairing substitute.

Method for generating a crystalline .sup.99 MoO.sub.3 product and the isolation .sup.99m Tc compositions therefrom

DOEpatents

Bennett, Ralph G.; Christian, Jerry D.; Kirkham, Robert J.; Tranter, Troy J.

1998-01-01

An improved method for producing .sup.99m Tc compositions. .sup.100 Mo metal is irradiated with photons in a particle (electron) accelerator to produce .sup.99 Mo metal which is dissolved in a solvent. A solvated .sup.99 Mo product is then dried to generate a supply of .sup.99 MoO.sub.3 crystals. The crystals are thereafter heated at a temperature which will sublimate the crystals and form a gaseous mixture containing vaporized .sup.99m TcO.sub.3 and vaporized .sup.99m TcO.sub.2 but will not cause the production of vaporized .sup.99 MoO.sub.3. The mixture is then combined with an oxidizing gas to generate a gaseous stream containing vaporized .sup.99m Tc.sub.2 O.sub.7. Next, the gaseous stream is cooled to a temperature sufficient to convert the vaporized .sup.99m Tc.sub.2 O.sub.7 into a condensed .sup.99m Tc-containing product. The product has high purity levels resulting from the use of reduced temperature conditions and ultrafine crystalline .sup.99 MoO.sub.3 starting materials with segregated .sup.99m Tc compositions therein which avoid the production of vaporized .sup.99 MoO.sub.3 contaminants.

Responses and recovery assessment of continuously cultured Nitrosomonas europaea under chronic ZnO nanoparticle stress: Effects of dissolved oxygen.

PubMed

Wu, Junkang; Chang, Yan; Gao, Huan; Liang, Geyu; Yu, Ran; Ding, Zhen

2018-03-01

Although the antibacterial performances of emerging nanoparticles (NPs) have been extensively explored in the nitrifying systems, the impacts of dissolved oxygen (DO) levels on their bio-toxicities to the nitrifiers and the impaired cells' recovery potentials have seldom been addressed yet. In this study, the physiological and transcriptional responses of the typical ammonia oxidizers - Nitrosomonas europaea in a chemostat to the chronic ZnO NP exposure under different DO conditions were investigated. The results indicated that the cells in steady-growth state in the chemostat were more persevering than batch cultured ones to resist ZnO NP stress despite the dose-dependent NP inhibitory effects were observed. In addition, the occurred striking over-expressions of amoA and hao genes at the initial NP exposure stage suggested the cells' self-regulation potentials at the transcriptional level. The low DO (0.5 mg/L) cultured cells displayed higher sensitivity to NP stress than the high DO (2.0 mg/L) cultured ones, probably owning to the inefficient oxygen-dependent electron transfer from ammonia oxidation for energy conversion/production. The following 12-h NP-free batch recovery assays revealed that both high and low DO cultured cells possessed the physiological and metabolic activity recovery potentials, which were in negative correlation with the NP exposure time. The duration of NP stress and the resulting NP dissolution were critical for the cells' damage levels and their performance recoverability. The membrane preservation processes and the associated metabolism regulations were expected to actively participate in the cells' self-adaption to NP stress and thus be responsible for their metabolic activities recovery. Copyright © 2017 Elsevier Ltd. All rights reserved.

Field continuous measurement of dissolved gases with a CF-MIMS: Applications to the physics and biogeochemistry of groundwater flow

NASA Astrophysics Data System (ADS)

Chatton, Eliot; Labasque, Thierry; de La Bernardie, Jérôme; Guihéneuf, Nicolas; Bour, Olivier; Aquilina, Luc

2017-04-01

In the perspective of a temporal and spatial exploration of aquatic environments (surface and ground water), we developed a technique for precise field continuous measurements of dissolved gases (N2, O2, CO2, CH4, N2O, H2, He, Ne, Ar, Kr, Xe). With a large resolution (from 1×10-9 to 1×10-2 ccSTP/g) and a capability of high frequency analysis (1 measure every 2 seconds), the CF-MIMS (Continuous Flow Membrane Inlet Mass Spectrometer) is an innovative tool allowing the investigation of a large panel of hydrological and biogeochemical processes in aquatic systems. Based on the available MIMS technology, this study introduces the development of the CF-MIMS (conception for field experiments, membrane choices, ionisation) and an original calibration procedure allowing the quantification of mass spectral overlaps and temperature effects on membrane permeability. This study also presents two field applications of the CF-MIMS (Chatton et al, 2016) involving the well-logging of dissolved gases and the implementation of groundwater tracer tests with dissolved 4He. The results demonstrate the analytical capabilities of the CF-MIMS in the field. Therefore, the CF-MIMS is a valuable tool for the field characterisation of biogeochemical reactivity, aquifer transport properties, groundwater recharge, groundwater residence time and aquifer-river exchanges from few hours to several weeks experiments. Eliot Chatton, Thierry Labasque, Jérôme de La Bernardie, Nicolas Guihéneuf, Olivier Bour and Luc Aquilina; Field Continuous Measurement of Dissolved Gases with a CF-MIMS: Applications to the Physics and Biogeochemistry of Groundwater Flow; Environmental Science & Technology, in press, 2016.

Low temperature dissolution flowsheet for plutonium metal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel, W. E.; Almond, P. M.; Rudisill, T. S.

2016-05-01

The H-Canyon flowsheet used to dissolve Pu metal for PuO 2 production utilizes boiling HNO 3. SRNL was requested to develop a complementary dissolution flowsheet at two reduced temperature ranges. The dissolution and H 2 generation rates of Pu metal were investigated using a dissolving solution at ambient temperature (20-30 °C) and for an intermediate temperature of 50-60 °C. Additionally, the testing included an investigation of the dissolution rates and characterization of the off-gas generated from the ambient temperature dissolution of carbon steel cans and the nylon bags that contain the Pu metal when charged to the dissolver.

Gas Transfer Controls Carbon Limitation During Biomass Production by Marine Microalgae.

PubMed

Tamburic, Bojan; Evenhuis, Christian R; Suggett, David J; Larkum, Anthony W D; Raven, John A; Ralph, Peter J

2015-08-24

This study presents the first in-depth analysis of CO2 limitation on the biomass productivity of the biofuel candidate marine microalga Nannochloropsis oculata. Net photosynthesis decreased by 60% from 125 to 50 μmol O2 L(-1)h(-1) over a 12 h light cycle as a direct result of carbon limitation. Continuous dissolved O2 and pH measurements were used to develop a detailed diurnal mechanism for the interaction between photosynthesis, gas exchange and carbonate chemistry in the photo-bioreactor. Gas exchange determined the degree of carbon limitation experienced by the algae. Carbon limitation was confirmed by delivering more CO2 , which increased net photosynthesis back to its steady-state maximum. This study highlights the importance of maintaining replete carbon concentrations in photo-bioreactors and other culturing facilities, either by constant pH operation or preferably by designing a feedback loop based on the dissolved O2 concentration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Singlet oxygen in the coupled photochemical and biochemical oxidation of dissolved organic matter.

PubMed

Cory, Rose M; McNeill, Kristopher; Cotner, James P; Amado, Andre; Purcell, Jeremiah M; Marshall, Alan G

2010-05-15

Dissolved organic matter (DOM) is a significant (>700 Pg) global C pool. Transport of terrestrial DOM to the inland waters and coastal zones represents the largest flux of reduced C from land to water (215 Tg yr(-1)) (Meybeck, M. Am. J. Sci. 1983, 282, 401-450). Oxidation of DOM by interdependent photochemical and biochemical processes largely controls the fate of DOM entering surface waters. Reactive oxygen species (ROS) have been hypothesized to play a significant role in the photooxidation of DOM, because they may oxidize the fraction of DOM that is inaccessible to direct photochemical degradation by sunlight. We followed the effects of photochemically produced singlet oxygen ((1)O(2)) on DOM by mass spectrometry with (18)O-labeled oxygen, to understand how (1)O(2)-mediated transformations of DOM may lead to altered DOM bioavailability. The photochemical oxygen uptake by DOM attributed to (1)O(2) increased with DOM concentration, yet it remained a minority contributor to photochemical oxygen uptake even at very high DOM concentrations. When DOM samples were exposed to (1)O(2)-generating conditions (Rose Bengal and visible light), increases were observed in DOM constituents with higher oxygen content and release of H(2)O(2) was detected. Differential effects of H(2)O(2) and (1)O(2)-treated DOM showed that (1)O(2)-treated DOM led to slower bacterial growth rates relative to unmodified DOM. Results of this study suggested that the net effect of the reactions between singlet oxygen and DOM may be production of partially oxidized substrates with correspondingly lower potential biological energy yield.

Oceanic Uptake of Oxygen During Deep Convection Events Through Diffusive and Bubble-Mediated Gas Exchange

NASA Astrophysics Data System (ADS)

Sun, Daoxun; Ito, Takamitsu; Bracco, Annalisa

2017-10-01

The concentration of dissolved oxygen (O2) plays fundamental roles in diverse chemical and biological processes throughout the oceans. The balance between the physical supply and the biological consumption controls the O2 level of the interior ocean, and the O2 supply to the deep waters can only occur through deep convection in the polar oceans. We develop a theoretical framework describing the oceanic O2 uptake during open-ocean deep convection events and test it against a suite of numerical sensitivity experiments. Our framework allows for two predictions, confirmed by the numerical simulations. First, both the duration and the intensity of the wintertime cooling contribute to the total O2 uptake for a given buoyancy loss. Stronger cooling leads to deeper convection and the oxygenation can reach down to deeper depths. Longer duration of the cooling period increases the total amount of O2 uptake over the convective season. Second, the bubble-mediated influx of O2 tends to weaken the diffusive influx by shifting the air-sea disequilibrium of O2 toward supersaturation. The degree of compensation between the diffusive and bubble-mediated gas exchange depends on the dimensionless number measuring the relative strength of oceanic vertical mixing and the gas transfer velocity. Strong convective mixing, which may occur under strong cooling, reduces the degree of compensation so that the two components of gas exchange together drive exceptionally strong oceanic O2 uptake.

Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water

PubMed Central

Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

2017-01-01

Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles. PMID:28182635

Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water.

PubMed

Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

2017-01-01

Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles.

Uptake, Distribution, and Transformation of CuO NPs in a Floating Plant Eichhornia crassipes and Related Stomatal Responses.

PubMed

Zhao, Jian; Ren, Wenting; Dai, Yanhui; Liu, Lijiao; Wang, Zhenyu; Yu, Xiaoyu; Zhang, Junzhe; Wang, Xiangke; Xing, Baoshan

2017-07-05

Engineered nanoparticles (NPs) are being released into aquatic environments with their increasing applications. In this work, we investigated the interaction of CuO NPs with a floating plant, water hyacinth (Eichhornia crassipes). CuO NPs (50 mg/L) showed significant growth inhibition on both roots and shoots of E. crassipes after 8-day exposure, much higher than that of the bulk CuO particles (50 mg/L) and their corresponding dissolved Cu 2+ ions (0.30 mg/L). Scanning electron and light microscopic observations showed that the root caps and meristematic zone of E. Crassipes were severely damaged after CuO NP exposure, with disordered cell arrangement and a destroyed elongation zone of root tips. It is confirmed that CuO NPs could be translocated to shoot from both roots and submerged leaves. As detected by X-ray absorption near-edge spectroscopy analysis (XANES), CuO NPs were observed in roots, submerged leaves, and emerged leaves. Cu 2 S and other Cu species were also detected in these tissues, providing solid evidence of the transformation of CuO NPs. In addition, stomatal closure was observed during CuO NPs-leaf contact, which was induced by the production of H 2 O 2 and increased Ca level in leaf guard cells. These findings are helpful for better understanding the fate of NPs in aquatic plants and related biological responses.

Sulfur formation by steady-state continuous cultures of a sulfoxidizing consortium and Thiobacillus thioparus ATCC 23645.

PubMed

Alcántara, S; Velasco, A; Revah, S

2004-10-01

The elemental sulfur formation by the partial oxidation of thiosulfate by both a sulfoxidizing consortium and by Thiobacillus thioparus ATCC 23645 was studied under aerobic conditions in chemostat. Steady state was attained with essentially total conversion to sulfate when the dissolved oxygen concentration was 5 mgO2 l(-1) and below a dilution rate (D) of 3.0 d(-1)for the consortium and 0.9 d(-1) for T thioparus. The consortium formed elemental sulfur in steady state under oxygen limitation. Fifty percent of the theoretical elemental sulfur yield was obtained with a dissolved oxygen concentration of 0.2 mgO2 l(-1). Growth of T thioparus was negatively affected with a concentration below 1.9 mgO2 l(-1). Consortium yield from batch cultures was 2.1 g(-1) (protein) mol(-1) (thiosulfate), which was comparable with the values obtained in the chemostat at dilution rates of 0.4 d(-1) and 1.2 d(-1). The consortium showed a maximum degradation rate of 0.105 g(thiosulfate) g(-1) (protein) min(-1) and a saturation rate for S2O3(2-) of 1.9 mM.

Soil carbon dioxide partial pressure and dissolved inorganic carbonate chemistry under elevated carbon dioxide and ozone

Treesearch

N.J. Karberg; K.S. Pregitzer; J.S. King; A.L. Friend; J.R. Wood

2004-01-01

Global emissions of atmospheric CO2 and tropospheric O3 are rising and expected to impact large areas of the Earth's forests. While CO2 stimulates net primary production, O3 reduces photosynthesis, altering plant C allocation and reducing ecosystem C storage. The effects...

Dissolved oxygen as a factor influencing nitrogen removal rates in a one-stage system with partial nitritation and Anammox process.

PubMed

Cema, G; Płaza, E; Trela, J; Surmacz-Górska, J

2011-01-01

A biofilm system with Kaldnes biofilm carrier was used in these studies to cultivate bacteria responsible for both partial nitritation and Anammox processes. Due to co-existence of oxygen and oxygen-free zones within the biofilm depth, both processes can occur in a single reactor. Oxygen that inhibits the Anammox process is consumed in the outer layer of the biofilm and in this way Anammox bacteria are protected from oxygen. The impact of oxygen concentration on nitrogen removal rates was investigated in the pilot plant (2.1 m3), supplied with reject water from the Himmerfjärden Waste Water Treatment Plant. The results of batch tests showed that the highest nitrogen removal rates were obtained for a dissolved oxygen (DO) concentration around 3 g O2 m(-3) At a DO concentration of 4 g O2 m(-3), an increase of nitrite and nitrate nitrogen concentrations in the batch reactor were observed. The average nitrogen removal rate in the pilot plant during a whole operating period oscillated around 1.3 g N m(-2)d(-1) (0.3 +/- 0.1 kg N m(-3)d(-1)) at the average dissolved oxygen concentration of 2.3 g O2 m(-3). The maximum value of a nitrogen removal rate amounted to 1.9 g N m(-2)d(-1) (0.47 kg N m(-3)d(-1)) and was observed for a DO concentration equal to 2.5 g O2 m(-3). It was observed that increase of biofilm thickness during the operational period, had no influence on nitrogen removal rates in the pilot plant.

Influence of under pressure dissolved oxygen on trichloroethylene degradation by the H2O2/TiO2 process.

PubMed

Hoseini, Mohammad; Nabizadeh, Ramin; Nazmara, Shahrokh; Safari, Gholam Hossein

2013-12-20

The widespread use of trichloroethylene (TCE) and its frequent release into the environment has caused many environmental and health problems. In this study the degradation of TCE at different micromolar concentrations was investigated in a stainless steel reactor with various concentrations of H2O2 and TiO2 at different oxygen pressures and three different pHs. To examine the synergistic effect of under pressure oxygen on TCE degradation, the concentrations of H2O2 and TiO2 as well as pH were first optimized, and then the experiments were performed under optimal conditions. Gas chromatography with a flame ionization detector (FID) was used to measure TCE concentrations. Results showed that the percentage of TCE degradation without pressurized oxygen was low and it increased with increasing pressure of oxygen at all initial concentrations of TCE. The degradation percentages without oxygen pressure were 48.27%, 51.22%, 58.13% and 64.33% for TCE concentrations of 3000, 1500, 300 and 150 μg/L respectively. At an oxygen pressure of 2.5 atmospheres (atm) the percent degradation of TCE reached 84.85%, 89.14%, 93.13% and 94.99% respectively for the aforementioned TCE concentrations. The results of this study show that the application of dissolved oxygen under pressure increases the efficiency of the H2O2/TiO2 process on the degradation of TCE and can be used along with other oxidants as an effective method for the removal of this compound from aqueous solutions.

Influence of under pressure dissolved oxygen on trichloroethylene degradation by the H2O2/TiO2 process

PubMed Central

2013-01-01

Background The widespread use of trichloroethylene (TCE) and its frequent release into the environment has caused many environmental and health problems. In this study the degradation of TCE at different micromolar concentrations was investigated in a stainless steel reactor with various concentrations of H2O2 and TiO2 at different oxygen pressures and three different pHs. Methods To examine the synergistic effect of under pressure oxygen on TCE degradation, the concentrations of H2O2 and TiO2 as well as pH were first optimized, and then the experiments were performed under optimal conditions. Gas chromatography with a flame ionization detector (FID) was used to measure TCE concentrations. Results Results showed that the percentage of TCE degradation without pressurized oxygen was low and it increased with increasing pressure of oxygen at all initial concentrations of TCE. The degradation percentages without oxygen pressure were 48.27%, 51.22%, 58.13% and 64.33% for TCE concentrations of 3000, 1500, 300 and 150 μg/L respectively. At an oxygen pressure of 2.5 atmospheres (atm) the percent degradation of TCE reached 84.85%, 89.14%, 93.13% and 94.99% respectively for the aforementioned TCE concentrations. Conclusions The results of this study show that the application of dissolved oxygen under pressure increases the efficiency of the H2O2/TiO2 process on the degradation of TCE and can be used along with other oxidants as an effective method for the removal of this compound from aqueous solutions. PMID:24359702

Thermodynamics of dissolved nitrogen, nitrous oxide, and ammonia in perfluorodecalin

NASA Astrophysics Data System (ADS)

Moshnyaga, A. V.; Khoroshilov, A. V.; Selivanova, D. I.; Aksenova, D. M.

2017-11-01

The solubility of N2, N2O, and NH3 is studied in different organic solvents. The best dissolution (0.27 ppm) is found to be for N2O in perfluorodecalin at 291 K and a pressure of 99 kPa. The dependence of N2O solubility in perfluorodecalin on pressure is studied at 291 K. The Gibbs energy of the solubility of nitrogen, nitrous oxide, and ammonia in perfluorodecalin is calculated.

No effect of H2O degassing on the oxidation state of hydrous rhyolite magmas: a comparison of pre- and post-eruptive Fe2+ concentrations in six obsidian samples from the Mexican and Cascade arcs

NASA Astrophysics Data System (ADS)

Waters, L.; Lange, R. A.

2011-12-01

The extent to which degassing affects the oxidation state of arc magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of magmas, and it has been proposed that degassing may induce either oxidation or reduction depending on the initial oxidation state. A commonly proposed oxidation reaction is related to H2O degassing: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt). Another mechanism by which H2O degassing can affect the iron redox state is if dissolved water affects the activity of ferrous and/or ferric iron in the melt. Although Moore et al. (1995) presented experiments showing no evidence of an affect of dissolved water on the activity of the ferric-ferrous ratio in silicate melts, other experimental results (e.g., Baker and Rutherford, 1996; Gaillard et al., 2001; 2003) indicate that there may be such an effect in rhyolite liquids. It has long been understood that rhyolites, owing to their low total iron concentrations, are more sensitive than other magma types to degassing-induced change in redox state. Therefore, a rigorous test of whether H2O degassing affects the redox state of arc magmas is best evaluated on rhyolites. In this study, a comparison is made between the pre-eruptive (pre-degassing) Fe2+ concentrations in six, phenocryst-poor (<5%), fresh, glassy obsidian samples with their post-eruptive (post-degassing) Fe2+ concentrations. Near-liquidus co-precipitation of two Fe-Ti oxides allows the pre-eruptive oxygen fugacity and temperature to be calculated in each rhyolite using the oxygen barometer and thermometer of Ghiorso and Evans (2008). Temperatures range from 793 (± 19) to 939 (± 15) °C, and ΔNNO values (log10fO2 of sample - log10fO2 of Ni-NiO buffer) range from -0.4 to +1.4. These ΔNNO values allow the ferric-ferrous ratio in the liquid to be calculated, using the experimental calibration of Kress and Carmichael (1991), which relates melt composition (not including dissolved water), oxygen fugacity and temperature to melt ferric-ferrous ratios. With temperature known, the plagioclase-liquid hygrometer of Lange et al. (2009) was applied and maximum melt water concentrations range from 4.2 to 7.5 wt%. Both the oxidation state and water concentration are known prior to eruption, at the time of phenocryst growth. After eruption, the rhyolites lost nearly all of their volatiles, as indicated by the low loss on ignition values (LOI ≤ 0.7 wt%). In order to test how much oxidation of ferrous iron occurred as a consequence of that degassing, we measured the ferrous iron concentration in the bulk samples by titration, using the Wilson (1960) method, which was successfully tested again three USGS and one Canadian Geological Survey standards. Our results indicate no detectable change within analytical error between pre- and post-eruptive FeO concentrations, with an average deviation of 0.09 wt% and a maximum deviation of 0.15 wt%. Our results show that H2O degassing has no effect on the redox state of rhyolite magmas, which requires that dissolved water has no resolvable affect on the activity ratio of the iron oxide components in melt.

From harmful Microcystis blooms to multi-functional core-double-shell microsphere bio-hydrochar materials.

PubMed

Bi, Lei; Pan, Gang

2017-11-13

Harmful algal blooms (HABs) induced by eutrophication is becoming a serious global environmental problem affecting public health and aquatic ecological sustainability. A novel strategy for the utilization of biomass from HABs was developed by converting the algae cells into hollow mesoporous bio-hydrochar microspheres via hydrothermal carbonization method. The hollow microspheres were used as microreactors and carriers for constructing CaO 2 core-mesoporous shell-CaO 2 shell microspheres (OCRMs). The CaO 2 shells could quickly increase dissolved oxygen to extremely anaerobic water in the initial 40 min until the CaO 2 shells were consumed. The mesoporous shells continued to act as regulators restricting the release of oxygen from CaO 2 cores. The oxygen-release time using OCRMs was 7 times longer than when directly using CaO 2 . More interestingly, OCRMs presented a high phosphate removal efficiency (95.6%) and prevented the pH of the solution from rising to high levels in comparison with directly adding CaO 2 due to the OH - controlled-release effect of OCRMs. The distinct core-double-shell micro/nanostructure endowed the OCRMs with triple functions for oxygen controlled-release, phosphorus removal and less impact on water pH. The study is to explore the possibility to prepare smarter bio-hydrochar materials by utilizing algal blooms.

Hydrologic and geochemical effects on oxygen uptake in bottom sediments of an effluent-dominated river

USGS Publications Warehouse

McMahon, P.B.; Tindall, J.A.; Collins, J.A.; Lull, K.J.; Nuttle, J.R.

1995-01-01

More than 95% of the water in the South Platte River downstream from the largest wastewater treatment plant serving the metropolitan Denver, Colorado, area consists of treated effluent during some periods of low flow. Fluctuations in effluent-discharge rates caused daily changes in river stage that promoted exchange of water between the river and bottom sediments. Groundwater discharge measurements indicated fluxes of water across the sediment-water interface as high as 18 m3 s−1 km−1. Laboratory experiments indicated that downward movement of surface water through bottom sediments at velocities comparable to those measured in the field (median rate ≈0.005 cm s−1) substantially increased dissolved oxygen uptake rates in bottom sediments (maximum rate 212 ± 10 μmol O2 L−1 h−1) compared with rates obtained when no vertical advective flux was generated (maximum rate 25 ± 8.8 μmol O2 L−1 h−1). Additions of dissolved ammonium to surface waters generally increased dissolved oxygen uptake rates relative to rates measured in experiments without ammonium. However, the magnitude of the advective flux through bottom sediments had a greater effect on dissolved oxygen uptake rates than did the availability of ammonium. Results from this study indicated that efforts to improve dissolved oxygen dynamics in effluent-dominated rivers might include stabilizing daily fluctuations in river stage.

Field Continuous Measurement of Dissolved Gases with a CF-MIMS: Applications to the Physics and Biogeochemistry of Groundwater Flow.

PubMed

Chatton, Eliot; Labasque, Thierry; de La Bernardie, Jérôme; Guihéneuf, Nicolas; Bour, Olivier; Aquilina, Luc

2017-01-17

In the perspective of a temporal and spatial exploration of aquatic environments (surface and groundwater), we developed a technique for field continuous measurements of dissolved gases with a precision better than 1% for N 2 , O 2 , CO 2 , He, Ar, 2% for Kr, 8% for Xe, and 3% for CH 4 , N 2 O and Ne. With a large resolution (from 1 × 10 -9 to 1 × 10 -2 ccSTP/g) and a capability of high frequency analysis (1 measure every 2 s), the CF-MIMS (Continuous Flow Membrane Inlet Mass Spectrometer) is an innovative tool allowing the investigation of a large panel of hydrological and biogeochemical processes in aquatic systems. Based on the available MIMS technology, this study introduces the development of the CF-MIMS (conception for field experiments, membrane choices, ionization) and an original calibration procedure allowing the quantification of mass spectral overlaps and temperature effects on membrane permeability. This study also presents two field applications of the CF-MIMS involving the well-logging of dissolved gases and the implementation of groundwater tracer tests with dissolved 4 He. The results demonstrate the analytical capabilities of the CF-MIMS in the field. Therefore, the CF-MIMS is a valuable tool for the field characterization of biogeochemical reactivity, aquifer transport properties, groundwater recharge, groundwater residence time and aquifer-river exchanges from few hours to several weeks experiments.

Transient Evolution of Nonmetallic Inclusions During Calcium Treatment of Molten Steel

NASA Astrophysics Data System (ADS)

Zhang, Lifeng; Liu, Yang; Zhang, Ying; Yang, Wen; Chen, Wei

2018-06-01

The transient evolution of nonmetallic inclusions after calcium addition in pipeline steels was investigated with a vacuum induction furnace. Samples were taken at 1, 5, 10, 15, and 20 minutes after calcium treatment in both MgO and Al2O3 crucibles. It was found that the total oxygen and the number density of inclusions were increased during calcium modification, while they were dropped to a low level in the last tapped sample. Due to the evaporation of calcium, inclusions were transferred from CaO-CaS to Al2O3-CaO-CaS, and then to Al2O3-CaO. The decomposition of CaS was highly dependent on the decrease of the total calcium and the increase of the total oxygen in the steel. Thermodynamic calculation was performed to predict the composition of inclusions considering the effect of the total oxygen and the total calcium and was validated by measurement. The relationship between the content of Al2O3 in inclusions and the ratio of the total calcium and the total oxygen in steels was measured and compared with the calculated one using thermodynamic software Factsage 7.0. The mass-transfer coefficient of the dissolved calcium in the steel was estimated in the range of 2.35 × 10-4 to 3.53 × 10-4 m/s.

Degassing history of water, sulfur, and carbon in submarine lavas from Kilauea Volcano, Hawaii

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dixon, J.E.; Stolper, E.M.; Clague, D.A.

1991-05-01

Major, minor, and dissolved volatile element concentrations were measured in tholeiitic glasses from the submarine portion (Puna Ridge) of the east rift zone of Kilauea Volcano, Hawaii. Dissolved H{sub 2}O and S concentrations display a wide range relative to nonvolatile incompatible elements at all depths. This range cannot be readily explained by fractional crystallization, degassing of H{sub 2}O and S during eruption on the seafloor, or source region heterogeneities. Dissolved CO{sub 2} concentrations, in contrast, show a positive correlation with eruption depth and typically agree within error with the solubility at that depth. The authors propose that most magmas alongmore » the Puna Ridge result from (1) mixing of a relatively volatile-rich, undegassed component with magmas that experienced low pressure (perhaps subaerial) degassing during which substantial H{sub 2}O, S, and CO{sub 2} were lost, followed by (2) fractional crystallization of olivine, clinopyroxene, and plagioclase from this mixture to generate a residual liquid; and (3) further degassing, principally of CO{sub 2} for samples erupted deeper than 1,000 m, during eruption on the seafloor. They predict that average Kilauean primary magmas with 16% MgO contain {approximately}0.47 wt % H{sub 2}0, {approximately}900 ppm S, and have {delta}D values of {approximately}{minus}30 to {minus}40%. The model predicts that submarine lavas from wholly submarine volcanoes (i.e., Loihi), for which there is no opportunity to generate the degassed end member by low pressure degassing, will be enriched in volatiles relative to those from volcanoes whose summits have breached the sea surface (i.e., Kilauea and Mauna Loa).« less

Transport and cycling of iron and hydrogen peroxide in a freshwater stream: Influence of organic acids

USGS Publications Warehouse

Scott, Durelle T.; Runkel, Robert L.; McKnight, Diane M.; Voelker, Bettina M.; Kimball, Briant A.; Carraway, Elizabeth R.

2003-01-01

An in-stream injection of two dissolved organic acids (phthalic and aspartic acids) was performed in an acidic mountain stream to assess the effects of organic acids on Fe photoreduction and H2O2 cycling. Results indicate that the fate of Fe is dependent on a net balance of oxidative and reductive processes, which can vary over a distance of several meters due to changes in incident light and other factors. Solution phase photoreduction rates were high in sunlit reaches and were enhanced by the organic acid addition but were also limited by the amount of ferric iron present in the water column. Fe oxide photoreduction from the streambed and colloids within the water column resulted in an increase in the diurnal load of total filterable Fe within the experimental reach, which also responded to increases in light and organic acids. Our results also suggest that Fe(II) oxidation increased in response to the organic acids, with the result of offsetting the increase in Fe(II) from photoreductive processes. Fe(II) was rapidly oxidized to Fe(III) after sunset and during the day within a well-shaded reach, presumably through microbial oxidation. H2O 2, a product of dissolved organic matter photolysis, increased downstream to maximum concentrations of 0.25 ??M midday. Kinetic calculations show that the buildup of H2O2 is controlled by reaction with Fe(III), but this has only a small effect on Fe(II) because of the small formation rates of H2O2 compared to those of Fe(II). The results demonstrate the importance of incorporating the effects of light and dissolved organic carbon into Fe reactive transport models to further our understanding of the fate of Fe in streams and lakes.

Preparation of xerogel SiO2 from roasted iron sand under various acidic solution

NASA Astrophysics Data System (ADS)

Ramelan, A. H.; Wahyuningsih, S.; Ismoyo, Y. A.; Pranata, H. P.; Munawaroh, H.

2016-11-01

Xerogel SiO2 had been prepared from roasted iron sand through variation of Na2CO3 addition and sol-gel process under various acidic solution. Roasting treatment was carried out on the compositional variation of iron sand:Na2CO3 = 1:2; 1:1 and 2:1 at 1100 °C. While the sol-gel process was conducted at room temperature and neutralized using HCl 0.1 M and 6 M. The color characteristics of roasted iron sand shown light brown, dark brown and dark gray of the compositional variation of iron sand:Na2CO3 = 1:2; 1:1 and 2:1, respectively. In addition, the levels of thoughness increased by increasing the ratio of sand in the composition of the mixture. The best composition of roasted treatment was at a variety of iron sand:Na2SiO3 = 1:2 with 57.72% had been dissolved in hot water. The addition of Na2CO3 will influence the Na2SiO3 formation, because of the increase of Na2CO3 capable produced the iron sand decomposition product. Na2SiO3 gel had been produced after it was neutralized with certain amount of HCl solution. The neutralization was more effective if using high concentration of HCl because of the formation of gel SiO2 will be easier occurred. The results of SiO2 had been identified by the FTIR spectra, which an absorption spectra of Si-O-Si asymmetric stretching at 1098.51 cm-1, symmetric stretching of Si-O-Si at 804.35 cm-1 and the bending O-Si-O at 469.69 cm'1. The result of SiO2 content by XRF analysis is about 85.15%.

Glacial alteration of volcanic terrains: A chemical investigation of the Three Sisters, Oregon, USA.

NASA Astrophysics Data System (ADS)

Rutledge, Alicia; Horgan, Briony; Havig, Jeff

2017-04-01

Glacial silica cycling is more efficient than previously reported, and in some settings, particularly glaciated mafic volcanics, can be the dominant weathering process. Based on field work at glaciated volcanic sites, we hypothesize that this is due to a combination of high rates of silica dissolution from mafic bedrock and reprecipitation of silica in the form of opaline silica coatings and other poorly crystalline silicate alteration phases. The high rate of bedrock comminution in subglacial environments results in high rates of both chemical and physical weathering, due to the increased reactive mineral surface area formed through glacial grinding. In most bedrock types, carbonate weathering is enhanced and silica fluxes are depressed in glacial outwash compared with global average riverine catchment runoff due to low temperatures and short residence times. However, in mafic systems, higher dissolved SiO2 concentrations have been observed. The major difference between observed glacial alteration of volcanic bedrock and more typical continental terrains is the absence of significant dissolved carbonate in the former. In the absence of carbonate minerals which normally dominate dissolution processes at glacier beds, carbonation of feldspar can become the dominant weathering process, which can result in a high proportion of dissolved silica fluxes in glacial outwash waters compared to the total cation flux. Mafic volcanic rocks are particularly susceptible to silica mobility, due to the high concentration of soluble minerals (i.e. plagioclase) as compared to the high concentration of insoluble quartz found in felsic rocks. To investigate melt-driven chemical weathering of mafic volcanics, water and rock samples were collected during July 2016 from glaciated volcanic bedrock in the Three Sisters Wilderness, Oregon, U.S.A. (44°9'N, 121°46'W): Collier Glacier (basaltic andesite, andesite), Hayden Glacier (andesite, dacite), and Diller Glacier (basalt). Here we report major anion and cation concentrations in meltwaters for the summer 2016 melt season, with emphasis on SiO2. Dissolved silica concentration (range: below detectable levels to 240 μM) tends to increase with pH (range: 4.3 to 8.5), consistent with silica solubility increasing with pH. Proglacial streams, springs, and lakes exhibit dissolved silica concentrations that are greater than observed in glacial snow/ice. The highest silica concentrations were measured in moraine-sourced springs. More mafic glaciovolcanic sites exhibit higher concentrations of dissolved silica in outwash waters compared to more felsic glaciovolcanic sites. Though basalts have lower SiO2 content than more felsic volcanic rocks, they are more susceptible to silica mobility due to their higher content of minerals such as olivine, pyroxene, and plagioclase, which are more soluble than quartz. These mineral breakdown reactions are potentially enhanced by microbial populations at the glacier bed. The measured high silica concentrations in springs are potentially due to moraines acting as sediment traps. Moraines are poorly sorted sediments with a high proportion of subglacially ground fine particles, and glacial flour further accumulates by aeolian deposition. The increased fine-grained component - and thus increased surface area - and longer residence times due to associated decreased permeability could contribute to the observed high dissolved silica concentrations.

Integrated chemical treatment of municipal wastewater using waste hydrogen peroxide and ultraviolet light

NASA Astrophysics Data System (ADS)

Bhatti, Zulfiqar Ahmed; Mahmood, Qaisar; Raja, Iftikhar Ahmad; Malik, Amir Haider; Rashid, Naim; Wu, Donglei

Dilemmas like water shortage, rapid industrialization, growing human population and related issues have seriously affected human health and environmental sustainability. For conservation and sustainable use of our water resources, innovative methods for wastewater treatment are continuously being explored. Advance Oxidation Processes (AOPs) show a promising approach to meet specific objectives of municipal wastewater treatment (MWW). The MWW samples were pretreated with Al 2(SO 4) 4·8H 2O (Alum) at different doses 4, 8, 12-50 mg/L to enhance the sedimentation. The maximum COD removal was observed at alum treatments in range of 28-32 mg/L without increasing total dissolved solids (TDS). TDS were found to increase when the alum dose was increased from 32-40 mg/L. In the present study, the optimum alum dose of 30 mg/L for 3 h of sedimentation and subsequent integrated H 2O 2/UV treatment was applied (using 2.5 mL/L of 40% waste H 2O 2 and 35% fresh H 2O 2 separately). Organic and inorganic pollutants, contributing towards chemical oxygen demand (COD), biological oxygen demand (BOD), turbidity and total dissolved solids were degraded by H 2O 2/UV. About 93% COD, 90% BOD and 83% turbidity reduction occurred when 40% waste H 2O 2 was used. When using fresh H 2O 2, 63% COD, 68% BOD and 86% turbidity reduction was detected. Complete disinfection of coliform bacteria occurred by using 40% H 2O 2/UV. The most interesting part of this research was to compare the effectiveness of waste H 2O 2 with fresh H 2O 2. Waste H 2O 2 generated from an industrial process of disinfection was found more effective in the treatment of MWW than fresh 35% H 2O 2.

Treatment of dye wastewater with permanganate oxidation and in situ formed manganese dioxides adsorption: cation blue as model pollutant.

PubMed

Liu, Ruiping; Liu, Huijuan; Zhao, Xu; Qu, Jiuhui; Zhang, Ran

2010-04-15

This study investigated the process of potassium permanganate (KMnO(4)) oxidation and in situ formed hydrous manganese dioxides (deltaMnO(2)) (i.e., KMnO(4) oxidation and deltaMnO(2) adsorption) for the treatment of dye wastewater. The effectiveness of decolorization, removing dissolved organic carbon (DOC), and increasing biodegradable oxygen demand (BOD) were compared among these processes of KMnO(4) oxidation, deltaMnO(2) adsorption, and KMnO(4) oxidation and deltaMnO(2) adsorption. DeltaMnO(2) adsorption contributed to the maximum DOC removal of 65.0%, but exhibited limited capabilities of decolorizing and increasing biodegradability. KMnO(4) oxidation alone at pH 0.5 showed satisfactory decrease of UV-vis absorption peaks, and the maximum BOD(5)/DOC value of 1.67 was achieved. Unfortunately, the DOC removal was as low as 27.4%. Additionally, the great amount of acid for pH adjustment and the much too low pH levels limited its application in practice. KMnO(4) oxidation and deltaMnO(2) adsorption at pH 2.0 was the best strategy prior to biological process, in balancing the objectives of decolorization, DOC removal, and BOD increase. The optimum ratio of KMnO(4) dosage to X-GRL concentration (R(KMnO(4)/X-GRL)) was determined to be 2.5, at which KMnO(4) oxidation and deltaMnO(2) adsorption contributed to the maximal DOC removal of 53.4%. Additionally, the optimum pH for X-GRL treatment was observed to be near 3.0. 2009 Elsevier B.V. All rights reserved.

Assessment of benthic flux of dissolved organic carbon in wetland and estuarine sediments using the eddy-correlation technique

NASA Astrophysics Data System (ADS)

Swett, M. P.; Amirbahman, A.; Boss, E.

2009-12-01

Wetland and estuarine sediments release significant amounts of dissolved organic carbon (DOC) due to high levels of microbial activity, particularly sulfate reduction. Changes in climate and hydrologic conditions have a potential to alter DOC release from these systems as well. This is a concern, as high levels of DOC can lead to mobilization of toxic metals and organics in natural waters. In addition, source waters high in DOC produce undesirable disinfection byproducts in water treatment. Various in situ methods, such as peepers and sediment core centrifugation, exist to quantify vertical benthic fluxes of DOC and other dissolved species from the sediment-water interface (SWI). These techniques, however, are intrusive and involve disturbance of the sediment environment. Eddy-correlation allows for real-time, non-intrusive, in situ flux measurement of important analytes, such as O2 and DOC. An Acoustic Doppler Velocimeter (ADV) is used to obtain three-dimensional fluid velocity measurements. The eddy-correlation technique employs the mathematical separation of fluid velocity into mean velocity and fluctuating velocity components, with the latter representing turbulent eddy velocity. DOC concentrations are measured using a colored dissolved organic matter (CDOM) fluorometer, and instantaneous vertical flux is determined from the correlated data. This study assesses DOC flux at three project sites: a beaver pond in the Lower Penobscot Watershed, Maine; a mudflat in Penobscot River, Maine; and a mudflat in Great Bay, New Hampshire. Eddy flux values are compared with results obtained using peepers and centrifugation, as well as vertical profiling.

Targeted Cancer Therapy: Correlative Light-Electron Microscopy Shows RGD-Targeted ZnO Nanoparticles Dissolve in the Intracellular Environment of Triple Negative Breast Cancer Cells and Cause Apoptosis with Intratumor Heterogeneity (Adv. Healthcare Mater. 11/2016).

PubMed

Othman, Basmah A; Greenwood, Christina; Abuelela, Ayman F; Bharath, Anil A; Chen, Shu; Theodorou, Ioannis; Douglas, Trevor; Uchida, Maskai; Ryan, Mary; Merzaban, Jasmeen S; Porter, Alexandra E

2016-06-01

On page 1310 J. S. Merzaban, A. E. Porter, and co-workers present fluorescently labeled RGD-targeted ZnO nanoparticles (NPs; green) for the targeted delivery of cytotoxic ZnO to integrin αvβ3 receptors expressed on triple negative breast cancer cells. Correlative light-electron microscopy shows that NPs dissolve into ionic Zn(2+) (blue) upon uptake and cause apoptosis (red) with intra-tumor heterogeneity, thereby providing a possible strategy for targeted breast cancer therapy. Cover design by Ivan Gromicho. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemical Production of Singlet Oxygen from Dissolved Organic Matter in Ice.

PubMed

Fede, Alexis; Grannas, Amanda M

2015-11-03

Dissolved natural organic matter (DOM) is a ubiquitous component of natural waters and an important photosensitizer. A variety of reactive oxygen species (ROS) are known to be produced from DOM photochemistry, including singlet oxygen, 1O2. Recently, it has been determined that humic-like substances and unknown organic chromophores are significant contributors to sunlight absorption in snowpack; however, DOM photochemistry in snow/ice has received little attention in the literature. We recently showed that DOM plays an important role in indirect photolysis processes in ice, producing ROS and leading to the efficient photodegradation of a probe hydrophobic organic pollutant, aldrin.1 ROS scavenger experiments indicated that 1O2 played a significant role in the indirect photodegradation of aldrin. Here we quantitatively examine 1O2 photochemically produced from DOM in frozen and liquid aqueous solutions. Steady-state 1O2 production is enhanced up to nearly 1000 times in frozen DOM samples compared to liquid samples. 1O2 production is dependent on the concentration of DOM, but the nature of the DOM source (terrestrial vs microbial) does not have a significant effect on 1O2 production in liquid or frozen samples, with different source types producing similar steady-state concentrations of 1O2. The temperature of frozen samples also has a significant effect on steady-state 1O2 production in the range of 228-262 K, with colder samples producing more steady-state 1O2. The large enhancement in 1O2 in frozen samples suggests that it may play a significant role in the photochemical processes that occur in snow and ice, and DOM could be a significant, but to date poorly understood, oxidant source in snow and ice.

Cooperative tin oxide fullerene electron selective layers for high-performance planar perovskite solar cells

DOE PAGES

Ke, Weijun; Zhao, Dewei; Xiao, Chuanxiao; ...

2016-08-17

Both tin oxide (SnO 2) and fullerenes have been reported as electron selective layers (ESLs) for producing efficient lead halide perovskite solar cells. Here, we report that SnO 2 and fullerenes can work cooperatively to further boost the performance of perovskite solar cells. We find that fullerenes can be redissolved during perovskite deposition, allowing ultra-thin fullerenes to be retained at the interface and some dissolved fullerenes infiltrate into perovskite grain boundaries. The SnO 2 layer blocks holes effectively; whereas, the fullerenes promote electron transfer and passivate both the SnO 2/perovskite interface and perovskite grain boundaries. With careful device optimization, themore » best-performing planar perovskite solar cell using a fullerene passivated SnO 2 ESL has achieved a steady-state efficiency of 17.75% and a power conversion efficiency of 19.12% with an open circuit voltage of 1.12 V, a short-circuit current density of 22.61 mA cm -2, and a fill factor of 75.8% when measured under reverse voltage scanning. In conclusion, we find that the partial dissolving of fullerenes during perovskite deposition is the key for fabricating high-performance perovskite solar cells based on metal oxide/fullerene ESLs.« less

Chemical dissolution of sulfide minerals

USGS Publications Warehouse

Chao, T.T.; Sanzolone, R.F.

1977-01-01

Chemical dissolution treatments involving the use of aqua regia, 4 N HNO3, H2O2-ascorbic acid, oxalic acid, KClO3+HCl, and KClO3+HCl followed by 4 N HNO3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO3+HCl followed by 4 N HNO3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.

Cyanobacterial and microcystins dynamics following the application of hydrogen peroxide to waste stabilisation ponds

NASA Astrophysics Data System (ADS)

Barrington, D. J.; Ghadouani, A.; Ivey, G. N.

2013-06-01

Cyanobacteria and cyanotoxins are a risk to human and ecological health, and a hindrance to biological wastewater treatment. This study investigated the use of hydrogen peroxide (H2O2) for the removal of cyanobacteria and cyanotoxins from within waste stabilization ponds (WSPs). The daily dynamics of cyanobacteria and microcystins (commonly occurring cyanotoxins) were examined following the addition of H2O2 to wastewater within both the laboratory and at the full scale within a maturation WSP, the final pond in a wastewater treatment plant. Hydrogen peroxide treatment at concentrations ≥ 0.1 mg H2O2 μg-1 total phytoplankton chlorophyll a led to the lysis of cyanobacteria, in turn releasing intracellular microcystins to the dissolved state. In the full-scale trial, dissolved microcystins were then degraded to negligible concentrations by H2O2 and environmental processes within five days. A shift in the phytoplankton assemblage towards beneficial Chlorophyta species was also observed within days of H2O2 addition. However, within weeks, the Chlorophyta population was significantly reduced by the re-establishment of toxic cyanobacterial species. This re-establishment was likely due to the inflow of cyanobacteria from ponds earlier in the treatment train, suggesting that whilst H2O2 may be a suitable short-term management technique, it must be coupled with control over inflows if it is to improve WSP performance in the longer term.

Elucidating the role of methyl viologen as a scavenger of photoactivated electrons from photosystem I under aerobic and anaerobic conditions.

PubMed

Bennett, Tyler; Niroomand, Hanieh; Pamu, Ravi; Ivanov, Ilia; Mukherjee, Dibyendu; Khomami, Bamin

2016-03-28

We present detailed electrochemical investigations into the role of dissolved O2 in electrolyte solutions in scavenging photoactivated electrons from a uniform photosystem I (PS I) monolayer assembled on alkanethiolate SAM (self-assembled monolayer)/Au surfaces while using methyl viologen (MV(2+)) as the redox mediator. To this end, we report results for direct measurements of light induced photocurrent from uniform monolayer assemblies of PS I on C9 alkanethiolate SAM/Au surfaces. These measurements, apart from demonstrating the ability of dissolved O2 in the electrolyte medium to act as an electron scavenger, also reveal its essential role in driving the solution-phase methyl viologen to initiate light-induced directional electron transfer from an electron donor surface (Au) via surface assembled PS I trimers. Specifically, our systematic electrochemical measurements have revealed that the dissolved O2 in aqueous electrolyte solutions form a complex intermediate species with MV that plays the essential role in mediating redox pathways for unidirectional electron transfer processes. This critical insight into the redox-mediated electron transfer pathways allows for rational design of electron scavengers through systematic tuning of mediator combinations that promote such intermediate formation. Our current findings facilitate the incorporation of PS I-based bio-hybrid constructs as photo-anodes in future photoelectrochemical cells and bio-electronic devices.

Facile Method to Study Catalytic Oxygen Evolution Using a Dissolved Oxygen Optical Probe: An Undergraduate Chemistry Laboratory to Appreciate Artificial Photosynthesis

ERIC Educational Resources Information Center

Renderos, Genesis; Aquino, Tawanda; Gutierrez, Kristian; Badiei, Yosra M.

2017-01-01

Artificial photosynthesis (AP) is a synthetic chemical process that replicates natural photosynthesis to mass produce hydrogen as a clean fuel from sunlight-driven water splitting (2H[subscript 2]O [right arrow] O[subscript 2] + H[subscript 2]). In both natural and artificial photosynthesis, an oxygen-evolving catalyst (OEC) is needed to catalyze…

Effects of Co2 Concentrations and light intensity on photosynthesis of a rootless submerged plant, ceratophyllum demersum L., used for aquatic food production in bioregenerative life support systems

NASA Astrophysics Data System (ADS)

Kitaya, Y.; Okayama, T.; Murakami, K.; Takeuchi, T.

Aquatic higher plants are likely to play an important role in aquatic food production modules in bioregenerative systems for producing feeds for fish, converting CO2 to O2 and remedying water quality in addition to green microalgae. In the present study, the effects of culture conditions on the net photosynthetic rate of a rootless submerged plant, Ceratophyllum demersum L., was investigated to determine the optimum culture conditions for plant function in aquatic food production modules including both plant culture and fish culture systems . The net photosynthetic rate in plants was determined by the increase in dissolved O2 concentrations in a closed vessel containing a plantlet and water. The water in the vessel was aerated sufficiently with a gas containing a known level CO 2 gas mixed with N2 gas before closing the vessel. The CO 2 concentrations in the aerating gas ranged from 0.3 to 100 mmol mol-1 . Photosynthetic photon flux density (PPFD) in the vessel ranged from 0 (dark) to 1.0 mmol m-2 s-1 , which was controlled with a metal halide lamp. Temperature was kept at 28 C. The net photosynthetic rate increased with increasing PPFD levels and was saturated at 0.2 and 0.5 mmol m-2 s-1 PPFD under CO 2 levels of 1.0 and 3.0 mmol mol-1 , respectively. The net photosynthetic rate increased with increasing CO2 levels from 0.3 to 3.0 mmol mol-1 showing the maximum value, 70 nmolO 2 gDW s at 3.0 mmol mol-1 CO2 and gradually decreased with increasing CO 2 levels from 3.0 to 100 mmol mol-1 . The results demonstrate that Ceratophyllum demersum L. could be an efficient CO 2 to O2 converter under a 3.0 mmol mol-1 CO2 level and relatively low PPFD levels in aquatic food production modules.

Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

NASA Astrophysics Data System (ADS)

Cao, Xiaoyan; Aiken, George R.; Spencer, Robert G. M.; Butler, Kenna; Mao, Jingdong; Schmidt-Rohr, Klaus

2016-05-01

Seasonal (spring freshet, summer-autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV-visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64-74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63-77%) and TPIA (54-78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OCnp, OCnpO and Cq, 13-17% of HPOA and 15-20% of TPIA) and isolated O-CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (∼5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C-O and O-C-O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

Analysis of maximum allowable fragment heights during dissolution of high flux isotope reactor fuel in an h-canyon dissolver

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel, G.; Rudisill, T.

2017-07-17

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3O 8) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2. The HFIR fuel cores will be dissolved using a flowsheet developed by the Savannahmore » River National Laboratory (SRNL) in either the 6.4D or 6.1D dissolver using a unique insert. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The recovered U will be down-blended into low-enriched U for subsequent use as commercial reactor fuel. During the development of the HFIR fuel dissolution flowsheet, the cycle time for the initial core was estimated at 28 to 40 h. Once the cycle is complete, H-Canyon personnel will open the dissolver and probe the HFIR insert wells to determine the height of any fuel fragments which did not dissolve. Before the next core can be charged to the dissolver, an analysis of the potential for H 2 gas generation must show that the combined surface area of the fuel fragments and the subsequent core will not generate H 2 concentrations in the dissolver offgas which exceeds 60% of the lower flammability limit (LFL) of H 2 at 200 °C. The objective of this study is to identify the maximum fuel fragment height as a function of the Al concentration in the dissolving solution which will provide criteria for charging successive HFIR cores to an H-Canyon dissolver.« less

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Evaluation of headspace equilibration methods for quantifying greenhouse gases in groundwater.

PubMed

Jahangir, M M R; Johnston, P; Khalil, M I; Grant, J; Somers, C; Richards, K G

2012-11-30

The objective of the study was to evaluate the different headspace equilibration methods for the quantification of dissolved greenhouse gases in groundwater. Groundwater samples were collected from wells with contrasting hydrogeochemical properties and degassed using the headspace equilibration method. One hundred samples from each well were randomly selected, treatments were applied and headspace gases analysed by gas chromatography. Headspace equilibration treatments varied helium (He):water ratio, shaking time and standing time. Mean groundwater N(2)O, CO(2) and CH(4) concentrations were 0.024 mg N L(-1), 13.71 mg C L(-1) and 1.63 μg C L(-1), respectively. All treatments were found to significantly influence dissolved gas concentrations. Considerable differences in the optimal He:water ratio and standing time were observed between the three gases. For N(2)O, CO(2) and CH(4) the optimum operating points for He:water ratio was 4.4:1, 3:1 and 3.4:1; shaking time was 13, 12 and 13 min; and standing time was 63, 17 and 108 min, respectively. The headspace equilibration method needs to be harmonised to ensure comparability between studies. The experiment reveals that He:water ratio 3:1 and shaking time 13 min give better estimation of dissolved gases than any lower or higher ratios and shaking times. The standing time 63, 17 and 108 min should be applied for N(2)O, CO(2) and CH(4), respectively. Copyright © 2012. Published by Elsevier Ltd.

Effect of soil organic matter content and pH on the toxicity of ZnO nanoparticles to Folsomia candida.

PubMed

Waalewijn-Kool, Pauline L; Rupp, Svenja; Lofts, Stephen; Svendsen, Claus; van Gestel, Cornelis A M

2014-10-01

Organic matter (OM) and pH may influence nanoparticle fate and effects in soil. This study investigated the influence of soil organic matter content and pH on the toxicity of ZnO-NP and ZnCl2 to Folsomia candida in four natural soils, having between 2.37% and 14.7% OM and [Formula: see text] levels between 5.0 and 6.8. Porewater Zn concentrations were much lower in ZnO-NP than in ZnCl2 spiked soils, resulting in higher Freundlich sorption constants for ZnO-NP. For ZnCl2 the porewater Zn concentrations were significantly higher in less organic soils, while for ZnO-NP the highest soluble Zn level (23mgZn/l) was measured in the most organic soil, which had the lowest pH. Free Zn(2+) ion concentrations were higher for ZnCl2 than for ZnO-NP and were greatly dependent on pH (pHpw) and dissolved organic carbon content of the pore water. The 28-d EC50 values for the effect of ZnCl2 on the reproduction of F. candida increased with increasing OM content from 356 to 1592mgZn/kg d.w. For ZnO-NP no correlation between EC50 values and OM content was found and EC50 values ranged from 1695 in the most organic soil to 4446mgZn/kg d.w. in the higher pH soil. When based on porewater and free Zn(2+) concentrations, EC50 values were higher for ZnCl2 than for ZnO-NP, and consistently decreased with increasing pHpw. This study shows that ZnO-NP toxicity is dependent on soil properties, but is mainly driven by soil pH. Copyright © 2014 Elsevier Inc. All rights reserved.

Long-term limnological data from the larger lakes of Yellowstone National Park, Wyoming, USA

USGS Publications Warehouse

Theriot, E.C.; Fritz, S.C.; Gresswell, Robert E.

1997-01-01

Long-term limnological data from the four largest lakes in Yellowstone National Park (Yellowstone, Lewis, Shoshone, Heart) are used to characterize their limnology and patterns of temporal and spatial variability. Heart Lake has distinctively high concentrations of dissolved materials, apparently reflecting high thermal inputs. Shoshone and Lewis lakes have the highest total SiO2 concentrations (averaging over 23.5 mg L-1), apparently as a result of the rhyolitic drainage basins. Within Yellowstone Lake spatial variability is low and ephemeral for most measured variables, except that the Southeast Arm has lower average Na concentrations. Seasonal variation is evident for Secchi transparency, pH, and total-SiO2 and probably reflects seasonal changes in phytoplankton biomass and productivity. Total dissolved solids (TDS) and total-SiO2 generally show a gradual decline from the mid-1970s through mid-1980s, followed by a sharp increase. Ratios of Kjeldahl-N to total-PO4 (KN:TP) suggest that the lakes, especially Shoshone, are often nitrogen limited. Kjeldahl-N is positively correlated with winter precipitation, but TP and total-SiO2 are counterintuitively negatively correlated with precipitation. We speculate that increased winter precipitation, rather than watershed fires, increases N-loading which, in turn, leads to increased demand for TP and total SiO2.

Concurrent estimates of carbon export reveal physical biases in ΔO2/Ar-based net community production estimates in the Southern California Bight

NASA Astrophysics Data System (ADS)

Haskell, William Z.; Fleming, John C.

2018-07-01

Net community production (NCP) represents the amount of biologically-produced organic carbon that is available to be exported out of the surface ocean and is typically estimated using measurements of the O2/Ar ratio in the surface mixed layer under the assumption of negligible vertical transport. However, physical processes can significantly bias NCP estimates based on this in-situ tracer. It is actively debated whether discrepancies between O2/Ar-based NCP and carbon export estimates are due to differences in the location of biological production and export, or the result of physical biases. In this study, we calculate export production across the euphotic depth during two months of upwelling in Southern California in 2014, based on an estimate of the consumption rate of dissolved organic carbon (DOC) and the dissolved: total organic carbon consumption ratio below the euphotic depth. This estimate equals the concurrent O2/Ar-based NCP estimates over the same period that are corrected for physical biases, but is significantly different than NCP estimated without a correction for vertical transport. This comparison demonstrates that concurrent physical transport estimates would significantly improve O2/Ar-based estimates of NCP, particularly in settings with vertical advection. Potential approaches to mitigate this bias are discussed.

Shallow groundwater denitrification capacity at three contrasting hydrogeological environments in Ireland

NASA Astrophysics Data System (ADS)

Mofizur Rahman Jahangir, Mohammad; Johnston, Paul; Khalil, Mohammad Ibrahim; Richards, Karl

2010-05-01

Denitrification may be regarded as the dominant nitrate removal or attenuation process in shallow groundwater. A major concern arising from the denitrification process is that it not only serves as a natural pathway for excess NO3- removal but its intermediate product, N2O, is a potent greenhouse gas. A groundwater monitoring network was established on grazed grassland at research farms at Johnstown Castle (JC) and Solohead (SH) on tillage at Oak Park (OP) in Ireland, to investigate the denitrification capacity and N2O:(N2O+N2) ratio within the shallow groundwater zone. The geology of this zone at the 3 sites was i) JC: sand and gravel intermixed with clay, ii) SH: silt and gravel intermixed with dense clay and iii) OP: dense gravel with interbedded clays. Average groundwater table was respectively 3.2, 2.4 and 4.0 m below ground level. Ten piezometers of 50 mm ID with 2 m screen sections were installed at 3.5-6.0 m below ground level using a rotary air drilling method at the three sites. Groundwater sampling was carried out monthly for 6 months (February to July, 2009) using a bladder pump following the USEPA low flow sampling procedures. Dissolved groundwater N2O was separated by degassing groundwater in a sealed serum bottle (160ml) using high purity He (water:He = 3:1) and the collected headspace equilibrium gas was analyzed on a Varian gas chromatograph. The N2/Ar ratio, measured using a Membrane Inlet Mass Spectrometer, was used to estimate the denitrified N2 concentrations. The mean NO3-N concentrations were 7.0, 2.5 and 11.0 mg L-1 in JC, SH and OP, respectively. Ground water dissolved N2O concentrations ranged from 0.01 to 0.05, 0.01 to 0.06 and 0.002 to 0.06 mg L-1, with corresponding mean values of 0.03, 0.02, 0.02 mg N.L-1 in JC, SH and OP, respectively. The mean values for total denitrification (N2O+N2) were 1.94, 1.03 and 0.38 mg N.L-1, which accounted for 22, 29 and 3% losses of total NO3- -N in JC, SH and OP, respectively. The higher denitrification measured on the grassland compared to tillage is most likely related to the hydrogeological conditions e.g. DOC, DO and redox-potential rather than land-use. More importantly, the mean N2O:N2O+N2 ratios, being 0.01, 0.02 and 0.05, respectively in JC, SH and OP indicated that 95-99% of total denitrification was molecular N2 (98-99% in grassland and 95% in tillage farm). With respect to temporal changes, denitrification losses were higher in May in grassland systems and in April in tillage farming systems. Shallow groundwater denitrification appeared to be an important process in reducing NO3- , with low N2O concentrations indicating low losses of this greenhouse gas to the atmosphere upon discharging to surface water.

Liquid phase deposition synthesis of hexagonal molybdenum trioxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deki, Shigehito; Beleke, Alexis Bienvenu; Kotani, Yuki

2009-09-15

Hexagonal molybdenum trioxide thin films with good crystallinity and high purity have been fabricated by the liquid phase deposition (LPD) technique using molybdic acid (H{sub 2}MoO{sub 4}) dissolved in 2.82% hydrofluoric acid (HF) and H{sub 3}BO{sub 3} as precursors. The crystal was found to belong to a hexagonal hydrate system MoO{sub 3}.nH{sub 2}O (napprox0.56). The unit cell lattice parameters are a=10.651 A, c=3.725 A and V=365.997 A{sup 3}. Scanning electron microscope (SEM) images of the as-deposited samples showed well-shaped hexagonal rods nuclei that grew and where the amount increased with increase in reaction time. X-ray photon electron spectroscopy (XPS) spectramore » showed a Gaussian shape of the doublet of Mo 3d core level, indicating the presence of Mo{sup 6+} oxidation state in the deposited films. The deposited films exhibited an electrochromic behavior by lithium intercalation and deintercalation, which resulted in coloration and bleaching of the film. Upon dehydration at about 450 deg. C, the hexagonal MoO{sub 3}.nH{sub 2}O was transformed into the thermodynamically stable orthorhombic phase. - Abstract: SEM photograph of typical h-MoO{sub 3}.nH{sub 2}O thin film nuclei obtained after 36 h at 40 deg. C by the LPD method. Display Omitted« less

Evaluating Microbial Indicators of Environmental Condition in Oregon Rivers

NASA Astrophysics Data System (ADS)

Pennington, Alan T.; Harding, Anna K.; Hendricks, Charles W.; Campbell, Heidi M. K.

2001-12-01

Traditional bacterial indicators used in public health to assess water quality and the Biolog® system were evaluated to compare their response to biological, chemical, and physical habitat indicators of stream condition both within the state of Oregon and among ecoregion aggregates (Coast Range, Willamette Valley, Cascades, and eastern Oregon). Forty-three randomly selected Oregon river sites were sampled during the summer in 1997 and 1998. The public health indicators included heterotrophic plate counts (HPC), total coliforms (TC), fecal coliforms (FC) and Escherichia coli (EC). Statewide, HPC correlated strongly with physical habitat (elevation, riparian complexity, % canopy presence, and indices of agriculture, pavement, road, pasture, and total disturbance) and chemistry (pH, dissolved O2, specific conductance, acid-neutralizing capacity, dissolved organic carbon, total N, total P, SiO2, and SO4). FC and EC were significantly correlated generally with the river chemistry indicators. TC bacteria significantly correlated with riparian complexity, road disturbance, dissolved O2, and SiO2 and FC. Analyzing the sites by ecoregion, eastern Oregon was characterized by high HPC, FC, EC, nutrient loads, and indices of human disturbance, whereas the Cascades ecoregion had correspondingly low counts of these indicators. The Coast Range and Willamette Valley presented inconsistent indicator patterns that are more difficult to characterize. Attempts to distinguish between ecoregions with the Biolog system were not successful, nor did a statistical pattern emerge between the first five principle components and the other environmental indicators. Our research suggests that some traditional public health microbial indicators may be useful in measuring the environmental condition of lotic systems.

Comparison of oxygen transfer parameters and oxygen demands in bioreactors operated at low and high dissolved oxygen levels.

PubMed

Mines, Richard O; Callier, Matthew C; Drabek, Benjamin J; Butler, André J

2017-03-21

The proper design of aeration systems for bioreactors is critical since it can represent up to 50% of the operational and capital cost at water reclamation facilities. Transferring the actual amount of oxygen needed to meet the oxygen demand of the wastewater requires α- and β-factors, which are used for calculating the actual oxygen transfer rate (AOTR) under process conditions based on the standard oxygen transfer rate (SOTR). The SOTR is measured in tap water at 20°C, 1 atmospheric pressure, and 0 mg L -1 of dissolved oxygen (DO). In this investigation, two 11.4-L bench-scale completely mixed activated process (CMAS) reactors were operated at various solid retention times (SRTs) to ascertain the relationship between the α-factor and SRT, and between the β-factor and SRT. The second goal was to determine if actual oxygen uptake rates (AOURs) are equal to calculated oxygen uptake rates (COURs) based on mass balances. Each reactor was supplied with 0.84 L m -1 of air resulting in SOTRs of 14.3 and 11.5 g O 2 d -1 for Reactor 1 (R-1) and Reactor 2 (R-2), respectively. The estimated theoretical oxygen demands of the synthetic feed to R-1 and R-2 were 6.3 and 21.9 g O 2 d -1 , respectively. R-2 was primarily operated under a dissolved oxygen (DO) limitation and high nitrogen loading to determine if nitrification would be inhibited from a nitrite buildup and if this would impact the α-factor. Nitrite accumulated in R-2 at DO concentrations ranging from 0.50 to 7.35 mg L -1 and at free ammonia (FA) concentrations ranging from 1.34 to 7.19 mg L -1 . Nonsteady-state reaeration tests performed on the effluent from each reactor and on tap water indicated that the α-factor increased as SRT increased. A simple statistical analysis (paired t-test) between AOURs and COURs indicated that there was a statistically significant difference at 0.05 level of significance for both reactors. The ex situ BOD bottle method for estimating AOUR appears to be invalid in bioreactors operated at low DO concentrations (<1.0 mg L -1 ).

Evolution of the Campanian Ignimbrite Magmatic System I: Constraints on Compositional Zonation and Eruption Probability Imposed By Phase Equilibria

NASA Astrophysics Data System (ADS)

Fowler, S.; Spera, F.; Bohrson, W.; Belkin, H.; Devivo, B.

2005-12-01

The eruption and deposition of the ~39.3 ka Campanian Ignimbrite (CI), a large volume (~200 km3 DRE) trachytic to phonolitic ignimbrite, is the dominant event in the history of the Campi Flegrei volcanic field near Naples, Italy. In an effort to comprehend its petrological evolution, we have conducted ~~110 MELTS (Ghiorso, 1997) phase equilibria simulations of the major element evolution of parental CI magma. The goals of this work are to approximate oxygen fugacity (fO2), initial dissolved water content and pressure at which isobaric closed system fractional crystallization of parental melt most accurately captures the observed liquid line of descent and to study the implications of heat extraction from parental CI magma with respect to the origin of compositional zonation and the probability of explosive eruption. Although the CI magma body did not evolve as a perfectly closed system, this assumption allows quantitative insight into magma-host rock mass exchange using trace element and isotopic data (see companion contribution by Bohrson et al.). The parental melt composition was reconstructed using data for melt inclusions trapped within CI clinopyroxene phenocrysts reported by Webster et al. (2003), while allowing for reaction between parental melt and clinopyroxene host. The inferred parental melt is a basaltic trachyandesite. The search space for pressure, (fO2) and initial dissolved H2O was 0.1-0.5 in 0.05 GPa increments, QFM-1 to QFM+3 and 1, 2 and 3 wt. % H2O, respectively. The criteria used to judge the quality of a simulation include correspondence of the MELTS prediction with CI liquid and phenocryst compositions. Results indicate that a good first-order model involves evolution from a basaltic trachyandesite parent by isobaric (~0.15 GPa) crystal fractionation initially containing ~3 wt% dissolved H2O along the QFM+1 buffer. H2O first saturates at 1127°C at 0.15 GPa when the dissolved water content is ~4 wt %. A striking result is the discovery of a pseudo-invariant point at ~883°C (Tip) and 0.15 GPa. The fraction of melt changes abruptly from ~0.5 to ~0.1 at Tip due to the simultaneous crystallization of alkali feldspar, plagioclase, spinel, biotite and apatite. At Tip, there is a dramatic decrease in the viscosity of melt (by a factor of four) and magma density (~5%) and an increase in the dissolved H2O content of the melt (from 4.4-5.1 wt%) and in the volume fraction,θ, of supercritical fluid in the multiphase system. In particular, θ increases from ~0.05 at 885°C to ~0.6 at 882°C. The liquid composition also changes discontinuously at Tip with Si, Na, and H2O increasing and K and Al decreasing as temperature falls below Tip. The marked variations in composition and properties of volatile-saturated melt and magma were the trigger that led to the catastrophic eruption and formation of the compositionally-zoned CI magma. Because phase equilibria modeling provides information on the enthalpy changes associated with fractional crystallization and because the dimensions of the CI magma chamber and heat extraction rate can be approximated, a time scale for CI magmatic evolution can be derived. The estimated crystallization duration (τ) is10-100 ka and 75% of τ is spent at or near Tip.

Attenuation of Microbial Stress Due to Nano-Ag and Nano-TiO2 Interactions under Dark Conditions.

PubMed

Wilke, Carolyn M; Tong, Tiezheng; Gaillard, Jean-François; Gray, Kimberly A

2016-10-04

Engineered nanomaterials (ENMs) are incorporated into thousands of commercial products, and their release into environmental systems creates complex mixtures with unknown toxicological outcomes. To explore this scenario, we probe the chemical and toxicological interactions of nanosilver (n-Ag) and nanotitania (n-TiO 2 ) in Lake Michigan water, a natural aqueous medium, under dark conditions. We find that the presence of n-Ag induces a stress response in Escherichia coli, as indicated by a decrease in ATP production observed at low concentrations (in the μg L -1 range), with levels that are environmentally relevant. However, when n-Ag and n-TiO 2 are present together in a mixture, n-TiO 2 attenuates the toxicity of n-Ag at and below 20 μg L -1 by adsorbing Ag + (aq) . We observe, however, that toxic stress cannot be explained by dissolved silver concentrations alone and, therefore, must also depend on silver associated with the nanoscale fraction. Although the attenuating effect of n-TiO 2 on n-Ag's toxicity is limited, this study emphasizes the importance of probing the toxicity of ENM mixtures under environmental conditions to assess how chemical interactions between nanoparticles change the toxicological effects of single ENMs in unexpected ways.

Spatial and temporal distribution of singlet oxygen in Lake Superior.

PubMed

Peterson, Britt M; McNally, Ann M; Cory, Rose M; Thoemke, John D; Cotner, James B; McNeill, Kristopher

2012-07-03

A multiyear field study was undertaken on Lake Superior to investigate singlet oxygen ((1)O(2)) photoproduction. Specifically, trends within the lake were examined, along with an assessment of whether correlations existed between chromophoric dissolved organic matter (CDOM) characteristics and (1)O(2) production rates and quantum yields. Quantum yield values were determined and used to estimate noontime surface (1)O(2) steady-state concentrations ([(1)O(2)](ss)). Samples were subdivided into three categories based on their absorbance properties (a300): riverine, river-impacted, or open lake sites. Using calculated surface [(1)O(2)](ss), photochemical half-lives under continuous summer sunlight were calculated for cimetidine, a pharmaceutical whose reaction with (1)O(2) has been established, to be on the order of hours, days, and a week for the riverine, river-impacted, and open lake waters, respectively. Of the CDOM properties investigated, it was found that dissolved organic carbon (DOC) and a300 were the best parameters for predicting production rates of [(1)O(2)](ss). For example, given the correlations found, one could predict [(1)O(2)](ss) within a factor of 4 using a300 alone. Changes in the quantum efficiency of (1)O(2) production upon dilution of river water samples with lake water samples demonstrated that the CDOM found in the open lake is not simply diluted riverine organic matter. The open lake pool was characterized by low absorption coefficient, low fluorescence, and low DOC, but more highly efficient (1)O(2) production and predominates the Lake Superior system spatially. This study establishes that parameters that reflect the quantity of CDOM (e.g., a300 and DOC) correlate with (1)O(2) production rates, while parameters that characterize the absorbance spectrum (e.g., spectral slope coefficient and E2:E3) correlate with (1)O(2) production quantum yields.

Transformation of molecular weight distributions of dissolved organic carbon and UV-absorbing compounds at full-scale wastewater-treatment plants.

PubMed

Esparza-Soto, Mario; Fox, Peter; Westerhoff, Paul

2006-03-01

The molecular-weight distribution (MWD) of wastewater dissolved-organic carbon (DOC) was determined in samples from seven full-scale wastewater-treatment plants (WWTPs) that use different biological treatments (air activated sludge [air-AS], pure-oxygen AS [O2-AS], and trickling filters). The research objective was to determine how different biological treatments influenced the MWD of wastewater DOC. Primary sedimentation effluent DOC from most of the WWTPs exhibited a skewed distribution toward the low-molecular-weight fraction (MWF) (40 to 50%, < 0.5 K Daltons [KDa]). The Air-AS effluent DOC exhibited a centrally clustered distribution, with the majority of DOC in the intermediate MWF (0.5 to 3 KDa). The O2-AS effluent DOC exhibited a skewed distribution toward the high MWF (> 3 KDa). The removal of DOC by air- and O2-AS bacteria followed trends predicted by a macromolecule degradation model. Trickling-filter effluent DOC exhibited a skewed distribution toward the high MWF (50% DOC, > 3 KDa).

Evaluating nanoparticle breakthrough during drinking water treatment.

PubMed

Abbott Chalew, Talia E; Ajmani, Gaurav S; Huang, Haiou; Schwab, Kellogg J

2013-10-01

Use of engineered nanoparticles (NPs) in consumer products is resulting in NPs in drinking water sources. Subsequent NP breakthrough into treated drinking water is a potential exposure route and human health threat. In this study we investigated the breakthrough of common NPs--silver (Ag), titanium dioxide (TiO2), and zinc oxide (ZnO)--into finished drinking water following conventional and advanced treatment. NPs were spiked into five experimental waters: groundwater, surface water, synthetic freshwater, synthetic freshwater containing natural organic matter, and tertiary wastewater effluent. Bench-scale coagulation/flocculation/sedimentation simulated conventional treatment, and microfiltration (MF) and ultrafiltration (UF) simulated advanced treatment. We monitored breakthrough of NPs into treated water by turbidity removal and inductively coupled plasma-mass spectrometry (ICP-MS). Conventional treatment resulted in 2-20%, 3-8%, and 48-99% of Ag, TiO2, and ZnO NPs, respectively, or their dissolved ions remaining in finished water. Breakthrough following MF was 1-45% for Ag, 0-44% for TiO2, and 36-83% for ZnO. With UF, NP breakthrough was 0-2%, 0-4%, and 2-96% for Ag, TiO2, and ZnO, respectively. Variability was dependent on NP stability, with less breakthrough of aggregated NPs compared with stable NPs and dissolved NP ions. Although a majority of aggregated or stable NPs were removed by simulated conventional and advanced treatment, NP metals were detectable in finished water. As environmental NP concentrations increase, we need to consider NPs as emerging drinking water contaminants and determine appropriate drinking water treatment processes to fully remove NPs in order to reduce their potential harmful health outcomes.

Temperature sensitivity of soil carbon dioxide and nitrous oxide emissions in mountain forest and meadow ecosystems in China

NASA Astrophysics Data System (ADS)

Zhang, Junjun; Peng, Changhui; Zhu, Qiuan; Xue, Wei; Shen, Yan; Yang, Yanzheng; Shi, Guohua; Shi, Shengwei; Wang, Meng

2016-10-01

An incubation experiment was conducted at three temperature levels (8, 18 and 28 °C) to quantify the response of soil CO2 and N2O emissions to temperature in three ecosystems (pine forest, oak forest, and meadow) located in the Qinling Mountains of China, which are considered to be susceptible to disturbance and climate changes, especially global warming. The soil CO2 emission rates increased with temperature and decreased with soil depth; they were the highest in the oak forest (broadleaf forest) and were lower in the pine forest (coniferous forest) and the meadow ecosystem. However, there was no significant difference in the soil N2O emission rates among the three ecosystems. The temperature sensitivity of CO2 and N2O was higher in the forest than in the meadow ecosystem. The Q10 values (temperature sensitivity coefficient) for CO2 and N2O were 1.07-2.25 and 0.82-1.22, respectively, for the three ecosystems. There was also evidence that the CO2 and N2O emission rates were positively correlated. The soil characteristics exhibited different effects on CO2 and N2O emissions among different ecosystems at the three temperature levels. Moreover, the soil dissolved organic carbon (DOC), specific ultraviolet absorbance (SUVA) and nitrate (NO3-) were important factors for CO2 emissions, whereas the soil ammonium (NH4+) and pH were the major controllers of N2O emissions. Unexpectedly, our results indicated that CO2 emissions are more sensitive to increasing temperature than N2O, noting the different feedback of CO2 and N2O emissions to global warming in this region. The different responses of greenhouse gas emissions in different forest types and a meadow ecosystem suggest that it is critical to conduct a comprehensive investigation of the complex mountain forest and meadow ecosystem in the transitional climate zone under global warming. Our research results provide new insight and advanced understanding of the variations in major greenhouse gas emissions (CO2 and N2O) and soil characteristics in response to warming.

Effects of CO2 concentration and light intensity on photosynthesis of a rootless submerged plant, Ceratophyllum demersum L., used for aquatic food production in bioregenerative life support systems

NASA Technical Reports Server (NTRS)

Kitaya, Y.; Okayama, T.; Murakami, K.; Takeuchi, T.

2003-01-01

In addition to green microalgae, aquatic higher plants are likely to play an important role in aquatic food production modules in bioregenerative systems for producing feed for fish, converting CO2 to O2 and remedying water quality. In the present study, the effects of culture conditions on the net photosynthetic rate of a rootless submerged plant, Ceratophyllum demersum L., was investigated to determine the optimum culture conditions for maximal function of plants in food production modules including both aquatic plant culture and fish culture systems. The net photosynthetic rate in plants was determined by the increase in dissolved O2 concentrations in a closed vessel containing a plantlet and water. The water in the vessel was aerated sufficiently with a gas containing a known concentration of CO2 gas mixed with N2 gas before closing the vessel. The CO2 concentrations in the aerating gas ranged from 0.3 to 10 mmol mol-1. Photosynthetic photon flux density (PPFD) in the vessel ranged from 0 (dark) to 1.0 mmol m-2 s-1, which was controlled with a metal halide lamp. Temperature was kept at 28 degrees C. The net photosynthetic rate increased with increasing PPFD levels and was saturated at 0.2 and 0.5 mmol m-2 s-1 PPFD under CO2 levels of 1.0 and 3.0 mmol mol-1, respectively. The net photosynthetic rate increased with increasing CO2 levels from 0.3 to 3.0 mmol mol-1 showing the maximum value, 75 nmol O2 gDW-1 s-1, at 2-3 mmol mol-1 CO2 and gradually decreased with increasing CO2 levels from 3.0 to 10 mmol mol-1. The results demonstrate that C. demersum could be an efficient CO2 to O2 converter under a 2.0 mmol mol-1 CO2 level and relatively low PPFD levels in aquatic food production modules. c2003 COSPAR. Published by Elsevier Science Ltd. All rights reserved.

Effects of CO 2 concentration and light intensity on photosynthesis of a rootless submerged plant, Ceratophyllumdemersum L., used for aquatic food production in bioregenerative life support systems

NASA Astrophysics Data System (ADS)

Kitaya, Y.; Okayama, T.; Murakami, K.; Takeuchi, T.

In addition to green microalgae, aquatic higher plants are likely to play an important role in aquatic food production modules in bioregenerative systems for producing feed for fish, converting CO 2 to O 2 and remedying water quality. In the present study, the effects of culture conditions on the net photosynthetic rate of a rootless submerged plant, Ceratophyllum demersum L., was investigated to determine the optimum culture conditions for maximal function of plants in food production modules including both aquatic plant culture and fish culture systems. The net photosynthetic rate in plants was determined by the increase in dissolved O 2 concentrations in a closed vessel containing a plantlet and water. The water in the vessel was aerated sufficiently with a gas containing a known concentration of CO 2 gas mixed with N 2 gas before closing the vessel. The CO 2 concentrations in the aerating gas ranged from 0.3 to 10 mmol mol -1. Photosynthetic photon flux density (PPFD) in the vessel ranged from 0 (dark) to 1.0 mmol M -2 s -1, which was controlled with a metal halide lamp. Temperature was kept at 28°C. The net photosynthetic rate increased with increasing PPFD levels and was saturated at 0.2 and 0.5 mmol m -2 s -1 PPFD under CO 2 levels of 1.0 and 3.0 mmol mol -1, respectively. The net photosynthetic rate increased with increasing CO 2 levels from 0.3 to 3.0 mmol mol -1 showing the maximum value, 75 nmolO 2 gDW -1 s -1, at 2-3 mmol mol -1 CO 2 and gradually decreased with increasing CO 2 levels from 3.0 to 10 mmol mol -1. The results demonstrate that C. demersum could be an efficient CO 2 to O 2 converter under a 2.0 mmol mol -1 CO 2 level and relatively low PPFD levels in aquatic food production modules.

Method for generating a crystalline {sup 99}MoO{sub 3} product and the isolation {sup 99m}Tc compositions therefrom

DOEpatents

Bennett, R.G.; Christian, J.D.; Kirkham, R.J.; Tranter, T.J.

1998-09-01

An improved method is described for producing {sup 99m}Tc compositions. {sup 100}Mo metal is irradiated with photons in a particle (electron) accelerator to produce {sup 99}Mo metal which is dissolved in a solvent. A solvated {sup 99}Mo product is then dried to generate a supply of {sup 99}MoO{sub 3} crystals. The crystals are thereafter heated at a temperature which will sublimate the crystals and form a gaseous mixture containing vaporized {sup 99m}TcO{sub 3} and vaporized {sup 99m}TcO{sub 2} but will not cause the production of vaporized {sup 99}MoO{sub 3}. The mixture is then combined with an oxidizing gas to generate a gaseous stream containing vaporized {sup 99m}Tc{sub 2}O{sub 7}. Next, the gaseous stream is cooled to a temperature sufficient to convert the vaporized {sup 99m}Tc{sub 2}O{sub 7} into a condensed {sup 99m}Tc-containing product. The product has high purity levels resulting from the use of reduced temperature conditions and ultrafine crystalline {sup 99}MoO{sub 3} starting materials with segregated {sup 99m}Tc compositions therein which avoid the production of vaporized {sup 99}MoO{sub 3} contaminants. 1 fig.

Dissolution behavior of MgO based inert matrix fuel for the transmutation of minor actinides

NASA Astrophysics Data System (ADS)

Mühr-Ebert, E. L.; Lichte, E.; Bukaemskiy, A.; Finkeldei, S.; Klinkenberg, M.; Brandt, F.; Bosbach, D.; Modolo, G.

2018-07-01

This study explores the dissolution properties of magnesia-based inert matrix nuclear fuel (IMF) containing transuranium elements (TRU). Pure MgO pellets as well as MgO pellets containing CeO2, as surrogate for TRU oxides, and are considered as model systems for genuine magnesia based inert matrix fuel were fabricated. The aim of this study is to identify conditions at which the matrix material can be selectively dissolved during the head-end reprocessing step, allowing a separation of MgO from the actinides, whereas the actinides remain undissolved. The dissolution behavior was studied in macroscopic batch experiments as a function of nitric acid concentration, dissolution medium volume, temperature, stirring velocity, and pellet density (85, 90, 96, and 99%TD). To mimic pellets with various burn-ups the density of the here fabricated pellets was varied. MgO is soluble even under mild conditions (RT, 2.5 mol/L HNO3). The dissolution rates of MgO at different acid concentrations are rather similar, whereas the dissolution rate is strongly dependent on the temperature. Via a microscopic approach, a model was developed to describe the evolution of the pellet surface area during dissolution and determine a surface normalized dissolution rate. Moreover, dissolution rates of the inert matrix fuel containing CeO2 were determined as a function of the acid concentration and temperature. During the dissolution of MgO/CeO2 pellets the MgO dissolves completely, while CeO2 (>99%) remains undissolved. This study intends to provide a profound understanding of the chemical performance of magnesia based IMF containing fissile material. The feasibility of the dissolution of magnesia based IMF with nitric acid is discussed.

Management effects on greenhouse gas dynamics in fen ditches.

PubMed

Peacock, Mike; Ridley, Luke M; Evans, Chris D; Gauci, Vincent

2017-02-01

Globally, large areas of peatland have been drained through the digging of ditches, generally to increase agricultural production. By lowering the water table it is often assumed that drainage reduces landscape-scale emissions of methane (CH 4 ) into the atmosphere to negligible levels. However, drainage ditches themselves are known to be sources of CH 4 and other greenhouse gases (GHGs), but emissions data are scarce, particularly for carbon dioxide (CO 2 ) and nitrous oxide (N 2 O), and show high spatial and temporal variability. Here, we report dissolved GHGs and diffusive fluxes of CH 4 and CO 2 from ditches at three UK lowland fens under different management; semi-natural fen, cropland, and cropland restored to low-intensity grassland. Ditches at all three fens emitted GHGs to the atmosphere, but both fluxes and dissolved GHGs showed extensive variation both seasonally and within-site. CH 4 fluxes were particularly large, with medians peaking at all three sites in August at 120-230mgm -2 d -1 . Significant between site differences were detected between the cropland and the other two sites for CO 2 flux and all three dissolved GHGs, suggesting that intensive agriculture has major effects on ditch biogeochemistry. Multiple regression models using environmental and water chemistry data were able to explain 29-59% of observed variation in dissolved GHGs. Annual CH 4 fluxes from the ditches were 37.8, 18.3 and 27.2gCH 4 m -2 yr -1 for the semi-natural, grassland and cropland, and annual CO 2 fluxes were similar (1100 to 1440gCO 2 m -2 yr -1 ) among sites. We suggest that fen ditches are important contributors to landscape-scale GHG emissions, particularly for CH 4 . Ditch emissions should be included in GHG budgets of human modified fens, particularly where drainage has removed the original terrestrial CH 4 source, e.g. agricultural peatlands. Copyright © 2016 Elsevier B.V. All rights reserved.

Agriculture-related trends in groundwater quality of the glacial deposits aquifer, central Wisconsin

USGS Publications Warehouse

Saad, D.A.

2008-01-01

Measuring and understanding trends in groundwater quality is necessary for determining whether changes in land-management practices have an effect on groundwater quality. This paper describes an approach that was used to measure and understand trends using data from two groundwater studies conducted in central Wisconsin as part of the USGS NAWQA program. One of the key components of this approach, determining the age of sampled groundwater, gave a temporal component to the snapshots of water quality that were obtained through synoptic-sampling efforts. This approach can be used at other locations where groundwater quality data are collected, groundwater age can be determined, and associated temporal data are available. Results of these studies indicate measured concentrations of nitrate and atrazine plus deethylatrazine were correlated to historical patterns of fertilizer and atrazine use. Concentrations of nitrate in groundwater have increased over time; concentrations of atrazine plus deethylatrazine increased and then decreased. Concentrations of nitrate also were correlated to screen depth below the water level and concentrations of dissolved O2; concentrations of atrazine plus deethylatrazine were correlated to dissolved O2 and annual precipitation. To measure trends in concentrations of atrazine plus deethylatrazine, the data, collected over a near-decadal period, were adjusted to account for changes in laboratory-reporting levels and analytical recoveries. Only after accounting for these changes was it apparent that the median concentrations of atrazine plus deethylatrazine decreased over the near-decadal interval between sampling efforts. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Antioxidant activities of nano-bubble hydrogen-dissolved water assessed by ESR and 2,2'-bipyridyl methods.

PubMed

Kato, Shinya; Matsuoka, Daigo; Miwa, Nobuhiko

2015-08-01

We prepared nano-bubble hydrogen-dissolved water (nano-H water) which contained hydrogen nano-bubbles of <717-nm diameter for 54% of total bubbles. In the DMPO-spin trap electron spin resonance (ESR) method, the DMPO-OH:MnO ratio, being attributed to amounts of hydroxyl radicals (OH), was 2.78 for pure water (dissolved hydrogen [DH]≤0.01 ppm, oxidation-reduction potential [ORP]=+324 mV), 2.73 for tap water (0.01 ppm, +286 mV), 2.93 for commercially available hydrogen water (0.075 ppm, +49 mV), and 2.66 for manufactured hydrogen water (0.788 ppm, -614 mV), whereas the nano-H water (0.678 ppm, -644 mV) exhibited 2.05, showing the superiority of nano-H water to other types of hydrogen water in terms of OH-scavenging activity. Then, the reduction activity of nano-H water was assessed spectrophotometrically by the 2,2'-bipyridyl method. Differential absorbance at 530 nm was in the order: 0.018 for pure water, 0.055 for tap water, 0.079 for nano-H water, 0.085 for commercially available hydrogen water, and 0.090 for manufactured hydrogen water, indicating a prominent reduction activity of hydrogen water and nano-H water against oxidation in ascorbate-coupled ferric ion-bipyridyl reaction. Thus, nano-H water has an improved antioxidant activity as compared to hydrogen water of similar DH-level, indicating the more marked importance of nano-bubbles rather than the concentration of hydrogen in terms of OH-scavenging. Copyright © 2015 Elsevier B.V. All rights reserved.

Annual methane and nitrous oxide emissions from rice paddies and inland fish aquaculture wetlands in southeast China

NASA Astrophysics Data System (ADS)

Wu, Shuang; Hu, Zhiqiang; Hu, Tao; Chen, Jie; Yu, Kai; Zou, Jianwen; Liu, Shuwei

2018-02-01

Inland aquaculture ponds have been documented as important sources of atmospheric methane (CH4) and nitrous oxide (N2O), while their regional or global source strength remains unclear due to lack of direct flux measurements by covering more typical habitat-specific aquaculture environments. In this study, we compared the CH4 and N2O fluxes from rice paddies and nearby inland fish aquaculture wetlands that were converted from rice paddies in southeast China. Both CH4 and N2O fluxes were positively related to water temperature and sediment dissolved organic carbon, but negatively related to water dissolved oxygen concentration. More robust response of N2O fluxes to water mineral N was observed than to sediment mineral N. Annual CH4 and N2O fluxes from inland fish aquaculture averaged 0.51 mg m-2 h-1 and 54.78 μg m-2 h-1, amounting to 42.31 kg CH4 ha-1 and 2.99 kg N2O-N ha-1, respectively. The conversion of rice paddies to conventional fish aquaculture significantly reduced CH4 and N2O emissions by 23% and 66%, respectively. The emission factor for N2O was estimated to be 0.46% of total N input in the feed or 1.23 g N2O-N kg-1 aquaculture production. The estimate of sustained-flux global warming potential of annual CH4 and N2O emissions and the net economic profit suggested that such conversion of rice paddies to inland fish aquaculture would help to reconcile the dilemma for simultaneously achieving both low climatic impacts and high economic benefits in China. More solid direct field measurements from inland aquaculture are in urgent need to direct the overall budget of national or global CH4 and N2O fluxes.

Methane and Nitrous Oxide Emissions Reduced Following Conversion of Rice Paddies to Inland Crab-Fish Aquaculture in Southeast China.

PubMed

Liu, Shuwei; Hu, Zhiqiang; Wu, Shuang; Li, Shuqing; Li, Zhaofu; Zou, Jianwen

2016-01-19

Aquaculture is an important source of atmospheric methane (CH4) and nitrous oxide (N2O), while few direct flux measurements are available for their regional and global source strength estimates. A parallel field experiment was performed to measure annual CH4 and N2O fluxes from rice paddies and rice paddy-converted inland crab-fish aquaculture wetlands in southeast China. Besides N2O fluxes dependent on water/sediment mineral N and CH4 fluxes related to water chemical oxygen demand, both CH4 and N2O fluxes from aquaculture were related to water/sediment temperature, sediment dissolved organic carbon, and water dissolved oxygen concentration. Annual CH4 and N2O fluxes from inland aquaculture averaged 0.37 mg m(-2) h(-1) and 48.1 μg m(-2) h(-1), yielding 32.57 kg ha(-1) and 2.69 kg N2O-N ha(-1), respectively. The conversion of rice paddies to aquaculture significantly reduced CH4 and N2O emissions by 48% and 56%, respectively. The emission factor for N2O was estimated to be 0.66% of total N input in the feed or 1.64 g N2O-N kg(-1) aquaculture production in aquaculture. The conversion of rice paddies to inland aquaculture would benefit for reconciling greenhouse gas mitigation and agricultural income increase as far as global warming potentials and net ecosystem economic profits are of concomitant concern. Some agricultural practices such as better aeration and feeding, and fallow season dredging would help to lower CH4 and N2O emissions from inland aquaculture. More field measurements from inland aquaculture are highly needed to gain an insight into national and global accounting of CH4 and N2O emissions.

Ketoprofen-β-cyclodextrin inclusion complexes formation by supercritical process technology

NASA Astrophysics Data System (ADS)

Sumarno, Rahim, Rizki; Trisanti, Prida Novarita

2017-05-01

Ketoprofen was a poorly soluble which anti-inflammatory, analgesic and antipyretic drug, solubility of which can be enchanced by form complexation with β-cyclodextrin. Besides that, the inclusion complex reduces the incidence of gastrointestinal side effect of drug. The aims of this research are to study the effect of H2O concentration in the supercritical carbondioxide and operation condition in the formation of ketoprofen-β-Cyclodextrin inclusion complex. This research was began by dissolved H2O in supercritical CO2 at 40°C and various saturation pressures. Then, dissolved H2O contacted with (1:5 w/w) ketoprofen-β-Cyclodextrin mixture at 50°C and various operation pressures. It called saturation process. Saturation was done for ±2 hours with agitation process and continued by decompression process. The products were characterized by drug Release, Differential Scanning Calorimetry (DCS) dan Scanning Electron Microscopy (SEM) analyses. The percentage from this work were 76,82%-89,99% for inclusion complexes. The percentage drug release of ketoprofen were 82,83%-88,36% on various inclusion pressure and various inclusion period.

Using altimetry to help explain patchy changes in hydrographic carbon measurements

NASA Astrophysics Data System (ADS)

Rodgers, Keith B.; Key, Robert M.; Gnanadesikan, Anand; Sarmiento, Jorge L.; Aumont, Olivier; Bopp, Laurent; Doney, Scott C.; Dunne, John P.; Glover, David M.; Ishida, Akio; Ishii, Masao; Jacobson, Andrew R.; Lo Monaco, Claire; Maier-Reimer, Ernst; Mercier, Herlé; Metzl, Nicolas; PéRez, Fiz F.; Rios, Aida F.; Wanninkhof, Rik; Wetzel, Patrick; Winn, Christopher D.; Yamanaka, Yasuhiro

2009-09-01

Here we use observations and ocean models to identify mechanisms driving large seasonal to interannual variations in dissolved inorganic carbon (DIC) and dissolved oxygen (O2) in the upper ocean. We begin with observations linking variations in upper ocean DIC and O2 inventories with changes in the physical state of the ocean. Models are subsequently used to address the extent to which the relationships derived from short-timescale (6 months to 2 years) repeat measurements are representative of variations over larger spatial and temporal scales. The main new result is that convergence and divergence (column stretching) attributed to baroclinic Rossby waves can make a first-order contribution to DIC and O2 variability in the upper ocean. This results in a close correspondence between natural variations in DIC and O2 column inventory variations and sea surface height (SSH) variations over much of the ocean. Oceanic Rossby wave activity is an intrinsic part of the natural variability in the climate system and is elevated even in the absence of significant interannual variability in climate mode indices. The close correspondence between SSH and both DIC and O2 column inventories for many regions suggests that SSH changes (inferred from satellite altimetry) may prove useful in reducing uncertainty in separating natural and anthropogenic DIC signals (using measurements from Climate Variability and Predictability's CO2/Repeat Hydrography program).

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy.

PubMed

Slenkamp, Karla M; Lynch, Michael S; Van Kuiken, Benjamin E; Brookes, Jennifer F; Bannan, Caitlin C; Daifuku, Stephanie L; Khalil, Munira

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O and formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm(-1). The mixed-mode anharmonicities range from 2 to 14 cm(-1). In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm(-1). This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.

The solidification behavior of calcium oxide-aluminum oxide slags

NASA Astrophysics Data System (ADS)

Prapakorn, Kritsada

The binary CaO-Al2O3 based slag and the ternary CaO-Al2O3-MgO based slag are common slags covering and inclusions that are found in calcium treated Al-killed, continuously cast steels. However, the effect of cooling conditions and chemistry on the solidification behavior of these slags is not well characterized. To better understand this phenomena, the solidification behavior of these slags was studied by using double hot thermocouple technique. TTT and CCT diagrams of these slags were determined to quantify the solidification behavior in both dry and humid atmospheres. In this work, these slag samples were easily undercooled and the solidification behavior of these slags was found to be a strong function of cooling conditions. The crystallization tendency of these slags follows the trends suggested by the phase diagram. In CaO-Al2O3 based slags, The eutectic composition (50%CaO) give the lowest crystallization tendency due to the lowest liquidus temperature. In a eutectic CaO-Al2O3 slag sample, dissolved water in the sample increases crystallization tendency and enhances the growth. It was also found that the crystalline phase that formed during cooling in both the dry and humid conditions is the mixture between 3CaO.Al2O 3 and CaO.Al2O3 phases. In CaO-Al2O3-MgO based slags, the crystallization tendency increases with MgO content because the high MgO content leads to the high liquidus temperature. The effect of dissolved of water on the crystallization of CaO-Al2O3-MgO based slags is not as prominent as in the eutectic CaO-Al2O3 slag. Thus, the addition of MgO to CaO-Al2O3 slags was seen to minimize or eliminate the effect of humidity on the solidification of CaO-Al2O3 based slags. In this work, Uhlmann's method was used to estimate the solid-liquid interfacial energy of CaO-Al2O3 based slag for the temperature between 1100--1250°C. The result is between 0.25--0.4 Joules/m 2.

Colloidal and electrochemical aspects of copper-CMP

NASA Astrophysics Data System (ADS)

Sun, Yuxia

Copper based interconnects with low dielectric constant layers are currently used to increase interconnect densities and reduce interconnect time delays in integrated circuits. The technology used to develop copper interconnects involves Chemical Mechanical Planarization (CMP) of copper films deposited on low-k layers (silica or silica based films), which is carried out using slurries containing abrasive particles. One issue using such a structure is copper contamination over dielectric layers (SiO2 film), if not reduced, this contamination will cause current leakage. In this study, the conditions conducive to copper contamination onto SiO2 films during Cu-CMP process were studied, and a post-CMP cleaning technique was discussed based on experimental results. It was found that the adsorption of copper onto a silica surface is kinetically fast (<0.5 minute). The amount of copper absorbed is pH and concentration dependent and affected by presence of H2O2, complexing agents, and copper corrosion inhibitor Benzotrazole. Based on de-sorption results, DI water alone was unable to reduce adsorbed copper to an acceptable level, especially for adsorption that takes place at a higher pH condition. The addition of complex agent, citric acid, proved effective in suppressing copper adsorption onto oxide silica during polishing or post-CMP cleaning by forming stable copper-CA complexes. Surface Complexation Modeling was used to simulate copper adsorption isotherms and predict the copper contamination levels on SiO2 surfaces. Another issue with the application of copper CMP is its environmental impact. CMP is a costly process due to its huge consumption of pure water and slurry. Additionally, Cu-CMP processing generates a waste stream containing certain amounts of copper and abrasive slurry particles. In this study, the separation technique electrocoagulation was investigated to remove both copper and abrasive slurry particles simultaneously. For effluent containing ˜40 ppm dissolved copper, it was found that ˜90% dissolved copper was removed from the waste streams through electroplating and in-situ chemical precipitation. The amount of copper removed through plating is impacted by membrane surface charge, type/amount of complexing agents, and solid content in the slurry suspension. The slurry particles can be removed ˜90% within 2 hours of EC through multiple mechanisms.

Labile dissolved organic carbon supply limits hyporheic denitrification

NASA Astrophysics Data System (ADS)

Zarnetske, Jay P.; Haggerty, Roy; Wondzell, Steven M.; Baker, Michelle A.

2011-12-01

We used an in situ steady state 15N-labeled nitrate (15NO3-) and acetate (AcO-) well-to-wells injection experiment to determine how the availability of labile dissolved organic carbon (DOC) as AcO-influences microbial denitrification in the hyporheic zone of an upland (third-order) agricultural stream. The experimental wells receiving conservative (Cl- and Br) and reactive (15NO3-) solute tracers had hyporheic median residence times of 7.0 to 13.1 h, nominal flowpath lengths of 0.7 to 3.7 m, and hypoxic conditions (<1.5 mg O2 L-1). All receiving wells demonstrated 15N2 production during ambient conditions, indicating that the hyporheic zone was an environment with active denitrification. The subsequent addition of AcO- stimulated more denitrification as evidenced by significant δ15N2 increases by factors of 2.7 to 26.1 in receiving wells and significant decreases of NO3- and DO in the two wells most hydrologically connected to the injection. The rate of nitrate removal in the hyporheic zone increased from 218 kg ha-1 yr-1 to 521 kg ha-1 yr-1 under elevated AcO- conditions. In all receiving wells, increases of bromide and 15N2 occurred without concurrent increases in AcO-, indicating that 100% of AcO- was retained or lost in the hyporheic zone. These results support the hypothesis that denitrification in anaerobic portions of the hyporheic zone is limited by labile DOC supply.

Oxidation and reduction rates for organic carbon in the Amazon mainstream tributary and floodplain, inferred from distributions of dissolved gases

NASA Technical Reports Server (NTRS)

Richey, Jeffrey E.; Devol, Allan H.; Wofsy, Steven C.; Victoria, Reynaldo; Riberio, Maria N. G.

1986-01-01

Concentrations of CO2, O2, CH4, and N2O in the Amazon River system reflect an oxidation-reduction sequence in combination with physical mixing between the floodplain and the mainstem. Concentrations of CO2 ranged from 150 microM in the Amazon mainstem to 200 to 300 microM in aerobic waters of the floodplain, and up to 1000 microM in oxygen-depleted environments. Apparent oxygen utilization (AOU) ranged from 80 to 250 microM. Methane was highly supersaturated, with concentrations ranging from 0.06 microM in the mainstem to 100 microM on the floodplain. Concentrations of N2O were slightly supersaturated in the mainstem, but were undersaturated on the floodplain. Fluxes calculated from these concentrations indicated decomposition of 1600 g C sq m y(-1) of organic carbon in Amazon floodplain waters. Analysis of relationships between CH4, O2, and CO2 concentrations indicated that approximately 50 percent of carbon mineralization on the floodplain is anaerobic, with 20 percent lost to the atmoshphere as CH4. The predominance of anaerobic metabolism leads to consumption of N2O on the flood plane. Elevated concentrations of CH4 in the mainstem probably reflect imput from the floodplain, while high levels of CO2 in the mainstem are derived from a combination of varzea drainage and in situ respiration.

Nitrous oxide fluxes from tree stems of temperate forests

NASA Astrophysics Data System (ADS)

Wen, Yuan; Corre, Marife D.; Rachow, Christine; Veldkamp, Edzo

2017-04-01

Although trees are recognized as conduits of soil-generated N2O, little is known about N2O fluxes from mature trees under field conditions and thier contributions to total forest N2O fluxes. Here, we quantified in situ stem N2O fluxes from mature alder trees on poorly-drained soil and mature beech and spruce trees on well-drained soils in Solling, Germany from March to October 2015. Soil N2O fluxes, soil N2O concentrations at 40-cm depth, and soil and climatic variables known to influence N2O fluxes were also measured concurrently with the stem N2O fluxes. Alder, beech and spruce consistently emitted N2O via stems and all displayed higher emission rates in summer than in spring and in autumn. Stem N2O fluxes from alder stand were higher than those from beech and spruce stands (P < 0.01), which was attributed to the presence of aerenchyma and lenticels as well as higher soil water content and soil C and N availability in the alder stand (P < 0.01-0.05). The correlations of stem N2O fluxes from alder with soil N2O fluxes, soil N2O concentrations, soil and air temperature and vapor pressure deficit (R = 0.60 - 0.90, P < 0.01-0.05) suggest that N2O transport in alder was facilitated by a combination of passive gas diffusion through aerenchyma and active transport of dissolved N2O through sap flow. In the beech and spruce stands, correlations of stem N2O fluxes with soil and air temperature and vapor pressure deficit (R = 0.57 - 0.78, P < 0.01-0.07) suggest that active transport of dissolved N2O via xylem sap was the major mechanism for stem N2O emissions in upland trees. Stem N2O fluxes represented 8-11% of the total (soil + stem) N2O fluxes in the spruce and beech stands whereas in the alder stand, with its large soil N2O emission, stem emission contributed only 1% of the total flux. Our results suggest that the relative contribution of tree-mediated N2O fluxes is more important in upland trees than in wetland trees.

Comparison of pharmaceutical abatement in various water matrices by conventional ozonation, peroxone (O3/H2O2), and an electro-peroxone process.

PubMed

Wang, Huijiao; Zhan, Juhong; Yao, Weikun; Wang, Bin; Deng, Shubo; Huang, Jun; Yu, Gang; Wang, Yujue

2018-03-01

Pharmaceutical abatement in a groundwater (GW), surface water (SW), and secondary effluent (SE) by conventional ozonation, the conventional peroxone (O 3 /H 2 O 2 ), and the electro-peroxone (E-peroxone) processes was compared in batch tests. SE had significantly more fast-reacting dissolved organic matter (DOM) moieties than GW and SW. Therefore, O 3 decomposed much faster in SE than in GW and SW. At specific ozone doses of 0.5-1.5 mg O 3 /mg dissolved organic carbon (DOC), the application of O 3 /H 2 O 2 and E-peroxone process (by adding external H 2 O 2 stocks or in-situ generating H 2 O 2 from cathodic O 2 reduction during ozonation) similarly enhanced the OH yield from O 3 decomposition by ∼5-12% and 5-7% in GW and SW, respectively, compared to conventional ozonation. In contrast, due to the slower reaction kinetics of O 3 with H 2 O 2 than O 3 with fast-reacting DOM moieties, the addition or electro-generation of H 2 O 2 hardly increased the OH yield (<4% increases) in SE. Corresponding to the changes in the OH yields, the abatement efficiencies of ozone-resistant pharmaceuticals (ibuprofen and clofibric acid) increased evidently in GW (up to ∼14-18% at a specific ozone dose of 1.5 mg O 3 /mg DOC), moderately in SW (up to 6-10% at 0.5 mg O 3 /mg DOC), and negligibly in SE during the O 3 /H 2 O 2 and E-peroxone treatment compared to conventional ozonation. These results indicate that similar to the conventional O 3 /H 2 O 2 process, the E-peroxone process can more pronouncedly enhance O 3 transformation to OH, and thus increase the abatement efficiency of ozone-resistant pharmaceuticals in water matrices exerting relatively high ozone stability (e.g., groundwater and surface water with low DOM contents). Therefore, by installing electrodes in existing ozone reactors, the E-peroxone process may provide a convenient way to enhance pharmaceutical abatement in drinking water applications, where groundwater and surface water with low DOM contents are used as the source waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Magnesium transport extraction of transuranium elements from LWR fuel

DOEpatents

Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a U-Fe alloy containing not less than about 84% by weight uranium at a temperature in the range of from about 800.degree. C. to about 850.degree. C. to produce additional uranium metal which dissolves in the U-Fe alloy raising the uranium concentration and having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The U-Fe alloy having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with Mg metal which takes up the actinide and rare earth fission product metals. The U-Fe alloy retains the noble metal fission products and is stored while the Mg is distilled and recycled leaving the transuranium actinide and rare earth fission products isolated.

Geochemistry and cosmochemistry of fullerenes 3: Reaction of C60 and C70 with ozone

NASA Technical Reports Server (NTRS)

Heymann, D.; Chibante, L. P. F.

1993-01-01

C60 and C70 dissolved in toluene were treated with O2 gas containing 2.6 volume percent ozone and with O3-free oxygen. No reaction products were detected for 0.1 mole of O2 passed through the solution, but destruction of C60 was clearly detectable for a dose of 10(exp -6) moles of O3. C70 was destroyed more slowly than C60. Among the substances remaining in solution, we identified C60O, C70O, C60O2, C60O3, and C60O4. C60 crystals exposed to O3 at room temperature became less soluble in toluene in a matter of days, but oxides were apparently not formed.

Carbon Fluxes in Dissolved and Gaseous Forms for a Restored Peatland in British Columbia, Canada

NASA Astrophysics Data System (ADS)

D'Acunha, B.; Johnson, M. S.; Lee, S. C.; Christen, A.

2016-12-01

Peatlands are wetlands where gross primary production exceeds organic matter decomposition causing an accumulation of partially decomposed matter, also called peat. These ecosystems can accumulate more carbon than tropical rainforests. However, dissolved and gaseous fluxes of carbon (as dissolved organic carbon (DOC), CO2 and methane (CH4)) must also be considered to determine if these ecosystems are net sinks or sources of greenhouse gases (GHGs) to the atmosphere, which depends in part on the environmental conditions and the state of the ecosystem. We conducted research in Burns Bog, Delta, BC, Canada, a raised domed peat bog located in the Fraser River Delta and one of the largest raised peat bogs on the west coast of the Americas, but which has been heavily impacted by a range of human activities. Currently, ecological restoration efforts are underway by a large-scale ditch blocking program, with the aim to re-establish a high water table. This is approached in partnership with research on the ecosystem services that the bog provides, including its role in a regional GHG inventory. Here we present data on ecosystem-scale fluxes of CO2 and CH4 determined by eddy covariance (EC) on a floating tower platform, and complementary data on (i) evasion fluxes of CO2, CH4 and nitrous oxide (N2O) from the water surface to the atmosphere, and (ii) the flux and composition of dissolved organic carbon in water draining Burns Bog. Concentrations of dissolved CO2, CH4 and N2O were determined by headspace equilibration, and evasion rates from the water surface were quantified and are used to estimate the role of the hydrosphere in the ecosystem-scale measurements. Water samples collected from five saturated areas in the flux tower footprint were analyzed for DOC concentrations and composition. Results indicated that, even though the whole system is a net C sink, the water surface behaved as a source of CO2 and CH4, and a sink for N2O throughout the study period. Drainage waters were high in DOC (> 30 mg L-1). DOC export was found to offset about 20% of the apparent net C uptake determined by EC, indicating that the EC system overestimates carbon accumulation by not accounting for DOC drainage.

Effect of high carbon dioxide atmosphere packaging and soluble gas stabilization pre-treatment on the shelf-life and quality of chicken drumsticks.

PubMed

Al-Nehlawi, A; Saldo, J; Vega, L F; Guri, S

2013-05-01

The effects of an aerobic modified atmosphere packaging (MAP) (70% CO2, 15% O2 and 15% N2) with and without a CO2 3-h soluble gas stabilization (SGS) pre-treatment of chicken drumsticks were determined for various package and product quality characteristics. The CO2 dissolved into drumsticks was determined. The equilibrium between CO2 dissolved in drumsticks and CO2 in head space was reached within 48h after packaging, showing highest values of CO2 in SGS pre-treated samples. This greater availability of CO2 resulted in lower counts of TAB and Pseudomonas in SGS than in MAP drumsticks. Package collapse was significantly reduced in SGS samples. The average of CO2 dissolved in the MAP treatment was 567mg CO2kg(-1) of chicken and, 361mg CO2kg(-1) of chicken during the MAP treatment, in SGS pre-treated samples. This difference could be the quantity of CO2 dissolved during SGS pre-treatment. These results highlight the advantages of using SGS versus traditional MAP for chicken products preservation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Tidal and spatial variability of nitrous oxide (N2O) in Sado estuary (Portugal)

NASA Astrophysics Data System (ADS)

Gonçalves, Célia; Brogueira, Maria José; Nogueira, Marta

2015-12-01

The estimate of the nitrous oxide (N2O) fluxes is fundamental to assess its impact on global warming. The tidal and spatial variability of N2O and the air-sea fluxes in the Sado estuary in July/August 2007 are examined. Measurements of N2O and other relevant environmental parameters (temperature, salinity, dissolved oxygen and dissolved inorganic nitrogen - nitrate plus nitrite and ammonium) were recorded during two diurnal tidal cycles performed in the Bay and Marateca region and along the estuary during ebb, at spring tide. N2O presented tidal and spatial variability and varied spatially from 5.0 nmol L-1 in Marateca region to 12.5 nmol L-1 in Sado river input. Although the Sado river may constitute a considerable N2O source to the estuary, the respective chemical signal discharge was rapidly lost in the main body of the estuary due to the low river flow during the sampling period. N2O varied with tide similarly between 5.2 nmol L-1 (Marateca) and 10.0 nmol L-1 (Sado Bay), with the maximum value reached two hours after flooding period. The influence of N2O enriched upwelled seawater (˜10.0 nmol L-1) was well visible in the estuary mouth and apparently represented an important contribution of N2O in the main body of Sado estuary. Despite the high water column oxygen saturation in most of Sado estuary, nitrification did not seem a relevant process for N2O production, probably as the concentration of the substrate, NH4+, was not adequate for this process to occur. Most of the estuary functioned as a N2O source, and only Marateca zone has acted as N2O sink. The N2O emission from Sado estuary was estimated to be 3.7 Mg N-N2O yr-1 (FC96) (4.4 Mg N-N2O yr-1, FRC01). These results have implications for future sampling and scaling strategies for estimating greenhouse gases (GHGs) fluxes in tidal ecosystems.

FIELD MEASUREMENT OF DISSOLVED OXYGEN: A COMPARISON OF METHODS

EPA Science Inventory

The ability to confidently measure the concentration of dissolved oxygen (D.O.) in ground water is a key aspect of remedial selection and assessment. Presented here is a comparison of the commonly practiced methods for determining D.O. concentrations in ground water, including c...

Polydopamine-Coated TiO2 Nanotubes for Selective Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde Under Visible Light.

PubMed

Tripathy, Jyotsna; Loget, Gabriel; Altomare, Marco; Schmuki, Patrik

2016-05-01

TiO2 nanotube arrays grown by anodization were coated with thin layers of polydopamine as visible light sensitizer. The PDA-coated TiO2 scaffolds were used as photocatalyst for selective oxidation of benzyl alcohol under monochromatic irradiation at 473 nm. Benzaldehyde was selectively formed and no by-products could be detected. A maximized reaction yield was obtained in O2-saturated acetonitrile. A mechanism is proposed that implies firstly the charge carrier generation in polydopamine as a consequence of visible light absorption. Secondly, photo-promoted electrons are injected in TiO2 conduction band, and subsequently transferred to dissolved O2 to form O*2- radicals. These radicals react with benzyl alcohol and lead to its selective dehydrogenation oxidation towards benzaldehyde.

Simultaneous and continuous measurements of dissolved CO2, CH4, N2O and CO in rivers using Fourier-Transform-InfraRed (FTIR) spectrometry

NASA Astrophysics Data System (ADS)

Warneke, Thorsten; Müller, Denise; Caldow, Christopher; Rixen, Tim; Notholt, Justus

2015-04-01

We have coupled a Fourier-Transform InfraRed (FTIR) trace gas analyser to an equilibrator, which allows the simultaneous and continuous measurement of dissolved CO2, CH4, N2O and CO in water. The FTIR-technique has a high precision over a wide range of concentrations, making it very suitable for the measurement of these gases in freshwater systems. We have employed this measurement system on a commercial river barge on the Elbe river (Czech Republic, Germany) and on a fisher boat in the coastal area of Sarawak (Malaysia). In addition we have performed stationary continuous measurements at a small river in Northern Germany over the duration of 3 months. The presentation will outline the advantages and disadvantages of the FTIR-technique for freshwater measurements and will present results from the measurement campaigns.

Hydrologic control on redox and nitrogen dynamics in a peatland soil.

PubMed

Rubol, Simonetta; Silver, Whendee L; Bellin, Alberto

2012-08-15

Soils are a dominant source of nitrous oxide (N(2)O), a potent greenhouse gas. However, the complexity of the drivers of N(2)O production and emissions has hindered our ability to predict the magnitude and spatial dynamics of N(2)O fluxes. Soil moisture can be considered a key driver because it influences oxygen (O(2)) supply, which feeds back on N(2)O sources (nitrification versus denitrification) and sinks (reduction to dinitrogen). Soil water content is directly linked to O(2) and redox potential, which regulate microbial metabolism and chemical transformations in the environment. Despite its importance, only a few laboratory studies have addressed the effects of hydrological transient dynamics on nitrogen (N) cycling in the vadose zone. To further investigate these aspects, we performed a long term experiment in a 1.5 m depth soil column supplemented by chamber experiments. With this experiment, we aimed to investigate how soil moisture dynamics influence redox sensitive N cycling in a peatland soil. As expected, increased soil moisture lowered O(2) concentrations and redox potential in the soil. The decline was more severe for prolonged saturated conditions than for short events and at deep than at the soil surface. Gaseous and dissolved N(2)O, dissolved nitrate (NO(3)(-)) and ammonium (NH(4)(+)) changed considerably along the soil column profile following trends in soil O(2) and redox potential. Hot spots of N(2)O concentrations corresponded to high variability in soil O(2) in the upper and lower parts of the column. Results from chamber experiments confirmed high NO(3)(-) reduction potential in soils, particularly from the bottom of the column. Under our experimental conditions, we identified a close coupling of soil O(2) and N(2)O dynamics, both of which lagged behind soil moisture changes. These results highlight the relationship among soil hydrologic properties, redox potential and N cycling, and suggest that models working at a daily scale need to consider soil O(2) dynamics in addition to soil moisture dynamics to accurately predict patterns in N(2)O fluxes. Copyright © 2012 Elsevier B.V. All rights reserved.

Lake Metabolism: Comparison of Lake Metabolic Rates Estimated from a Diel CO2- and the Common Diel O2-Technique.

PubMed

Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar

2016-01-01

Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer.

Lake Metabolism: Comparison of Lake Metabolic Rates Estimated from a Diel CO2- and the Common Diel O2-Technique

PubMed Central

Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar

2016-01-01

Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer. PMID:28002477

Removal of elevated level of chromium in groundwater by the fabricated PANI/Fe3O4 nanocomposites.

PubMed

Ramachandran, Aruna; Prasankumar, T; Sivaprakash, S; Wiston, Biny R; Biradar, Santhosh; Jose, Sujin

2017-03-01

In this work, we report the reduction of chromium concentration in the polluted groundwater samples from Madurai Kamaraj University area, India, where the dissolved salts in groundwater are reported as serious health hazards for its inhabitants. The water samples have intolerable amounts of total dissolved solids (TDS) and chromium is a prominent pollutant among them. Chromium reduction was achieved by treating the polluted groundwater with PANI/Fe 3 O 4 nanocomposites synthesized by in situ polymerization method. Further experimentation showed that the nanocomposites exhibit better chromium removal characteristics upon increasing the aniline concentration during the synthesis. We were able to reduce chromium concentration in the samples from 0.295 mg L -1 to a tolerable amount of 0.144 mg L -1 . This work is expected to open doors for chromium-free groundwater in various regions of India, when improved to an industrial scale.

Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer

NASA Astrophysics Data System (ADS)

Brown, C. J.; Schoonen, M. A. A.; Candela, J. L.

2000-11-01

Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O 2 and SO 42- in the aerobic zone, and to the reduction of SO 42- in the anaerobic zone; estimated rates of CO 2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO 2 production calculated from dissolved inorganic carbon mass transfer (2.55×10 -4 to 48.6×10 -4 mmol l -1 yr-1) generally were comparable to the calculated rates of CO 2 production by the combined reduction of O 2, Fe(III) and SO 42- (1.31×10 -4 to 15×10 -4 mmol l -1 yr-1). The overall increase in SO 42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in δ34S values along the flow path indicate that SO 42- loss through microbial reduction is exceeded by SO 42- gain through diffusion from sediments and through the oxidation of FeS 2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO 42--rich zones have been depleted by microbial reduction and resulted in localized SO 42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO 42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.

Circulation and oxygen cycling in the Mediterranean Sea: Sensitivity to future climate change

NASA Astrophysics Data System (ADS)

Powley, Helen R.; Krom, Michael D.; Van Cappellen, Philippe

2016-11-01

Climate change is expected to increase temperatures and decrease precipitation in the Mediterranean Sea (MS) basin, causing substantial changes in the thermohaline circulation (THC) of both the Western Mediterranean Sea (WMS) and Eastern Mediterranean Sea (EMS). The exact nature of future circulation changes remains highly uncertain, however, with forecasts varying from a weakening to a strengthening of the THC. Here we assess the sensitivity of dissolved oxygen (O2) distributions in the WMS and EMS to THC changes using a mass balance model, which represents the exchanges of O2 between surface, intermediate, and deep water reservoirs, and through the Straits of Sicily and Gibraltar. Perturbations spanning the ranges in O2 solubility, aerobic respiration kinetics, and THC changes projected for the year 2100 are imposed to the O2 model. In all scenarios tested, the entire MS remains fully oxygenated after 100 years; depending on the THC regime, average deep water O2 concentrations fall in the ranges 151-205 and 160-219 µM in the WMS and EMS, respectively. On longer timescales (>1000 years), the scenario with the largest (>74%) decline in deep water formation rate leads to deep water hypoxia in the EMS but, even then, the WMS deep water remains oxygenated. In addition, a weakening of THC may result in a negative feedback on O2 consumption as supply of labile dissolved organic carbon to deep water decreases. Thus, it appears unlikely that climate-driven changes in THC will cause severe O2 depletion of the deep water masses of the MS in the foreseeable future.

Effects of acetylacetone on the photoconversion of pharmaceuticals in natural and pure waters.

PubMed

Zhang, Guoyang; Wu, Bingdang; Zhang, Shujuan

2017-06-01

Acetylacetone (AcAc) has proven to be a potent photo-activator in the degradation of color compounds. The effects of AcAc on the photochemical conversion of five colorless pharmaceuticals were for the first time investigated in both pure and natural waters with the UV/H 2 O 2 process as a reference. In most cases, AcAc played a similar role to H 2 O 2 . For example, AcAc accelerated the photodecomposition of carbamazepine, oxytetracycline, and tetracycline in pure water. Meanwhile, the toxicity of tetracyclines and carbamazepine were reduced to a similar extent to that in the UV/H 2 O 2 process. However, AcAc worked in a way different from that of H 2 O 2 . Based on the degradation kinetics, solvent kinetic isotope effect, and the inhibiting effect of O 2 , the underlying mechanisms for the degradation of pharmaceuticals in the UV/AcAc process were believed mainly to be direct energy transfer from excited AcAc to pharmaceuticals rather than reactive oxygen species-mediated reactions. In natural waters, dissolved organic matter (DOM) played a crucial role in the photoconversion of pharmaceuticals. The role of H 2 O 2 became negligible due to the scavenging effects of DOM and inorganic ions. Interestingly, in natural waters, AcAc first accelerated the photodecomposition of pharmaceuticals and then led to a dramatic reduction with the depletion of dissolved oxygen. Considering the natural occurrence of diketones, the results here point out a possible pathway in the fate and transport of pharmaceuticals in aquatic ecosystems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Targeted Gold Nanoparticle Contrast Agent for Digital Breast Tomosynthesis and Computed Tomography

DTIC Science & Technology

2010-03-01

hearing mantle and magnetic stirrer, and the gold solution was brought to a boil (Figure 1a). Next, 0.93 g of sodium citrate dihydrate...C6H5Na3O7.2H2O ) was dissolved in 45 mL of DI-H2O and added to the boiling gold solution. Upon addition of the sodium citrate, the solution rapidly changed...diatrizoate and related triiodinated benzoates by Trametes versicolor. Appl Environ Microbiol, 1998. 64(8): p. 3114-7. 2. Baselga, J., A.D. Seidman, P.P

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

USGS Publications Warehouse

Amos, R.T.; Bekins, B.A.; Delin, G.N.; Cozzarelli, I.M.; Blowes, D.W.; Kirshtein, J.D.

2011-01-01

High resolution direct-push profiling over short vertical distances was used to investigate CH4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH4 and CO2, and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in ??13CCH4 from an average of - 57.6??? (?? 1.7???) in the methanogenic zone to - 39.6??? (?? 8.7???) at 105 m downgradient, strongly suggest CH4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O2 across the water table is leading to aerobic degradation of CH4 at this interface. Dissolved N2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O2 through aerobic degradation of CH4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O2 transport mechanisms. ?? 2011 Elsevier B.V. All rights reserved.

Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation of Fe oxides at near-neutral pH

USGS Publications Warehouse

Burrows, Jill E.; Cravotta, Charles A.; Peters, Stephen C.

2017-01-01

Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L FeII and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H2O2) to test the hypothesis that aeration increases pH, FeII oxidation, hydrous FeIII oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H2O2 treatment. Aeration accelerated removal of dissolved CO2, Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H2O2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn.Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO2, Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO2 available to form ZnCO30 and Zn(CO3)22− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH < 7.5 and desorption at higher pH where Al(OH)4− was predominant. Thus, aeration or chemical oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.

Radiochemical synthesis of a carbon-supported Pt-SnO2 bicomponent nanostructure exhibiting enhanced catalysis of ethanol oxidation

NASA Astrophysics Data System (ADS)

Okazaki, Tomohisa; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro; Ohkubo, Yuji; Akita, Tomoki; Nitani, Hiroaki; Yamamoto, Takao A.

2015-03-01

Carbon-supported Pt-SnO2 electrocatalysts with various Sn/Pt molar ratios were prepared by an electron beam irradiation method. These catalysts were composed of metallic Pt particles approximately 5 nm in diameter together with low crystalline SnO2. The contact between the Pt and SnO2 in these materials varied with the amount of dissolved oxygen in the precursor solutions and it was determined that intimate contact between the Pt and SnO2 significantly enhanced the catalytic activity of these materials during the ethanol oxidation reaction. The mechanism by which the contact varies is discussed based on the radiochemical reduction process.

First stage of reaction of molten Al with MgO substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morgiel, J., E-mail: j.morgiel@imim.pl; Sobczak, N.; Motor Transport Institute, 80 Jagiellońska St., 03-301 Warsaw

The Al/MgO couple was produced in vacuum (~ 5 × 10{sup −} {sup 4} Pa) by contact heating from RT up to 1000 °C and holding at that temperature for 1 h of a small 4 × 4 × 4 mm aluminium (5 N) sample placed on the [100] MgO single crystal substrate. TEM observations backed with electron diffraction analysis indicated that the interaction between liquid aluminium and MgO starts from a redox reaction producing a continuous layer of MgAl{sub 2}O{sub 4} spinel on the substrate surface. Its growth is controlled by solid state out-diffusion of magnesium and oxygen towardsmore » the surface being in contact with liquid metal. The thickening of spinel layer is accompanied by its cracking and infiltration with aluminium. The above process enables local dissolution of the MgO substrate and formation in it of a thin region of interpenetrating metallic channels walled with spinel. The removal of dissolved magnesium through open aluminium channels towards the drop and to vacuum locally produces areas of aluminium enriched with dissolved oxygen, which results in the nucleation of α-Al{sub 2}O{sub 3} at spinel clad walls. The growth of α-Al{sub 2}O{sub 3} is controlled only by the dissolution rate of MgO by aluminium, liquid state diffusion of Mg to drop/vacuum and oxygen to the front of the of α-Al{sub 2}O{sub 3} crystallites growing into MgO substrate. - Highlights: • New unique evidence of first stages of interaction of liquid Al with MgO substrates • Interaction of liquid Al with MgO starts with the formation of a layer MgAl{sub 2}O{sub 4}. • Growth of MgAl{sub 2}O{sub 4} is slow as controlled by solid state out-diffusion of Mg and O. • MgAl{sub 2}O{sub 4} serves as a nucleation site for Al{sub 2}O{sub 3} and consumed by it soon after. • Growth of Al{sub 2}O{sub 3} is fast as controlled by diffusion in liquid state.« less

[Sediment-water flux and processes of nutrients and gaseous nitrogen release in a China River Reservoir].

PubMed

Chen, Zhu-hong; Chen, Neng-wang; Wu, Yin-qi; Mo, Qiong-li; Zhou, Xing-peng; Lu, Ting; Tian, Yun

2014-09-01

The key processes and fluxes of nutrients (N and P) and gaseous N (N2 and N2O) across the sediment-water interface in a river reservoir (Xipi) of the Jiulong River watershed in southeast China were studied. Intact core sediment incubation of nutrients exchange, in-situ observation and lab incubation of excess dissolved N2 and N2O (products of nitrification, denitrification and Anammox), and determination of physiochemical and microbe parameters were carried out in 2013 for three representative sites along the lacustrine zone of the reservoir. Results showed that ammonium and phosphate were generally released from sediment to overlying water [with averaged fluxes of N (479.8 ± 675.4) mg. (m2. d)-1 and P (4. 56 ± 0.54) mg. (m2 d) -1] , while nitrate and nitrite diffused into the sediment. Flood events in the wet season could introduce a large amount of particulate organic matter that would be trapped by the dam reservoir, resulting in the high release fluxes of ammonium and phosphate observed in the following low-flow season. No clear spatial variation of sediment nutrient release was found in the lacustrine zone of the reservoir. Gaseous N release was dominated by excess dissolved N2 (98% of total), and the N2 flux from sediment was (15.8 ± 12. 5) mg (m2. d) -1. There was a longitudinal and vertical variation of excess dissolved N2, reflecting the combined results of denitrification and Anammox occurring in anoxic sediment and fluvial transport. Nitrification mainly occurred in the lower lacustrine zone, and the enrichment of N2O was likely regulated by the ratio of ammonium to DIN in water.

Coupled oxygen-carbon dioxide modelling to partition potential external contribution to stream carbon dioxide concentrations.

NASA Astrophysics Data System (ADS)

Butman, D. E.; Holtgrieve, G. W.

2017-12-01

Recent modelling studies in large catchments have estimated that in excess of 74% of the dissolved carbon dioxide found in first and second order streams originate from allochthonous sources. Stable isotopes of carbon-13 in carbon dioxide have been used to identify ground water seeps in stream systems, where decreases in δ13CO2 occur along gaining stream reaches, suggesting that carbon dioxide in ground water is more depleted than what is found in surface water due to fractionation of CO2 during emissions across the air water interface. Although isotopes represent a chemical tracer in stream systems for potential groundwater contribution, the temporal resolution of discrete samples make partitioning allochthonous versus autochthonous sources of CO2 difficult on hydrologically relevant time scales. Here we show results of field deployments of high frequent dissolved CO2, O2, PAR, Temperature and pH from the Thornton Creek Watershed, the largest urban watershed in Seattle, WA. We present an exploration into using high resolution time series of dissolved oxygen and carbon dioxide in a dual gas approach to separate the contribution of in stream respiration from external sources. We extend upon previous efforts to model stream metabolism across diel cycles by incorporating simultaneous direct measurements of dissolved oxygen, PCO2, and pH within an inverse modeling framework and Bayesian parameter estimation. With an initial assumption of a stoichiometric ratio of 1:1 for O2 and CO2 for autochthonous driven metabolism, we investigate positive or negative departures from this ratio as an indicator of external CO2 to the stream (terrestrial or atmospheric) and factors contributing to this flux.

Activation of Hydrogen Peroxide by Iron-Containing Minerals and Catalysts in Circumneutral pH Solutions: Implications for ex situ and in situ Treatment of Contaminated Water and Soil

NASA Astrophysics Data System (ADS)

Pham, Anh Le Tuan

The decomposition of hydrogen peroxide (H2O2) on iron minerals can generate hydroxyl radical (•OH), a strong oxidant capable of transforming a wide range of contaminants. This reaction is critical to ex situ advanced oxidation processes employed in waste treatment systems, as well as in situ chemical oxidation processes used for soil and groundwater remediation. Unfortunately, the process in the ex situ treatment systems is relatively inefficient at circumneutral pH values. In this research, the development of iron-containing catalysts with improved efficiency was investigated. In addition, little is known about the factors that control the performance of in situ treatment systems. Another aim of this dissertation was to elucidate those factors to provide a basis for improving the efficiency of the remediation method. Two types of silica- and alumina-containing iron (hydr)oxide catalysts were synthesized by sol-gel processing techniques (Chapter 2). Relative to iron oxides, such as hematite and goethite, these catalysts were 10 to 80 times more effective in catalyzing the production of •OH from H2O2 under circumneutral conditions. The higher efficiency makes these catalysts promising candidates for ex situ advanced oxidation processes. Moreover, because alumina and silica alter the reactivity of the iron oxides with H2O2, understanding the activity of iron associated with natural aluminosilicates and silica-containing minerals in the subsurface is crucial to explaining the variability of •OH production observed in in situ treatment systems. In addition to the sol-gel technique used in Chapter 2, silica-containing iron (hydr)oxide catalysts were synthesized by immobilizing iron oxide onto mesoporous silica supports, such as SBA-15 (Chapter 5). The iron-containing SBA-15 was 10 times more effective than iron oxides in catalyzing the production of •OH from H2O2. Moreover, this catalyst could be employed for selective oxidation of small organic contaminants based on size exclusion. However, a major drawback of the mesoporous silica-based catalysts is their instability under circumneutral conditions (Chapter 6). The dissolution of mesoporous silica materials raises questions about their use for water treatment, because silica dissolution might compromise the behavior of the material. To gain insight into factors that control H2O2 persistence and •OH yield in in situ processes, the decomposition of H2O2 and transformation of contaminants were investigated in the presence of iron-containing minerals and aquifer materials (Chapter 3). Consistent with the observation described in Chapter 2, iron-containing aluminosilicates were more effective than iron oxides in converting H2O2 into •OH. In both iron-containing mineral and aquifer material systems, the yield of •OH was inversely correlated with the rate of H 2O2 decomposition. In the aquifer material systems, the yield also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce •OH. The inverse correlation between Mn content and H2O2 loss rate and •OH yield suggests that the amount of Mn in aquifer materials could serve as a proxy for predicting H2O2 decomposition rates and contaminant oxidation efficiency. In addition to the surface and structure properties of iron solids, the presence of solutes, such as dissolved silica, also affected the decomposition of H2O2 (Chapter 4). The adsorption of dissolved silica onto mineral surfaces altered the catalytic sites, thereby decreasing the reactivity of iron- and manganese-containing minerals with H2O 2. Therefore, the presence of dissolved SiO2 could lead to greater persistence of H2O2 in groundwater, which should be considered in the design of in situ H2O 2-based treatment systems. In addition to in situ treatment, dissolved silica also can affect the reactivity of iron-containing catalysts used in ex situ processes. Therefore, its presence in contaminated industrial wastewater should be considered when ex situ treatment systems are designed.

Intensification of electrochemiluminescence of luminol on TiO2 supported Au atomic cluster nano-hybrid modified electrode.

PubMed

Yu, Zhimin; Wei, Xiuhua; Yan, Jilin; Tu, Yifeng

2012-04-21

With TiO(2) nanoparticles as carrier, a supported nano-material of Au atomic cluster/TiO(2) nano-hybrid was synthesized. It was then modified onto the surface of indium tin oxide (ITO) by Nafion to act as a working electrode for exciting the electrochemiluminescence (ECL) of luminol. The properties of the nano-hybrid and the modified electrode were characterized by XRD, XPS, electronic microscopy, electrochemistry and spectroscopy. The experimental results demonstrated that the modification of this nano-hybrid onto the ITO electrode efficiently intensified the ECL of luminol. It was also revealed that the ECL intensity of luminol on this modified electrode showed very sensitive responses to oxygen and hydrogen peroxide. The detection limits for dissolved oxygen and hydrogen peroxide were 2 μg L(-1) and 5.5 × 10(-12) M, respectively. Besides the discussion of the intensifying mechanism of this nano-hybrid for ECL of luminol, the developed method was also applied for monitoring dissolved oxygen and evaluating the scavenging efficiency of reactive oxygen species of the Ganoderma lucidum spore.

Direct 1H NMR evidence of spin-rotation coupling as a source of para → ortho-H2 conversion in diamagnetic solvents

NASA Astrophysics Data System (ADS)

Terenzi, Camilla; Bouguet-Bonnet, Sabine; Canet, Daniel

2017-04-01

At ambient temperature, conversion from 100% enriched para-hydrogen (p-H2; singlet state) to ortho-hydrogen (o-H2; triplet state) leads necessarily to the thermodynamic equilibrium proportions: 75% of o-H2 and 25% of p-H2. When p-H2 is dissolved in a diamagnetic organic solvent, conversion is very slow and can be considered as arising from nuclear spin relaxation phenomena. A first relaxation mechanism, specific to the singlet state and involving a combination of auto-correlation and cross correlation spectral densities, can be retained: randomly fluctuating magnetic fields due to inter-molecular dipolar interactions. We demonstrate here that (i) this dipolar mechanism is not sufficient for accounting for the p a r a →o r t h o conversion rate, (ii) spin-rotation interaction, an intra-molecular mechanism, behaves similarly to random-field interaction and, thus, may be involved in the singlet relaxation rate. Also, as the p a r a →o r t h o conversion is monitored by proton nuclear magnetic resonance (NMR) of dissolved o-H2 (p-H2 is NMR-silent), one has to account for H2 exchange between the liquid phase and the gas phase within the NMR tube, as well as for dissolution effects. Experimental evidence of the above statements is brought here in the case of two organic solvents: acetone-d6 and carbon disulfide. The observed temperature dependence of the p a r a →o r t h o conversion rate shows that spin-rotation can be the dominant contribution to the p-H2 relaxation rate in the absence of tangible dipolar interactions. Our findings shed new light on the "mysterious" mechanism of the p a r a →o r t h o conversion which has been searched for several decades.

Water quality and dissolved inorganic fluxes of N, P, SO₄, and K of a small catchment river in the Southwestern Coast of India.

PubMed

Padmalal, D; Remya, S I; Jyothi, S Jissy; Baijulal, B; Babu, K N; Baiju, R S

2012-03-01

The southwestern coast of India is drained by many small rivers with lengths less than 250 km and catchment areas less than 6,500 km(2). These rivers are perennial and are also the major drinking water sources in the region. But, the fast pace of urbanization, industrialization, fertilizer intensive agricultural activities and rise in pilgrim tourism in the past four to five decades have imposed marked changes in water quality and solute fluxes of many of these rivers. The problems have aggravated further due to leaching of ionic constituents from the organic-rich (peaty) impervious sub-surface layers that are exposed due to channel incision resulting from indiscriminate instream mining for construction-grade sand and gravel. In this context, an attempt has been made here to evaluate the water quality and the net nutrient flux of one of the important rivers in the southwestern coast of India, the Manimala river which has a length of about 90 km and catchment area of 847 km(2). The river exhibits seasonal variation in most of the water quality parameters (pH, electrical conductivity, dissolved oxygen, total dissolved solids, Ca, Mg, Na, K, Fe, HCO(3), NO(2)-N, NO(3)-N, P[Formula: see text], P[Formula: see text], chloride, SO(4), and SiO(2)). Except for NO(3)-N and SiO(2), all the other parameters are generally enriched in non-monsoon (December-May) samples than that of monsoon (June-November). The flux estimation reveals that the Manimala river transports an amount of 2,308 t y(-1) of dissolved inorganic nitrogen, 87 t y(-1) dissolved inorganic phosphorus, and 9246 t y(-1) of SO(4), and 1984 t y(-1) K into the receiving coastal waters. These together constitute about 23% of the total dissolved fluxes transported by the Manimala river. Based on the study, a set of mitigation measures are also suggested to improve the overall water quality of small catchment rivers of the densely populated tropics in general and the south western coast in particular.

Smart operation of nitritation/denitritation virtually abolishes nitrous oxide emission during treatment of co-digested pig slurry centrate.

PubMed

Peng, Lai; Carvajal-Arroyo, José M; Seuntjens, Dries; Prat, Delphine; Colica, Giovanni; Pintucci, Cristina; Vlaeminck, Siegfried E

2017-12-15

The implementation of nitritation/denitritation (Nit/DNit) as alternative to nitrification/denitrification (N/DN) is driven by operational cost savings, e.g. 1.0-1.8 EUR/ton slurry treated. However, as for any biological nitrogen removal process, Nit/DNit can emit the potent greenhouse gas nitrous oxide (N 2 O). Challenges remain in understanding formation mechanisms and in mitigating the emissions, particularly at a low ratio of organic carbon consumption to nitrogen removal (COD rem /N rem ). In this study, the centrate (centrifuge supernatant) from anaerobic co-digestion of pig slurry was treated in a sequencing batch reactor. The process removed approximately 100% of ammonium a satisfactory nitrogen loading rate (0.4 g N/L/d), with minimum nitrite and nitrate in the effluent. Substantial N 2 O emission (around 17% of the ammonium nitrogen loading) was observed at the baseline operational condition (dissolved oxygen, DO, levels averaged at 0.85 mg O 2 /L; COD rem /N rem of 2.8) with ∼68% of the total emission contributed by nitritation. Emissions increased with higher nitrite accumulation and lower organic carbon to nitrogen ratio. Yet, higher DO levels (∼2.2 mg O 2 /L) lowered the aerobic N 2 O emission and weakened the dependency on nitrite concentration, suggesting a shift in N 2 O production pathway. The most effective N 2 O mitigation strategy combined intermittent patterns of aeration, anoxic feeding and anoxic carbon dosage, decreasing emission by over 99% (down to ∼0.12% of the ammonium nitrogen loading). Without anaerobic digestion, mitigated Nit/DNit decreases the operational carbon footprint with about 80% compared to N/DN. With anaerobic digestion included, about 4 times more carbon is sequestered. In conclusion, the low COD rem /N rem feature of Nit/DNit no longer offsets its environmental sustainability provided the process is smartly operated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Seasonal water chemistry variability in the Pangani River basin, Tanzania.

PubMed

Selemani, Juma R; Zhang, Jing; Muzuka, Alfred N N; Njau, Karoli N; Zhang, Guosen; Maggid, Arafa; Mzuza, Maureen K; Jin, Jie; Pradhan, Sonali

2017-11-01

The stable isotopes of δ 18 O, δ 2 H, and 87 Sr/ 86 Sr and dissolved major ions were used to assess spatial and seasonal water chemistry variability, chemical weathering, and hydrological cycle in the Pangani River Basin (PRB), Tanzania. Water in PRB was NaHCO 3 type dominated by carbonate weathering with moderate total dissolved solids. Major ions varied greatly, increasing from upstream to downstream. In some stations, content of fluoride and sodium was higher than the recommended drinking water standards. Natural and anthropogenic factors contributed to the lowering rate of chemical weathering; the rate was lower than most of tropical rivers. The rate of weathering was higher in Precambrian than volcanic rocks. 87 Sr/ 86 Sr was lower than global average whereas concentration of strontium was higher than global average with mean annual flux of 0.13 × 10 6  mol year -1 . Evaporation and altitude effects have caused enrichment of δ 18 O and δ 2 H in dry season and downstream of the river. Higher d-excess value than global average suggests that most of the stations were supplied by recycled moisture. Rainfall and groundwater were the major sources of surface flowing water in PRB; nevertheless, glacier from Mt. Kilimanjaro has insignificant contribution to the surface water. We recommend measures to be taken to reduce the level of fluoride and sodium before domestic use.

Annual dynamics of N2O, CH4 and CO2 fluxes from the agricultural irrigation watersheds in southeast China

NASA Astrophysics Data System (ADS)

Wu, S.; Zou, J.; Liu, S.; Chen, J.; Kong, D.; Geng, Y.

2017-12-01

Agricultural irrigation watershed covers a large area in southeast of China and is a potentially important source of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). However, the flux magnitudes contribution to the overall catchment greenhouse gas (GHGs) fluxes and their drivers of seasonal variability are limited in agricultural irrigation watersheds. An in-situ observation was performed to measure annual CO2, CH4 and N2O fluxes from an agricultural irrigation watershed in southeast of China from September 2014 to September 2016. GHGs fluxes were measured using floating chambers and a gas exchange model was also used to predict CH4 and N2O fluxes. All GHGs showed varied seasonally with highest fluxes in early summer (July) and lowest in winter. Estimated seasonal CH4-C fluxes (11.5-97.6 mg m-2 hr-1) and N2O-N fluxes (2.8-80.8μg m-2 hr-1) were in relative agreement with measured CH4-C fluxes (0.05-74.9mg m-2 hr-1) and N2O-N fluxes (3.9-68.7μg m-2 hr-1) fluxes using floating chambers. Both CH4 and N2O fluxes were positively related to water temperature. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to sediment dissolved organic carbon (DOC). The N2O fluxes were positively related to water NH4+ and NO3-. The calculated EF5-r value in this study (mean = 0.0016; range = 0.0013-0.0018) was below the current IPCC (2006) default value of 0.0025. This implied that IPCC methodology may over estimates of N2O emissions associated with nitrogen leaching and runoff from agriculture.

Dissolved heavy metal determination and ecotoxicological assessment: a case study of the corumbataí river (são paulo, Brazil).

PubMed

Aparecida Maranho, Lucineide; Teresinha Maranho, Leila; Grossi Botelho, Rafael; Luiz Tornisielo, Valdemar

2014-09-29

The aim of this one-year study (August 2009 to July 2010) was to evaluate the Corumbataí River water polluted by anthropogenic sources and see how it affects the reproduction of the microcrustacean Ceriodaphnia dubia (Richard, 1984) in laboratory conditions over seven days of exposure to water samples collected monthly at six different locations. We determined the concentrations of zinc (Zn), copper (Cu), nickel (Ni), lead (Pb), and cadmium (Cd), as well as physicochemical parameters such as dissolved oxygen, conductivity, water temperature, and pH. Dissolved oxygen and conductivity demonstrated anthropogenic influence, as dissolved oxygen concentration decreased and conductivity increased from the upstream to the downstream stretch of the river. The effects on C. dubia were observed in the months with high precipitation, but the toxicity cannot be associated with any particular contaminant. Heavy metal levels kept well below the limit values. Zn and Pb had the highest concentrations in the water during the sampling period, probably due to the industrial and agricultural influence. However, these levels do not seem to be associated with precipitation, which suggests that their primary source was industry. Physicochemical parameters, the ecotoxicological assay, and determination of heavy metals proved to be efficient tools to evaluate aquatic environments.

Emission properties of Ga2O3 nano-flakes: effect of excitation density.

PubMed

Pozina, G; Forsberg, M; Kaliteevski, M A; Hemmingsson, C

2017-02-08

In the quest of developing high performance electronic and optical devices and more cost effective fabrication processes of monoclinic β-Ga 2 O 3 , new growth techniques and fundamental electronic and optical properties of defects have to be explored. By heating of dissolved metallic Ga in HCl in a NH 3 and N 2 atmosphere, nano-flake films of monoclinic β-phase Ga 2 O 3 were grown as confirmed by XRD. From optical measurements, we observe two strong emissions. A red band peaking at ~2.0 eV and a UV band at ~3.8 eV. The band at ~2.0 eV is attributed to donor-acceptor pair recombination where the donor and acceptor level is suggested to be related to V O and nitrogen, respectively. By studying the dependence of the intensity of the UV band at 3.8 eV versus excitation density, a model is suggested. In the model, it is assumed that local potential fluctuations forming minima (maxima), where the carriers would be localized with a summarized band offset for conduction and valence band of 1 eV. The origin of the fluctuations is tentatively suggested to be related to micro-inclusions of different phases in the film.

Comparative performance of CO2 measuring methods: marine aquaculture recirculation system application

USGS Publications Warehouse

Pfeiffer, T.J.; Summerfelt, S.T.; Watten, B.J.

2011-01-01

Many methods are available for the measurement of dissolved carbon dioxide in an aqueous environment. Standard titration is the typical field method for measuring dissolved CO2 in aquaculture systems. However, titrimetric determination of dissolved CO2 in marine water aquaculture systems is unsuitable because of the high dissolved solids, silicates, and other dissolved minerals that interfere with the determination. Other methods used to measure dissolved carbon dioxide in an aquaculture water included use of a wetted CO2 probe analyzer, standard nomographic methods, and calculation by direct measurements of the water's pH, temperature, and alkalinity. The determination of dissolved CO2 in saltwater based on partial pressure measurements and non-dispersive infra-red (NDIR) techniques with a CO2 gas analyzer are widely employed for oceanic surveys of surface ocean CO2 flux and are similar to the techniques employed with the head space unit (HSU) in this study. Dissolved carbon dioxide (DC) determination with the HSU using a infra-red gas analyzer (IRGA) was compared with titrimetric, nomographic, calculated, and probe measurements of CO2 in freshwater and in saltwater with a salinity ranging from 5.0 to 30 ppt, and a CO2 range from 8 to 50 mg/L. Differences in CO2 measurements between duplicate HSUs (0.1–0.2 mg/L) were not statistically significant different. The coefficient of variation for the HSU readings averaged 1.85% which was better than the CO2 probe (4.09%) and that for the titrimetric method (5.84%). In all low, medium and high salinity level trials HSU precision was good, averaging 3.39%. Differences existed between comparison testing of the CO2 probe and HSU measurements with the CO2 probe readings, on average, providing DC estimates that were higher than HSU estimates. Differences between HSU and titration based estimates of DC increased with salinity and reached a maximum at 32.2 ppt. These differences were statistically significant (P < 0.05) at all salinity levels greater than 0.3 ppt. Results indicated reliable replicated results from the head space unit with varying salinity and dissolved carbon dioxide concentrations.

URANIUM SEPARATION PROCESS

DOEpatents

Lyon, W.L.

1962-04-17

A method of separating uranium oxides from PuO/sub 2/, ThO/sub 2/, and other actinide oxides is described. The oxide mixture is suspended in a fused salt melt and a chlorinating agent such as chlorine gas or phosgene is sparged through the suspension. Uranium oxides are selectively chlorinated and dissolve in the melt, which may then be filtered to remove the unchlorinated oxides of the other actinides. (AEC)

Quantification of N2O and NO emissions from a small-scale pond-ditch circulation system for rural polluted water treatment.

PubMed

Ma, Lin; Tong, Weijun; Chen, Hongguang; Sun, Jian; Wu, Zhenbin; He, Feng

2018-04-01

The pond-ditch circulation system (PDCS) is an efficient and economical solution for the restoration of degraded rural water environments. However, little is known about nitrous oxide (N 2 O) and nitric oxide (NO) emissions in the microbial removal process of nitrogen in PDCSs, and their contribution to nitrogen removal. The aim of this study was to quantify N 2 O and NO emissions from the PDCS, evaluate their capacities, and elucidate the key environmental factors controlling them. The results showed that N 2 O and NO fluxes were in the ranges 1.1-2055.1μgNm -2 h -1 and 0.1-6.8μgNm -2 h -1 for the PDCS, respectively. Meanwhile, the N 2 O and NO fluxes from the two ponds in the PDCS were significantly higher than those in the static system. Moreover, the amount of N 2 O and NO emissions in the PDCS accounted for 0.17-4.32% of the total nitrogen (TN) removal. According to the partial least squares (PLS) approach and Pearson's correlation coefficients, nitrate nitrogen in water (W-NO 3 - -N), dissolved oxygen in water (W-DO), dissolved oxygen in sediment (DO), pH in water (W-pH), pH in sediment (pH), total kjeldahl nitrogen (TKN), and soil organic carbon (SOC) significantly affected the N 2 O flux (p<0.05), whereas W-NO 3 - -N, DO, and nitrite nitrogen in sediment (NO 2 - -N) significantly affected the NO emission (p<0.05). Copyright © 2017 Elsevier B.V. All rights reserved.

Nitrous oxide production from temperate and tropical oyster species in response to nutrient loading

NASA Astrophysics Data System (ADS)

Chan, H.; Garate, M.; Moseman-Valtierra, S.

2016-02-01

Anthropogenic pollution, such as nitrogen (N), has the potential to increase greenhouse gas (GHG) emissions in marine ecosystems. Some organisms can be used as important biological indicators for GHG emissions to their environment based on their feeding habits. With large inputs of these anthropogenic pollutants, emissions of nitrous oxide (N2O), a potent GHG, can be potentially increased from temperate invertebrates, though not much is known about tropical invertebrates. Thus, we compared N2O emissions in response to N additions from the temperate oyster species Crassostrea virginica and compared it to a tropical species, Isognomon alatus, found in Puerto Rico. Oysters were exposed to two seawater treatments: (1) no nutrient addition (control) and (2) 100µM ammonium nitrate. Each treatment had 4-5 replicates. Measurements for dissolved N2O and nutrients were taken at the start of the incubation and then at two, four, and five hours by collecting water samples of each tank. Dissolved N2O concentrations were analyzed using gas chromatography. We hypothesized that the N addition treatment would produce more N2O for both Rhode Island and Puerto Rico. We found that there was no significant difference between the control and N enriched treatments for C. virginica over the short timespan, although the N enriched treatment did have a steady trend in increasing in N2O concentration over time. Further analysis is needed for the I. alatus, though we expect an increase in N2O emissions due to warmer water temperatures, which might enhance microbial metabolism and production of N2O. This differs from work previously done in a long-term experiment on C. virginica, which showed that N2O significantly in the N enriched treatment over 28-days. Our study shows that short-term pulses of N may not potentially increase N2O emissions, though further analysis is needed for longer-term exposures.

Thermodynamic Analysis of Secondary Minerals Stability in Altered Carbonatites of the Oldoinyo Lengai Volcano, Northern Tanzania

NASA Astrophysics Data System (ADS)

Perova, E. N.; Zaitsev, A. N.

2017-12-01

Carbonatites from the Oldoinyo Lengai volcano, northern Tanzania, are unstable under normal atmospheric conditions. Owing to carbonatite interaction with water, the major minerals—gregoryite Na2(CO3), nyerereite Na2Ca(CO3)2, and sylvite KCl—are dissolved and replaced with secondary low-temperature minerals: thermonatrite Na2(CO3) · H2O, trona Na3(CO3)(HCO3) · 2H2O, nahcolite Na(HCO3), pirssonite Na2Ca(CO3)2 · 2H2O, calcite Ca(CO3), and shortite Na2Ca2(CO3)3. Thermodynamic calculations show that the formation of secondary minerals in Oldoinyo Lengai carbonatites are controlled by the pH of the pore solution, H2O and CO2 fugacity, and the ratio of Ca and Na activity in the Na2O-CaO-CO2-H2O system.

Bulk Dissolution Rates of Cadmium and Bismuth Tellurides As a Function of pH, Temperature and Dissolved Oxygen.

PubMed

Biver, Marc; Filella, Montserrat

2016-05-03

The toxicity of Cd being well established and that of Te suspected, the bulk, surface-normalized steady-state dissolution rates of two industrially important binary tellurides-polycrystalline cadmium and bismuth tellurides- were studied over the pH range 3-11, at various temperatures (25-70 °C) and dissolved oxygen concentrations (0-100% O2 in the gas phase). The behavior of both tellurides is strikingly different. The dissolution rates of CdTe monotonically decreased with increasing pH, the trend becoming more pronounced with increasing temperature. Activation energies were of the order of magnitude associated with surface controlled processes; they decreased with decreasing acidity. At pH 7, the CdTe dissolution rate increased linearly with dissolved oxygen. In anoxic solution, CdTe dissolved at a finite rate. In contrast, the dissolution rate of Bi2Te3 passed through a minimum at pH 5.3. The activation energy had a maximum in the rate minimum at pH 5.3 and fell below the threshold for diffusion control at pH 11. No oxygen dependence was detected. Bi2Te3 dissolves much more slowly than CdTe; from one to more than 3.5 orders of magnitude in the Bi2Te3 rate minimum. Both will readily dissolve under long-term landfill deposition conditions but comparatively slowly.

Urea Hydrogen Peroxide Reduces the Numbers of Lactobacilli, Nourishes Yeast, and Leaves No Residues in the Ethanol Fermentation

PubMed Central

Narendranath, N. V.; Thomas, K. C.; Ingledew, W. M.

2000-01-01

Urea hydrogen peroxide (UHP) at a concentration of 30 to 32 mmol/liter reduced the numbers of five Lactobacillus spp. (Lactobacillus plantarum, L. paracasei, Lactobacillus sp. strain 3, L. rhamnosus, and L. fermentum) from ∼107 to ∼102 CFU/ml in a 2-h preincubation at 30°C of normal-gravity wheat mash at ∼21 g of dissolved solids per ml containing normal levels of suspended grain particles. Fermentation was completed 36 h after inoculation of Saccharomyces cerevisiae in the presence of UHP, even when wheat mash was deliberately contaminated (infected) with L. paracasei at ∼107 CFU/ml. There were no significant differences in the maximum ethanol produced between treatments when urea hydrogen peroxide was used to kill the bacteria and controls (in which no bacteria were added). However, the presence of L. paracasei at ∼107 CFU/ml without added agent resulted in a 5.84% reduction in the maximum ethanol produced compared to the control. The bactericidal activity of UHP is greatly affected by the presence of particulate matter. In fact, only 2 mmol of urea hydrogen peroxide per liter was required for disinfection when mashes had little or no particulate matter present. No significant differences were observed in the decomposition of hydrogen peroxide in normal-gravity wheat mash at 30°C whether the bactericidal agent was added as H2O2 or as urea hydrogen peroxide. NADH peroxidase activity (involved in degrading H2O2) increased significantly (P = 0.05) in the presence of 0.75 mM hydrogen peroxide (sublethal level) in all five strains of lactobacilli tested but did not persist in cells regrown in the absence of H2O2. H2O2-resistant mutants were not expected or found when lethal levels of H2O2 or UHP were used. Contaminating lactobacilli can be effectively managed by UHP, a compound which when used at ca. 30 mmol/liter happens to provide near-optimum levels of assimilable nitrogen and oxygen that aid in vigorous fermentation performance by yeast. PMID:11010858

Geochemistry and geohydrology of the West Decker and Big Sky coal-mining areas, southeastern Montana

USGS Publications Warehouse

Davis, R.E.

1984-01-01

In the West Decker Mine area, water levels west of the mine at post-mining equilibrium may be almost 12 feet higher than pre-mining levels. Dissolved-solids concentration in water from coal aquifers is about 1,400 milligrams per liter and from mine spoils is about 2,500 milligrams per liter. About 13 years will be required for ground water moving at an average velocity of 2 feet per day to flow from the spoils to the Tongue River Reservoir. The increase in dissolved-solids load to the reservoir due to mining will be less than 1 percent. In the Big Sky Mine area, water levels at post-mining equilibrium will closely resemble pre-mining levels. Dissolved-solids concentration in water from coal aquifers is about 2,700 milligrams per liter and from spoils is about 3,700 milligrams per liter. About 36 to 60 years will be required for ground water moving at an average velocity of 1.2 feet per day to flow from the spoils to Rosebud Creek. The average annual increase in dissolved-solids load to the creek due to mining will be about 2 percent, although a greater increase probably will occur during summer months when flow in the creek is low. (USGS)

Pilot plant demonstration of stable and efficient high rate biological nutrient removal with low dissolved oxygen conditions.

PubMed

Keene, Natalie A; Reusser, Steve R; Scarborough, Matthew J; Grooms, Alan L; Seib, Matt; Santo Domingo, Jorge; Noguera, Daniel R

2017-09-15

Aeration in biological nutrient removal (BNR) processes accounts for nearly half of the total electricity costs at many wastewater treatment plants. Even though conventional BNR processes are usually operated to have aerated zones with high dissolved oxygen (DO) concentrations, recent research has shown that nitrification can be maintained using very low-DO concentrations (e.g., below 0.2 mg O 2 /L), and therefore, it may be possible to reduce energy use and costs in BNR facilities by decreasing aeration. However, the effect of reduced aeration on enhanced biological phosphorus removal (EBPR) is not understood. In this study, we investigated, at the pilot-scale level, the effect of using minimal aeration on the performance of an EBPR process. Over a 16-month operational period, we performed stepwise decreases in aeration, reaching an average DO concentration of 0.33 mg O 2 /L with stable operation and nearly 90% phosphorus removal. Under these low-DO conditions, nitrification efficiency was maintained, and nearly 70% of the nitrogen was denitrified, without the need for internal recycling of high nitrate aeration basin effluent to the anoxic zone. At the lowest DO conditions used, we estimate a 25% reduction in energy use for aeration compared to conventional BNR operation. Our improved understanding of the efficiency of low-DO BNR contributes to the global goal of reducing energy consumption during wastewater treatment operations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of the δ13C of dissolved inorganic carbon in water; RSIL lab code 1710

USGS Publications Warehouse

Singleton, Glenda L.; Revesz, Kinga; Coplen, Tyler B.

2012-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ13C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl2) solution to form strontium carbonate (SrCO3). The δ13C is analyzed by reacting SrCO3 with 100-percent phosphoric acid (H3PO4) to liberate carbon quantitatively as carbon dioxide (CO2), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge (m/z) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO2 = 12C16O16O, m/z 45 = CO2 = 13C16O16O primarily, and m/z 46 = CO2 = 12C16O18O primarily. The data acquisition and control software calculates δ13C values.

Methylmercury photodegradation in surface water of the Florida Everglades: importance of dissolved organic matter-methylmercury complexation.

PubMed

Tai, Chao; Li, Yanbin; Yin, Yongguang; Scinto, Leonard J; Jiang, Guibin; Cai, Yong

2014-07-01

Photodegradation is the major pathway of methylmercury (MeHg) degradation in many surface waters. However, the mechanism of MeHg photodegradation is still not completely understood. Dissolved organic matter (DOM) is expected to play a critical role in MeHg photodegradation. By using several techniques, including N2/O2 purging and the addition of stable isotope (Me(201)Hg), scavengers, competing ligands, and a singlet oxygen ((1)O2) generator, the role played by MeHg-DOM complexation in MeHg photodegradation of Everglades surface water was investigated. DOM appeared to be involved in MeHg photodegradation via the formation MeHg-DOM complexes based on three findings: (1) MeHg was quickly photodegraded in solutions containing DOM extracts; (2) degradation of MeHg did not occur in deionized water; and (3) addition of competing complexation reagents (dithiothreitol-DTT) dramatically prohibited the photodegradation of MeHg in Everglades water. Further experiments indicated that free radicals/reactive oxygen species, including hydroxyl radical (·OH), (1)O2, triplet excited state of DOM ((3)DOM*), and hydrated electron (e(-)aq), played a minor role in MeHg photodegradation in Everglades water, based on the results of scavenger addition, (1)O2 generator addition and N2/O2 purging. A pathway, involving direct photodegradation of MeHg-DOM complexes via intramolecular electron transfer, is proposed as the dominant mechanism for MeHg photodegradation in Everglades water.

Atmospheric hydrogen peroxide and Eoarchean iron formations.

PubMed

Pecoits, E; Smith, M L; Catling, D C; Philippot, P; Kappler, A; Konhauser, K O

2015-01-01

It is widely accepted that photosynthetic bacteria played a crucial role in Fe(II) oxidation and the precipitation of iron formations (IF) during the Late Archean-Early Paleoproterozoic (2.7-2.4 Ga). It is less clear whether microbes similarly caused the deposition of the oldest IF at ca. 3.8 Ga, which would imply photosynthesis having already evolved by that time. Abiological alternatives, such as the direct oxidation of dissolved Fe(II) by ultraviolet radiation may have occurred, but its importance has been discounted in environments where the injection of high concentrations of dissolved iron directly into the photic zone led to chemical precipitation reactions that overwhelmed photooxidation rates. However, an outstanding possibility remains with respect to photochemical reactions occurring in the atmosphere that might generate hydrogen peroxide (H2 O2 ), a recognized strong oxidant for ferrous iron. Here, we modeled the amount of H2 O2 that could be produced in an Eoarchean atmosphere using updated solar fluxes and plausible CO2 , O2 , and CH4 mixing ratios. Irrespective of the atmospheric simulations, the upper limit of H2 O2 rainout was calculated to be <10(6) molecules cm(-2) s(-1) . Using conservative Fe(III) sedimentation rates predicted for submarine hydrothermal settings in the Eoarchean, we demonstrate that the flux of H2 O2 was insufficient by several orders of magnitude to account for IF deposition (requiring ~10(11) H2 O2 molecules cm(-2) s(-1) ). This finding further constrains the plausible Fe(II) oxidation mechanisms in Eoarchean seawater, leaving, in our opinion, anoxygenic phototrophic Fe(II)-oxidizing micro-organisms the most likely mechanism responsible for Earth's oldest IF. © 2014 John Wiley & Sons Ltd.

Plasma corticosteroid dynamics in channel catfish, Ictalurus punctatus (Rafinesque), during and after oxygen depletion

USGS Publications Warehouse

Tomasso J.R., Davis; Parker, N.C.

1981-01-01

Plasma corticosteroid concentrations in channel catfish, Ictalurus punctatus, (normally 1.0 ± 0.3 μg/100 ml) increased significantly (to 5.9 ± 1.2μg/100 ml) in response to acute oxygen depletion and then returned to control levels within 30 min after the dissolved oxygen concentration was increased; however, a secondary increase in plasma corticosteroid levels was observed 6 h after exposure. Corticosteroid levels also increased in fish exposed to dissolved oxygen concentration of <0.2 mg/1 for three days. Methylene blue was not effective in preventing interrenal response to low dissolved oxygen. No diurnal plasma corticosteroid rhythm was observed in fish exposed to diurnal chemical rhythms of culture ponds.

Influence of dissolved oxygen concentration on the start-up of the anammox-based process: ELAN®.

PubMed

Morales, N; Val del Río, A; Vázquez-Padín, J R; Gutiérrez, R; Fernández-González, R; Icaran, P; Rogalla, F; Campos, J L; Méndez, R; Mosquera-Corral, A

2015-01-01

The anammox-based process ELAN® was started-up in two different sequencing batch reactor (SBR) pilot plant reactors treating municipal anaerobic digester supernatant. The main difference in the operation of both reactors was the dissolved oxygen (DO) concentration in the bulk liquid. SBR-1 was started at a DO value of 0.4 mg O2/L whereas SBR-2 was started at DO values of 3.0 mg O2/L. Despite both reactors working at a nitrogen removal rate of around 0.6 g N/(L d), in SBR-1, granules represented only a small fraction of the total biomass and reached a diameter of 1.1 mm after 7 months of operation, while in SBR-2 the biomass was mainly composed of granules with an average diameter of 3.2 mm after the same operational period. Oxygen microelectrode profiling revealed that granules from SBR-2 where only fully penetrated by oxygen with DO concentrations of 8 mg O2/L while granules from SBR-1 were already oxygen penetrated at DO concentrations of 1 mg O2/L. In this way granules from SBR-2 performed better due to the thick layer of ammonia oxidizing bacteria, which accounted for up to 20% of all the microbial populations, which protected the anammox bacteria from non-suitable liquid media conditions.

Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

USGS Publications Warehouse

Cao, Xiaoyan; Aiken, George R.; Spencer, Robert G. M.; Butler, Kenna D.; Mao, Jingdong; Schmidt-Rohr, Klaus

2016-01-01

Seasonal (spring freshet, summer–autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV–visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64–74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63–77%) and TPIA (54–78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OCnp, OCnpO and Cq, 13–17% of HPOA and 15–20% of TPIA) and isolated O–CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (∼5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C–O and O–C–O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

Characteristics of N2O production and hydroxylamine variation in short-cut nitrification SBR process.

PubMed

Hu, Bo; Ye, Junhong; Zhao, Jianqiang; Ding, Xiaoqian; Yang, Liwei; Tian, Xiaolei

2018-01-01

In order to study the characteristics of nitrous oxide (N 2 O) production and hydroxylamine (NH 2 OH) variation under oxic conditions, concentrations of NH 2 OH and N 2 O were simultaneously monitored in a short-cut nitrification sequencing batch reactor (SBR) operated with different influent ammonia concentrations. In the short-cut nitrification process, N 2 O production was increased with the increasing of ammonia concentration in influent. The maximum concentrations of dissolved N 2 O-N in the reactor were 0.11 mg/L and 0.52 mg/L when ammonia concentrations in the influent were 50 mg/L and 70 mg/L respectively. Under the low and medium ammonia load phases, the concentrations of NH 2 OH-N in the reactor were remained at a low level which fluctuated around 0.06 mg/L in a small range, and did not change with the variation of influent NH 4 + -N concentration. Based on the determination results, the half-saturation of NH 2 OH in the biochemical conversion process of NH 2 OH to NO 2 - -N was very small, and the value of 0.05 mg NH 2 OH-N/L proposed in the published literature was accurate. NH 2 OH is an important intermediate in the nitrification process, and the direct determination of NH 2 OH in the nitrification process was beneficial for revealing the kinetic process of NH 2 OH production and consumption as well as the effects of NH 2 OH on N 2 O production in the nitrification process.

Cerium dioxide (CeO2) nanoparticles decrease arsenite (As(III)) cytotoxicity to 16HBE14o- human bronchial epithelial cells.

PubMed

Zeng, Chao; Nguyen, Chi; Boitano, Scott; Field, Jim A; Shadman, Farhang; Sierra-Alvarez, Reyes

2018-07-01

The production and application of engineered nanoparticles (NPs) are increasing in demand with the rapid development of nanotechnology. However, there are concerns that some of these novel materials could lead to emerging environmental and health problems. Some NPs are able to facilitate the transport of contaminants into cells/organisms via a "Trojan Horse" effect which enhances the toxicity of the adsorbed materials. In this work, we evaluated the toxicity of arsenite (As(III)) adsorbed onto cerium dioxide (CeO 2 ) NPs to human bronchial epithelial cells (16HBE14o-) using the xCELLigence real time cell analyzing system (RTCA). Application of 0.5 mg/L As(III) resulted in 81.3% reduction of cell index (CI, an RTCA measure of cell toxicity) over 48 h when compared to control cells exposed to medium lacking As(III). However, when the cells were exposed to 0.5 mg/L As(III) in the presence of CeO 2 NPs (250 mg/L), the CI was only reduced by 12.9% compared to the control. The CeO 2 NPs had a high capacity for As(III) adsorption (20.2 mg/g CeO 2 ) in the bioassay medium, effectively reducing dissolved As(III) in the aqueous solution and resulting in reduced toxicity. Transmission electron microscopy was used to study the transport of CeO 2 NPs into 16HBE14o- cells. NP uptake via engulfment was observed and the internalized NPs accumulated in vesicles. The results demonstrate that dissolved As(III) in the aqueous solution was the decisive factor controlling As(III) toxicity of 16HBE14o- cells, and that CeO 2 NPs effectively reduced available As(III) through adsorption. These data emphasize the evaluation of mixtures when assaying toxicity. Copyright © 2018 Elsevier Inc. All rights reserved.

[Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing

NASA Astrophysics Data System (ADS)

Frank, Patrick; Benfatto, Maurizio; Qayyum, Munzarin

2018-05-01

High resolution (k = 18 Å-1 or k = 17 Å-1) copper K-edge EXAFS and MXAN (Minuit X-ray Absorption Near Edge) analyses have been used to investigate the structure of dissolved [Cu(aq)]2+ in 1,3-propanediol (1,3-P) or 1,5-pentanediol (1,5-P) aqueous frozen glasses. EXAFS analysis invariably found a single axially asymmetric 6-coordinate (CN6) site, with 4×Oeq = 1.97 Å, Oax1 = 2.22 Å, and Oax2 = 2.34 Å, plus a second-shell of 4×Owater = 3.6 Å. However, MXAN analysis revealed that [Cu(aq)]2+ occupies both square pyramidal (CN5) and axially asymmetric CN6 structures. The square pyramid included 4×H2O = 1.95 Å and 1×H2O = 2.23 Å. The CN6 sites included either a capped, near perfect, square pyramid with 5×H2O = 1.94 ± 0.04 Å and H2Oax = 2.22 Å (in 1,3-P) or a split axial configuration with 4×H2O = 1.94, H2Oax1 = 2.14 Å, and H2Oax2 = 2.28 Å (in 1,5-P). The CN6 sites also included an 8-H2O second-shell near 3.7 Å, which was undetectable about the strictly pyramidal sites. Equatorial angles averaging 94° ± 5° indicated significant departures from tetragonal planarity. MXAN assessment of the solution structure of [Cu(aq)]2+ in 1,5-P prior to freezing revealed the same structures as previously found in aqueous 1M HClO4, which have become axially compressed in the frozen glasses. [Cu(aq)]2+ in liquid and frozen solutions is dominated by a 5-coordinate square pyramid, but with split axial CN6 appearing in the frozen glasses. Among these phases, the Cu-O axial distances vary across 1 Å, and the equatorial angles depart significantly from the square plane. Although all these structures remove the dx2-y2, dz2 degeneracy, no structure can be described as a Jahn-Teller (JT) axially elongated octahedron. The JT-octahedral description for dissolved [Cu(aq)]2+ should thus be abandoned in favor of square pyramidal [Cu(H2O)5]2+. The revised ligand environments have bearing on questions of the Cu(i)/Cu(ii) self-exchange rate and on the mechanism for ligand exchange with bulk water. The plasticity of dissolved Cu(ii) complex ions falsifies the foundational assumption of the rack-induced bonding theory of blue copper proteins and obviates any need for a thermodynamically implausible protein constraint.

Isotopic Monitoring of N2O Emissions from Wastewater Treatment: Evidence for N2O Production Associated with Anammox Metabolism?

NASA Astrophysics Data System (ADS)

Harris, E. J.; Wunderlin, P.; Joss, A.; Emmenegger, L.; Kipf, M.; Wolf, B.; Mohn, J.

2015-12-01

Microbial production is the major source of N2O, the strongest greenhouse gas produced within the nitrogen cycle, and the most important stratospheric ozone destructant released in the 21st century. Wastewater treatment is an important and growing source of N2O, with best estimates predicting N2O emissions from this sector will have increased by >25% by 2020. Novel treatment employing partial nitritation-anammox, rather than traditional nitrification-denitrification, has the potential to achieve a neutral carbon footprint due to increased biogas production - if N2O production accounts for <0.5-1% of total nitrogen turnover. As a further motivation for this research, microbial pathways identified from wastewater treatment can be applied to our understanding of N cycling in the natural environment. This study presents the first online isotopic measurements of offgas N2O from a partial-nitritation anammox reactor 1. The measured N2O isotopic composition - in particular the N2O isotopic site preference (SP = δ15Nα - δ15Nβ) - was used to understand N2O production pathways in the reactor. When N2O emissions peaked due to high dissolved oxygen concentrations, low SP showed that N2O was produced primarily via nitrifier denitrification by ammonia oxidizing bacteria (AOBs). N2O production by AOBs via NH2OH oxidation, in contrast, did not appear to be important under any conditions. Over the majority of the one-month measurement period, the measured SP was much higher than expected following our current understanding of N2O production pathways 2. SP reached 41‰ during normal operating conditions and achieved a maximum of 45‰ when nitrite was added under anoxic conditions. These results could be explained by unexpectedly strong heterotrophic N2O reduction despite low dissolved organic matter concentrations, or by an incomplete understanding of isotopic fractionation during N2O production from NH2OH oxidation by AOBs - however the explanation most consistent with all results is a previously unknown N2O production pathway associated with anammox metabolism. Harris et al. (2015) Water Res., 83: 258-270. Wunderlin et al. (2013) Env. Sci. Tech., 47: 1339-1348.

Formation of iodo-trihalomethanes (I-THMs) during disinfection with chlorine or chloramine: Impact of UV/H2O2 pre-oxidation.

PubMed

Zhang, Jie; Liu, Jing; He, Chuan-Shu; Qian, Chen; Mu, Yang

2018-06-04

Ultraviolet/hydrogen peroxide (UV/H 2 O 2 ) pre-oxidation has the potential to induce reactions with dissolved organic matter (DOM) and alter the generation of disinfection byproducts (DBPs). This study evaluated the influence of UV/H 2 O 2 pretreatment on the formation of iodo-trihalomethanes (I-THMs) during disinfection with chlorine or chloramine. The changes of precursors, I - and Br - , after UV/H 2 O 2 pretreatment were investigated, and then, the formation and speciation of I-THMs during chlorination or chloramination after pre-oxidation were explored. Additionally, the effects of UV doses and H 2 O 2 concentrations on the formation and speciation of I-THMs were studied. It was found that UV/H 2 O 2 pretreatment could change larger molecular weight (MW) DOM to smaller MW species, which had less aromatic organic compounds and fluorescence substances. Additionally, insignificant transformations of I - and Br - were observed after UV/H 2 O 2 treatment. Compared to direct disinfection, UV/H 2 O 2 pretreatment resulted in 23.0 ± 3.5% reduction in I-THMs formation during post-chlorination while an enhancement was observed during post-chloramination at a UV dose of 460 mJ/cm 2 and 20 mg/L H 2 O 2 . Moreover, total I-THM concentration increased from 43.7 ± 2.4 to 97.6 ± 14.9 nM with the increase of UV doses from 0 to 1400 mJ/cm 2 during the post-chlorination process, while reduced when the UV fluence was >460 mJ/cm 2 during the post-chloramination. Additionally, the generation of I-THMs during both post-chlorination and post-chloramination was positively related to the H 2 O 2 levels from 0 to 20 mg/L in the UV/H 2 O 2 pretreatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Sol-gel Synthesis, Photo- and Electrocatalytic Properties of Mesoporous TiO2 Modified with Transition Metal Ions

NASA Astrophysics Data System (ADS)

Smirnova, N.; Petrik, I.; Vorobets, V.; Kolbasov, G.; Eremenko, A.

2017-03-01

Mesoporous nanosized titania films modified with Co2+, Ni2+, Mn3+, and Cu2+ ions have been produced by templated sol-gel method and characterized by optical spectroscopy, X-ray diffraction (XRD), and Brunauer, Emmett, and Teller (BET) surface area measurement. Band gap energy and the position of flat band potentials were estimated by photoelectrochemical measurements. The films doped with transition metals possessed higher photocurrent quantum yield, as well as photo- and electrochemical activity compared to undoped samples. Mn+/TiO2 (M-Co, Ni, Mn, Cu) electrodes with low dopant content demonstrate high efficiency in electrocatalytic reduction of dissolved oxygen. Polarization curves of TiO2, TiO2/Ni2+, TiO2/Co2+/3+, and TiO2/Mn3+ electrodes contain only one current wave (oxygen reduction current). It means that reaction proceeds without the formation of an intermediate product H2O2.

Exploring drivers of sodium salt toxicity to the mayfly Neocloeon triangulifer, and comparing trends in mayfly and daphnid responses to major ions

EPA Science Inventory

Field studies have shown that mayflies (Ephemeroptera) tend to be more sensitive than other benthic macroinvertebrates to elevated levels of total dissolved solids in streams. While work with other species has shown that major ion toxicity is dependent on the ionic composition o...

Evaluation of calcium-bearing material for treatment of CO2 leakage-induced pollution

NASA Astrophysics Data System (ADS)

Park, J.; Park, M.; Jeong, H. Y.

2017-12-01

Several Ca2+-bearing materials were evaluated for their capability to treat CO2 leakage-induced pollution for the application of permeable reactive barriers (PRBs). In this regard, a series of batch experiments were carried out with Portland cement, quick lime (CaO), and gypsum (CaSO4). Each of these materials was added to 50 mL of CO2-saturated solutions ( 7.5-8.5 mM) in serum vials sealed with Teflon-coated grey butyl stopper. Subsequently, the resultant batches were agitated at room temperature for 24 h. At predetermined intervals, each vial was sacrificed to monitor changes in pH, EC, and dissolved CO2 concentration. Despite the pH-neutralizing capacity, 0.15 g of Portland cement did not lower any dissolved CO2. When amended with 0.05 g of Ca(OH)2 or Mg(OH)2, the cement at this loading could sequester dissolved CO2, with the former being more effective. Even without such amendments, the cement at or greater than 0.2 g was shown to completely sequester dissolved CO2. In case of quick lime, its loading as low as 0.05 g instantaneously removed all dissolved CO2, which was also noted for Portland cement at 0.5 g. For gypsum, its loading at 0.12 g was not effective for immobilizing dissolved CO2. By both X-ray diffraction (XRD) and thermogravimetry (TG) analyses, the CO2 sequestration by Ca2+-bearing materials was found to be mainly due to the formation of calcite (CaCO3). Funding source: The "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003).

Corrosion Behavior of Alloy 625 in PbSO4-Pb3O4-PbCl2-ZnO-10 Wt Pct CdO Molten Salt Medium

NASA Astrophysics Data System (ADS)

Mohammadi Zahrani, E.; Alfantazi, A. M.

2012-08-01

Corrosion behavior and degradation mechanisms of alloy 625 under a 47.288 PbSO4-12.776 Pb3O4-6.844PbCl2-23.108ZnO-10CdO (wt pct) molten salt mixture under air atmosphere were studied at 873 K, 973 K, and 1073 K (600 °C, 700 °C, and 800 °C). Electrochemical impedance spectroscopy (EIS), open circuit potential (OCP) measurements, and potentiodynamic polarization techniques were used to evaluate the degradation mechanisms and characterize the corrosion behavior of the alloy. Morphology, chemical composition, and phase structure of the corrosion products and surface layers of the corroded specimens were studied by scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) and X-ray map analyses. Results confirmed that during the exposure of alloy 625 to the molten salt, chromium was mainly dissolved through an active oxidation process as CrO3, Cr2O3, and CrNbO4, while nickel dissolved only as NiO in the system. Formation of a porous and nonprotective oxide layer with low resistance is responsible for the weak protective properties of the barrier layer at high temperatures of 973 K and 1073 K (700 °C and 800 °C). There were two kinds of attack for INCONEL 625, including general surface corrosion and pitting. Pitting corrosion occurred due to the breakdown of the initial oxide layer by molten salt dissolution of the oxide or oxide cracking.

Dissolved inorganic carbon dynamics in the waters surrounding forested mangroves of the Ca Mau Province (Vietnam)

NASA Astrophysics Data System (ADS)

Koné, Y. J.-M.; Borges, A. V.

2008-04-01

Dissolved inorganic carbon (DIC) and ancillary data were obtained during the dry and rainy seasons in the waters surrounding two 10-year-old forested mangrove sites (Tam Giang and Kiên Vàng) located in the Ca Mau Province (South-West Vietnam). During both seasons, the spatial variations of partial pressure of CO 2 (pCO 2) were marked, with values ranging from 704 ppm to 11481 ppm during the dry season, and from 1209 ppm to 8136 ppm during the rainy season. During both seasons, DIC, pCO 2, total alkalinity (TAlk) and oxygen saturation levels (%O 2) were correlated with salinity in the mangrove creeks suggesting that a combination of lower water volume and longer residence time (leading to an increase in salinity due to evaporation) enhanced the enrichment in DIC, pCO 2 and TAlk, and an impoverishment in O 2. The low O 2 and high DIC and pCO 2 values suggest that heterotrophic processes in the water column and sediments controlled these variables. The latter processes were meaningful since the high DIC and TAlk values in the creek waters were related to some extent to the influx of pore waters, consistent with previous observations. This was confirmed by the stochiometric relationship between TAlk and DIC that shows that anaerobic processes control these variables, although this approach did not allow identifying unambiguously the dominant diagenetic carbon degradation pathway. During the rainy season, dilution led to significant decreases of salinity, TAlk and DIC in both mangrove creeks and adjacent main channels. In the Kiên Vàng mangrove creeks a distinct increase of pCO 2 and decrease of %O 2 were observed. The increase of TSM suggested enhanced inputs of organic matter probably from land surrounding the mangrove creeks, that could have led to higher benthic and water column heterotrophy. However, the flushing of water enriched in dissolved CO 2 originating from soil respiration and impoverished in O 2 could also have explained to some extent the patterns observed during the rainy season. Seasonal variations of pCO 2 were more pronounced in the Kiên Vàng mangrove creeks than in the Tam Giang mangrove creeks. The air-water CO 2 fluxes were 5 times higher during the rainy season than during the dry season in the Kiên Vàng mangrove creeks. In the Tam Giang mangrove creeks, the air-water CO 2 fluxes were similar during both seasons. The air-water CO 2 fluxes ranged from 27.1 mmol C m -2 d -1 to 141.5 mmol C m -2 d -1 during the dry season, and from 81.3 mmol m -2 d -1 to 154.7 mmol m -2 d -1 during the rainy season. These values are within the range of values previously reported in other mangrove creeks and confirm that the emission of CO 2 from waters surrounding mangrove forests are meaningful for the carbon budgets of mangrove forests.

Solvent dependence of the steady-state rate of 1O 2 generation upon excitation of dissolved oxygen by cw 1267 nm laser radiation in air-saturated solutions: Estimates of the absorbance and molar absorption coefficients of oxygen at the excitation wavelength

NASA Astrophysics Data System (ADS)

Krasnovsky, A. A., Jr.; Roumbal, Ya. V.; Ivanov, A. V.; Ambartzumian, R. V.

2006-10-01

The rates of oxygenation of the 1O 2 trap, 1,3-diphenylisobenzofuran were measured in air-saturated organic solvents and heterogeneous D 2O-sodium dodecyl sulfate dispersions upon infrared (1267 ± 4 nm) laser irradiation. The absorbance and molar absorption coefficients of oxygen corresponding to this wavelength were estimated from the observed oxygenation rates. The data suggest that 1O 2 was formed due to direct oxygen excitation without appreciable involvement of vibrationally excited solvent molecules. The minor 'pseudophase' of detergent micelles was shown to strongly enhance overall 1O 2 production in D 2O-detergent dispersions.

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

DOE PAGES

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.; ...

2018-02-09

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Nacystelyn, a novel lysine salt of N-acetylcysteine, to augment cellular antioxidant defence in vitro.

PubMed

Gillissen, A; Jaworska, M; Orth, M; Coffiner, M; Maes, P; App, E M; Cantin, A M; Schultze-Werninghaus, G

1997-03-01

Nacystelyn (NAL), a recently-developed lysine salt of N-acetylcysteine (NAC), and NAG, both known to have excellent mucolytic capabilities, were tested for their ability to enhance cellular antioxidant defence mechanisms. To accomplish this, both drugs were tested in vitro for their capacity: (1) to inhibit O2- and H2O2 in cell-free assay systems; (2) to reduce O2- and H2O2 released by polymorphonuclear leukocytes (PMN); and (3) for their cellular glutathione (GSH) precursor effect. In comparison with GSH, NAL and NAC inhibited H2O2, but not O2-, in cell-free, in vitro test systems in a similar manner. The anti-H2O2 effect of these drugs was as potent as that of GSH, an important antioxidant in mammalian cells. To enhance cellular GSH levels, increasing concentrations (0-2 x 10(-4) mol l-1) of both substances were added to a transformed alveolar cell line (A549 cells). After NAC administration (2 x 10(-4) mol l-1), total intracellular GSH (GSH + 2GSSG) levels reached 4.5 +/- 1.1 x 10(-6) mol per 10(6) cells, whereas NAL increased GSH to 8.3 +/- 1.6 x 10(-6) mol per 10(6) cells. NAC and NAL administration also induced extracellular GSH secretion; about two-fold (NAC), and 1.5-fold (NAL), respectively. The GSH precursor potency of cystine was about two-fold higher than that of NAL and NAC, indicating that the deacetylation process of NAL and NAC slows the ability of both drugs to induce cellular glut production and secretion. Buthionine-sulphoximine, which is an inhibitor of GSH synthetase, blocked the cellular GSH precursor effect of all substances. In addition, these data demonstrate that NAC and NAL reduce H2O2 released by freshly-isolated cultured blood PMN from smokers with chronic obstructive pulmonary disease (COPD) (n = 10) in a similar manner (about 45% reduction of H2O2 activity by NAC or NAL at 4 x 10(-6) mol l-1). In accordance with the results obtained from cell-free, in vitro assays, O2- released by PMN was not affected. Ambroxol (concentrations: 10(-9)-10(-3) mol l-1) did not reduce activity levels of H2O2 and O2- in vitro. Due to the basic effect of dissolved lysine, which separates easily in solution from NAL, the acidic function of the remaining NAC molecule is almost completely neutralized [at concentration 2 x 10(-4) M: pH 3.6 (NAC), pH 6.4 (NAL)]. Due to their function as H2O2 scavengers, and due to their ability to enhance cellular glutathione levels, NAL and NAC both have potent antioxidant capabilities in vitro. The advantage of NAL over NAC is two-fold; it enhances intracellular GSH levels twice as effectively, and it forms neutral pH solutions whereas NAC is acidic. Concluding from these in vitro results, NAL could be an interesting alternative to enhance the antioxidant capacity at the epithelial surface of the lung by aerosol administration.

Evaluation of Primary Production in the Lower Amazon River Based on a Dissolved Oxygen Stable Isotopic Mass Balance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gagne-Maynard, William C.; Ward, Nicholas D.; Keil, Richard G.

The Amazon River outgasses nearly an equivalent amount of CO 2 as the rainforest sequesters on an annual basis due to microbial decomposition of terrigenous and aquatic organic matter. Most research performed in the Amazon has been focused on unraveling the mechanisms driving CO 2 production since the recognition of a persistent state of CO 2 supersaturation. However, although the river system is clearly net heterotrophic, the interplay between primary production and respiration is an essential aspect to understanding the overall metabolism of the ecosystem and potential transfer of energy up trophic levels. For example, an efficient ecosystem is capablemore » of both decomposing high amounts of organic matter at lower trophic levels, driving CO 2 emissions, and accumulating energy/biomass in higher trophic levels, stimulating fisheries production. Early studies found minimal evidence for primary production in the Amazon River mainstem and it has since been assumed that photosynthesis is strongly limited by low light penetration attributed to the high sediment load. Here, we test this assumption by measuring the stable isotopic composition of O 2 (δ 18O-O 2) and O 2 saturation levels in the lower Amazon River from Óbidos to the river mouth and its major tributaries, the Xingu and Tapajós rivers, during high and low water periods. An oxygen mass balance model was developed to estimate the input of photosynthetic oxygen in the discrete reach from Óbidos to Almeirim, midway to the river mouth. Based on the oxygen mass balance we estimate that primary production occurred at a rate of 0.39 ± 0.24 g O m 3 d -1 at high water and 1.02 ± 0.55 g O m 3 d -1 at low water. This translates to 41 ± 24% of the rate of O 2 drawdown via respiration during high water and 67 ± 33% during low water. These primary production rates are 2-7 times higher than past estimates for the Amazon River mainstem. In conclusion, it is possible that at high water much of this productivity signal is the result of legacy advection from floodplains, whereas limited floodplain connectivity during low water implies that most of this signal is the result of in situ primary production in the Amazon River mainstem.« less

Influence of soil pH on the toxicity of zinc oxide nanoparticles to the terrestrial isopod Porcellionides pruinosus.

PubMed

Tourinho, Paula S; van Gestel, Cornelis A M; Lofts, Stephen; Soares, Amadeu M V M; Loureiro, Susana

2013-12-01

The effects of soil pH on the toxicity of ZnO nanoparticles (NPs) to the terrestrial isopod Porcellionides pruinosus were evaluated. Isopods were exposed to a natural soil amended with CaCO3 to reach 3 different pH(CaCl2) levels (4.5, 6.2, and 7.3) and to standard LUFA 2.2 soil (pH 5.5) spiked with ZnO NPs (30 nm), non-nano ZnO (200 nm), and ionic Zn as ZnCl₂. Toxicity was expressed based on total Zn concentration in soil, as well as total Zn and free Zn²⁺ ion concentrations in porewater. Compared with ZnO-spiked soils, the ZnCl₂-spiked soils had lower pH and higher porewater Ca²⁺ and Zn levels. Isopod survival did not differ between Zn forms and soils, but survival was higher for isopods exposed to ZnO NPs at pH 4.5. Median effect concentrations (EC50s) for biomass change showed similar trends for all Zn forms in all soils, with higher values at intermediate pH. Median lethal concentration (LC50) and EC50 values based on porewater Zn or free Zn ion concentrations were much lower for ZnO than for ionic zinc. Zn body concentrations increased in a dose-related manner, but no effect of soil pH was found. It is suggested not only that dissolved or free Zn in porewater contributed to uptake and toxicity, but also that oral uptake (i.e., ingestion of soil particles) could be an important additional route of exposure. © 2013 SETAC.

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

NASA Technical Reports Server (NTRS)

Pawley, Alison R.; Holloway, John R.; Mcmillan, Paul F.

1992-01-01

The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

In Situ Natural Abundance 17 O and 25 Mg NMR Investigation of Aqueous Mg(OH) 2 Dissolution in the Presence of Supercritical CO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Mary Y.; Deng, Xuchu; Thanthiriwatte, K. Sahan

We report the development of an in situ high pressure NMR capability that permits natural abundance 17O and 25Mg NMR characterization of dissolved species in aqueous solution and in the presence of supercritical CO 2 fluid (scCO 2). The dissolution of Mg(OH) 2 (brucite) in a multiphase water/scCO 2 fluid at 90 atm pressure and 50 C was studied in situ, with relevance to geological carbon sequestration. 17O NMR spectra allowed identification and distinction of various fluid species including dissolved CO 2 in the H 2O-rich phase, scCO 2, aqueous H 2O, and HCO 3 -. The widely separated spectralmore » peaks for various species can all be observed both dynamically and quantitatively at concentrations of as low as 20 mM. Measurement of the concentrations of these individual species also allows an in situ estimate of the hydrogen ion concentration, or pCH + values, of the reacting solutions. The concentration of Mg 2+ can be observed by natural abundance 25Mg NMR at a concentration as low as 10 mM. Quantum chemistry calculations of the NMR chemical shifts on cluster models aided in the interpretation of the experimental results. Evidence for the formation of polymeric Mg 2+ clusters at high concentrations in the H 2O-rich phase, a possible critical step needed for magnesium carbonate formation, was found. The approach and findings enable insight into metal carbonation reactions associated with geological carbon sequestration that cannot be probed by ex situ methods.« less

Determination of the δ15N of nitrate in solids; RSIL lab code 2894

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping; Revesz, Kinga; Casciotti, Karen; Hannon, Janet E.

2007-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2894 is to determine the δ15N of nitrate (NO3-) in solids. The nitrate fraction of the nitrogen species is dissolved by water (called leaching) and can be analyzed by the bacterial method covered in RSIL lab code 2899. After leaching, the δ15N of the dissolved NO3- is analyzed by conversion of the NO3- to nitrous oxide (N2O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of NO3- to N2O, which follows the pathway shown in equation 1: NO3- → NO2- → NO → 1/2 N2O (1) Because the bacteria Pseudomonas aureofaciens lack N2O reductive activity, the reaction stops at N2O, unlike the typical denitrification reaction that goes to N2. After several hours, the conversion is complete, and the N2O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO4)2), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N2O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge (m/z) of the N2O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N2O = 14N14N16O; m/z = 45 = N2O = 14N15N16O or 14N14N17O; m/z = 46 = N2O = 14N14N18O. The 17O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ15N values are reported.

An investigation onto the molecular structure of 5-chloro-3-(2-(4-ethylpiperazine-1-il)-2-oxoethyl)benzo[d]thiazole-2(3H)-on drug molecule before and after atmospheric pressure plasma treatment

NASA Astrophysics Data System (ADS)

Tanışlı, Murat; Taşal, Erol; Şahin, Neslihan; Dikmen, Gökhan

2018-05-01

The spectra of molecular structure for the 5-chloro-3-(2-(4-ethylpiperazine-1-il)-2-oxoethyl)benzo[d]thiazole-2(3H)-on drug molecule (abbreviated as 5KEB) before and after the atmospheric pressure plasma treatments (APPTs) of neon (Ne) and argon (Ar) were investigated. The Fourier transform infrared (FT-IR), ultraviolet visible (UV-Vis) spectra and NMR measurements of the 5KEB drug molecule dissolved in toluene and ethanol solvents were recorded and examined for liquid phases. Then FT-IR, UV-Vis spectra and NMR measurements were analysed. It is seen that some bonds of 5KEB molecule were decomposed. There were also unobserved vibrational modes. After the Ne plasma at the atmospheric pressure applied to 5KEB drug molecule dissolved in toluene, the bonds as 9Ssbnd 8C; 9Ssbnd 8C = 10 O, 8Csbnd 7N, 7Nsbnd 8C = 10O were vanished, and then the new bonds of the 7N = 8C, 7N = 8C = 10 O, 9Ssbnd 5Csbnd 4Csbnd 7N = 8C = 10O were observed. New photoproducts may be defined as the stretching peaks, stretching vibrational modes for 5KEB drug molecule in liquid phase prepared with ethanol and toluene solvents after APPT. Also, after Ar plasma at atmospheric pressure applied here, the 9Ssbnd 8C bond of the 5KEB drug molecule dissolved in toluene was broken. The isomerization process in UV-Vis was defined by π-π* and n-π* electronic transitions. According to NMR results, protons of pyridine ring, protons of CH2 group bonded to carbonyl group and protons of CH3 group more affected than other protons from Ar and Ne APPTs and these protons were eliminated by Ar and Ne APPTs.

Investigating vibrational relaxation in cyanide-bridged transition metal mixed-valence complexes using two-dimensional infrared and infrared pump-probe spectroscopies

PubMed Central

Slenkamp, Karla M.; Lynch, Michael S.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira

2016-01-01

Using polarization-selective two-dimensional infrared (2D IR) and infrared pump-probe spectroscopies, we study vibrational relaxation of the four cyanide stretching (νCN) vibrations found in [(NH3)5RuIIINCFeII(CN)5]− (FeRu) dissolved in D2O or formamide and [(NC)5FeIICNPtIV(NH3)4NCFeII(CN)5]4− (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as models for understanding the role high frequency vibrational modes play in metal-to-metal charge transfers over a bridging ligand. However, there is currently little information about vibrational relaxation and dephasing dynamics of the anharmonically coupled νCN modes in the electronic ground state of these complexes. IR pump-probe experiments reveal that the vibrational lifetimes of the νCN modes are ∼2 times faster when FeRu is dissolved in D2O versus formamide. They also reveal that the vibrational lifetimes of the νCN modes of FePtFe in D2O are almost four times as long as for FeRu in D2O. Combined with mode-specific relaxation dynamics measured from the 2D IR experiments, the IR pump-probe experiments also reveal that intramolecular vibrational relaxation is occurring in all three systems on ∼1 ps timescale. Center line slope dynamics, which have been shown to be a measure of the frequency-frequency correlation function, reveal that the radial, axial, and trans νCN modes exhibit a ∼3 ps timescale for frequency fluctuations. This timescale is attributed to the forming and breaking of hydrogen bonds between each mode and the solvent. The results presented here along with our previous work on FeRu and FePtFe reveal a picture of coupled anharmonic νCN modes where the spectral diffusion and vibrational relaxation dynamics depend on the spatial localization of the mode on the molecular complex and its specific interaction with the solvent. PMID:27158634

Investigating vibrational relaxation in cyanide-bridged transition metal mixed-valence complexes using two-dimensional infrared and infrared pump-probe spectroscopies.

PubMed

Slenkamp, Karla M; Lynch, Michael S; Brookes, Jennifer F; Bannan, Caitlin C; Daifuku, Stephanie L; Khalil, Munira

2016-03-01

Using polarization-selective two-dimensional infrared (2D IR) and infrared pump-probe spectroscopies, we study vibrational relaxation of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O or formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as models for understanding the role high frequency vibrational modes play in metal-to-metal charge transfers over a bridging ligand. However, there is currently little information about vibrational relaxation and dephasing dynamics of the anharmonically coupled νCN modes in the electronic ground state of these complexes. IR pump-probe experiments reveal that the vibrational lifetimes of the νCN modes are ∼2 times faster when FeRu is dissolved in D2O versus formamide. They also reveal that the vibrational lifetimes of the νCN modes of FePtFe in D2O are almost four times as long as for FeRu in D2O. Combined with mode-specific relaxation dynamics measured from the 2D IR experiments, the IR pump-probe experiments also reveal that intramolecular vibrational relaxation is occurring in all three systems on ∼1 ps timescale. Center line slope dynamics, which have been shown to be a measure of the frequency-frequency correlation function, reveal that the radial, axial, and trans νCN modes exhibit a ∼3 ps timescale for frequency fluctuations. This timescale is attributed to the forming and breaking of hydrogen bonds between each mode and the solvent. The results presented here along with our previous work on FeRu and FePtFe reveal a picture of coupled anharmonic νCN modes where the spectral diffusion and vibrational relaxation dynamics depend on the spatial localization of the mode on the molecular complex and its specific interaction with the solvent.

Formation of inorganic nitrogenous byproducts in aqueous solution under ultrasound irradiation.

PubMed

Yao, Juanjuan; Chen, Longfu; Chen, Xiangyu; Zhou, Lingxi; Liu, Wei; Zhang, Zhi

2018-04-01

The effects of ultrasonic frequency, power intensity, temperature and sparged gas on the generation of nitrogenous by-products NO 2 - and NO 3 - have been investigated, and the new kinetics model of NO 2 - and NO 3 - generation was also explored. The results show that the highest primary generation rate of NO 2 - and NO 3 - by direct sonolysis in the cavitation bubbles (represented by k 1 ' and k 2 ', respectively) was obtained at 600 kHz and 200 kHz, respectively, in the applied ultrasonic frequency range of 200 to 800 kHz. The primary generation rate of NO 2 - (represented by k 1 ') increased with the increasing ultrasonic intensity while the primary generation rate of NO 3 - (represented by k 2 ') decreased. The lower temperature is beneficial to the primary generation of both NO 2 - and NO 3 - in the cavitation bubbles. The optimal overall yields of both NO 2 - and NO 3 - were obtained at the N 2 /O 2 volume (in the sparged gas) ratio of 3:1 which is near to the ratio of N 2 /O 2 in air. The dissolved O 2 is the dominant oxygen element source for both NO and NO 2 , compared with water vapor. Ultrasonic irradiation can significant enhance the recovery rates of dissolved N 2 and O 2 and thus keep the N 2 fixation reaction going even without aeration. Copyright © 2017 Elsevier B.V. All rights reserved.

Strategies of Nitrosomonas europaea 19718 to counter low dissolved oxygen and high nitrite concentrations.

PubMed

Yu, Ran; Chandran, Kartik

2010-03-04

Nitrosomonas europaea is a widely studied chemolithoautotrophic ammonia oxidizing bacterium. While significant work exists on the ammonia oxidation pathway of N. europaea, its responses to factors such as dissolved oxygen limitation or sufficiency or exposure to high nitrite concentrations, particularly at the functional gene transcription level are relatively sparse. The principal goal of this study was to investigate responses at the whole-cell activity and gene transcript levels in N. europaea 19718 batch cultures, which were cultivated at different dissolved oxygen and nitrite concentrations. Transcription of genes coding for principal metabolic pathways including ammonia oxidation (amoA), hydroxylamine oxidation (hao), nitrite reduction (nirK) and nitric oxide reduction (norB) were quantitatively measured during batch growth, at a range of DO concentrations (0.5, 1.5 and 3.0 mg O2/L). Measurements were also conducted during growth at 1.5 mg O2/L in the presence of 280 mg-N/L of externally added nitrite. Several wide ranging responses to DO limitation and nitrite toxicity were observed in N. europaea batch cultures. In contrast to our initial hypothesis, exponential phase mRNA concentrations of both amoA and hao increased with decreasing DO concentrations, suggesting a mechanism to metabolize ammonia and hydroxylamine more effectively under DO limitation. Batch growth in the presence of 280 mg nitrite-N/L resulted in elevated exponential phase nirK and norB mRNA concentrations, potentially to promote utilization of nitrite as an electron acceptor and to detoxify nitrite. This response was in keeping with our initial hypothesis and congruent with similar responses in heterotrophic denitrifying bacteria. Stationary phase responses were distinct from exponential phase responses in most cases, suggesting a strong impact of ammonia availability and metabolism on responses to DO limitation and nitrite toxicity. In general, whole-cell responses to DO limitation or nitrite toxicity, such as sOUR or nitrite reduction to nitric oxide (NO) did not parallel the corresponding mRNA (nirK) profiles, suggesting differences between the gene transcription and enzyme translation or activity levels. The results of this study show that N. europaea possesses specific mechanisms to cope with growth under low DO concentrations and high nitrite concentrations. These mechanisms are additionally influenced by the physiological growth state of N. europaea cultures and are possibly geared to enable more efficient substrate utilization or nitrite detoxification.

Characteristics of Al2O3, MnS, and TiN inclusions in the remelting process of bearing steel

NASA Astrophysics Data System (ADS)

Yang, Liang; Cheng, Guo-guang

2017-08-01

The Al2O3, MnS, and TiN inclusions in bearing steel will deteriorate the steel's mechanical properties. Therefore, elucidating detailed characteristics of these inclusions in consumable electrode during the electroslag remelting process is important for achieving a subsequently clean ingot. In this study, a confocal scanning violet laser microscope was used to simulate the remelting process and observe, in real time, the behaviors of inclusions. The obtained images show that, after the temperature exceeded the steel solidus temperature, MnS and TiN inclusions in the specimen began to dissolve. Higher temperatures led to faster dissolution, and the inclusions disappeared before the steel was fully liquid. In the case of an observed Al2O3 inclusion, its shape changed from angular to a smooth ellipsoid in the region where the solid and liquid coexisted and it began to dissolve as the temperature continued to increase. This dissolution was driven by the difference in oxygen potential between the inclusion and the liquid steel.

Optimized alumina coagulants for water treatment

DOEpatents

Nyman, May D [Albuquerque, NM; Stewart, Thomas A [Albuquerque, NM

2012-02-21

Substitution of a single Ga-atom or single Ge-atom (GaAl.sub.12 and GeAl.sub.12 respectively) into the center of an aluminum Keggin polycation (Al.sub.13) produces an optimal water-treatment product for neutralization and coagulation of anionic contaminants in water. GaAl.sub.12 consistently shows .about.1 order of magnitude increase in pathogen reduction, compared to Al.sub.13. At a concentration of 2 ppm, GaAl.sub.12 performs equivalently to 40 ppm alum, removing .about.90% of the dissolved organic material. The substituted GaAl.sub.12 product also offers extended shelf-life and consistent performance. We also synthesized a related polyaluminum chloride compound made of pre-hydrolyzed dissolved alumina clusters of [GaO.sub.4Al.sub.12(OH).sub.24(H.sub.2O).sub.12].sup.7+.

Chemical evidence of the changes of the Antarctic Bottom Water ventilation in the western Ross Sea between 1997 and 2003

NASA Astrophysics Data System (ADS)

Rivaro, Paola; Massolo, Serena; Bergamasco, Andrea; Castagno, Pasquale; Budillon, Giorgio

2010-05-01

Data from three Italian CLIMA project cruises between 1997 and 2003 were used to obtain sections of the hydrographic and chemical properties of the main water masses across the shelf break off Cape Adare (western Ross Sea, Antarctica). Dissolved oxygen, nitrate and phosphate data were combined on the basis of the Redfield ratio to obtain the quasi-conservative tracers NO (9[NO 3]+[O 2]), PO (135[PO 4]+[O 2]) and phosphate star PO4* ( PO4*=[PO 4]+[O 2]/175-1.95). In 1997 and 2003 the presence of the High Salinity Shelf Water at the bottom depth near the sill was traced by both physical and chemical measurements. In 2001 the Modified Shelf Water, characterized by warmer temperature and by a lower dissolved oxygen content than High Salinity Shelf Water, was observed at the shelf edge. The distribution of the chemical tracers together with the hydrographic observations showed recently formed Antarctic Bottom Water on the continental slope during all of the cruises. These observations were confirmed by the extended optimum multiparameter analysis. The calculated thickness of the new Antarctic Bottom Water, as well as the tracer content, were variable in time and in space. The estimated volume of the new Antarctic Bottom Water and the export of dissolved oxygen and nutrient associated with the overflowing water were different over the examined period. In particular, a lower (˜55%) export was evidenced in 2001 compared to 1997.

To Float or Not to Float: How Interactions between Light and Dissolved Inorganic Carbon Species Determine the Buoyancy of Stratiotes aloides

PubMed Central

Harpenslager, Sarah F.; Smolders, Alfons J. P.; Kieskamp, Ariët A. M.; Roelofs, Jan G. M.; Lamers, Leon P. M.

2015-01-01

Structural diversity formed by dense, floating Stratiotes aloides stands, generates hotspots of biodiversity of flora and fauna in wetlands. However, only part of the populations become emergent and provide this important facilitation. Since it has been hypothesised that its buoyancy depends on the rates of underwater photosynthesis, we investigated the role of dissolved CO2 availability and PAR on photosynthesis, biomass production and buoyancy in a controlled greenhouse experiment. Photosynthesis and growth were strongly influenced by both PAR and CO2 availability. At low PAR, plants formed less biomass and produced no emergent leaves, even when CO2 was abundant. At low CO2 levels, S. aloides switched to HCO3 - use, resulting in a lower photosynthetic O2 production, decreased emergent leaf formation and increased CaCO3 precipitation on its leaves, all of which impaired buoyancy. At high PAR, low CO2 availability resulted in slower colonisation of the water layer, whereas CO2 availability did not influence PAR-limited plants. Our study shows that site conditions, rather than the sole abundance of potentially facilitating species, may strongly determine whether or not they form the structure necessary to act as a facilitator for biodiversity in aquatic environments. PMID:25909504

Dissolved greenhouse gases (nitrous oxide and methane) associated with the natural iron-fertilized Kerguelen region (KEOPS 2 cruise) in the Southern Ocean

NASA Astrophysics Data System (ADS)

Farías, L.; Florez-Leiva, L.; Besoain, V.; Fernández, C.

2014-08-01

The concentrations of greenhouse gases (GHGs) like nitrous oxide (N2O) and methane (CH4) were measured in the Kerguelen Plateau Region (KPR), an area with annual microalgal bloom caused by natural Fe fertilization, which may stimulate microbes involved in GHG cycling. This study was carried out during the KEOPS 2 cruise during the austral spring of 2011. Two transects were sampled along and across the KRP, the north-south (N-S) transect (46-51° S, 72° E meridian) and the west-east (W-E) transect (66-75° E, 48.3° S latitude), both associated with the presence of a plateau, polar fronts and other mesoscale features. The W-E transect had N2O levels ranging from equilibrium (105%) to light supersaturation (120%) with respect to the atmosphere. CH4 levels fluctuated dramatically, with intense supersaturations (120-970%) in areas close to the coastal waters of Kerguelen Island and in the polar front (PF). There, Fe and nutrient fertilization seem to promote high total chlorophyll a (TChl a) levels. The distribution of both gases was more homogenous in the N-S transect, but CH4 peaked at southeastern stations of the KPR (A3 stations), where phytoplankton bloom was observed. Both gases responded significantly to the patchy distribution of particulate matter as Chl a, stimulated by Fe supply by complex mesoscale circulation. While CH4 appears to be produced mainly at the pycnoclines, N2O seems to be consumed superficially. Air-sea fluxes for N2O (from -10.5 to 8.65, mean 1.71 μmol m-2d-1), and for CH4 (from 0.32 to 38.1, mean 10.07 μmol m-2d-1) reflected sink and source behavior for N2O and source behavior for CH4, with considerable variability associated with a highly fluctuating wind regime and, in the case of CH4, due to its high superficial levels that had not been reported before in the Southern Ocean and may be caused by an intense microbial CH4 cycling.

Salt transport extraction of transuranium elements from LWR fuel

DOEpatents

Pierce, R.D.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Miller, W.E.

1992-11-03

A process is described for separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl[sub 2] and a Cu--Mg alloy containing not less than about 25% by weight Mg at a temperature in the range of from about 750 C to about 850 C to precipitate uranium metal and some of the noble metal fission products leaving the Cu--Mg alloy having transuranium actinide metals and rare earth fission product metals and some of the noble metal fission products dissolved therein. The CaCl[sub 2] having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO[sub 2]. The Ca metal and CaCl[sub 2] is recycled to reduce additional oxide fuel. The Cu--Mg alloy having transuranium metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with a transport salt including MgCl[sub 2] to transfer Mg values from the transport salt to the Cu--Mg alloy while transuranium actinide and rare earth fission product metals transfer from the Cu--Mg alloy to the transport salt. Then the transport salt is mixed with a Mg--Zn alloy to transfer Mg values from the alloy to the transport salt while the transuranium actinide and rare earth fission product values dissolved in the salt are reduced and transferred to the Mg--Zn alloy. 2 figs.

Concentration dependences of the density, viscosity, and refraction index of Cu(NO3)2 · 3H2O solutions in DMSO at 298 K

NASA Astrophysics Data System (ADS)

Mamyrbekova, A. K.

2013-03-01

Physicochemical properties (density, dynamic viscosity, refraction index) of the DMSO-Cu(NO3)2 · 3H2O system are studied in the concentration range of 0.01-2 M at 298 K. The refraction index of a solution of copper(II) nitrate in dimethylsulfoxide (DMSO) is measured at 288-318 K. The excess and partial molar volumes of the solvent and dissolved substance are calculated analytically.

Rapid nitrous oxide cycling in the suboxic ocean

NASA Astrophysics Data System (ADS)

Babbin, Andrew R.; Bianchi, Daniele; Jayakumar, Amal; Ward, Bess B.

2015-06-01

Nitrous oxide (N2O) is a powerful greenhouse gas and a major cause of stratospheric ozone depletion, yet its sources and sinks remain poorly quantified in the oceans. We used isotope tracers to directly measure N2O reduction rates in the eastern tropical North Pacific. Because of incomplete denitrification, N2O cycling rates are an order of magnitude higher than predicted by current models in suboxic regions, and the spatial distribution suggests strong dependence on both organic carbon and dissolved oxygen concentrations. Furthermore, N2O turnover is 20 times higher than the net atmospheric efflux. The rapid rate of this cycling coupled to an expected expansion of suboxic ocean waters implies future increases in N2O emissions.

Nitrogen fixation in the activated sludge treatment of thermomechanical pulping wastewater: effect of dissolved oxygen.

PubMed

Slade, A H; Anderson, S M; Evans, B G

2003-01-01

N-ViroTech, a novel technology which selects for nitrogen-fixing bacteria as the bacteria primarily responsible for carbon removal, has been developed to treat nutrient limited wastewaters to a high quality without the addition of nitrogen, and only minimal addition of phosphorus. Selection of the operating dissolved oxygen level to maximise nitrogen fixation forms a key component of the technology. Pilot scale activated sludge treatment of a thermomechanical pulping wastewater was carried out in nitrogen-fixing mode over a 15 month period. The effect of dissolved oxygen was studied at three levels: 14% (Phase 1), 5% (Phase 2) and 30% (Phase 3). The plant was operated at an organic loading of 0.7-1.1 kg BOD5/m3/d, a solids retention time of approximately 10 d, a hydraulic retention time of 1.4 d and a F:M ratio of 0.17-0.23 mg BOD5/mg VSS/d. Treatment performance was very stable over the three dissolved oxygen operating levels. The plant achieved 94-96% BOD removal, 82-87% total COD removal, 79-87% soluble COD removal, and >99% total extractives removal. The lowest organic carbon removals were observed during operation at 30% DO but were more likely to be due to phosphorus limitation than operation at high dissolved oxygen, as there was a significant decrease in phosphorus entering the plant during Phase 3. Discharge of dissolved nitrogen, ammonium and oxidised nitrogen were consistently low (1.1-1.6 mg/L DKN, 0.1-0.2 mg/L NH4+-N and 0.0 mg/L oxidised nitrogen). Discharge of dissolved phosphorus was 2.8 mg/L, 0.1 mg/L and 0.6 mg/L DRP in Phases 1, 2 and 3 respectively. It was postulated that a population of polyphosphate accumulating bacteria developed during Phase 1. Operation at low dissolved oxygen during Phase 2 appeared to promote biological phosphorus uptake which may have been affected by raising the dissolved oxygen to 30% in Phase 3. Total nitrogen and phosphorus discharge was dependent on efficient secondary clarification, and improved over the course of the study as suspended solids discharge improved. Nitrogen fixation was demonstrated throughout the study using an acetylene reduction assay. Based on nitrogen balances around the plant, there was a 55, 354 and 98% increase in nitrogen during Phases 1, 2 and 3 respectively. There was a significant decrease in phosphorus between Phases 1 and 2, and Phase 3 of the study, as well as a significant increase in nitrogen between Phases 2 and 3 which masked the effect of changing the dissolved oxygen. Operation at low dissolved oxygen appeared to confer a competitive advantage to the nitrogen-fixing bacteria.

The influence of tides on biogeochemical dynamics at the mouth of the Amazon River

NASA Astrophysics Data System (ADS)

Ward, N. D.; Sawakuchi, H. O.; Neu, V.; de Matos Valerio, A.; Less, D.; Guedes, V.; Wood, J.; Brito, D. C.; Cunha, A. C.; Kampel, M.; Richey, J. E.

2017-12-01

A major barrier to computing the flux of constituents from the world's largest rivers to the ocean is understanding the dynamic processes that occur along tidally-influenced river reaches. Here, we examine the response of a suite of biogeochemical parameters to tide-induced flow reversals at the mouth of the Amazon River. Continuous measurements of pCO2, pCH4, dissolved O2, pH, turbidity, and fluorescent dissolved organic matter (FDOM) were made throughout tidal cycles while held stationary in the center of the river and during hourly transects for ADCP discharge measurements. Samples were collected hourly from the surface and 50% depth during stationary samplings and from the surface during ADCP transects for analysis of suspended sediment concentrations along with other parameters such as nutrient and mercury concentrations. Suspended sediment and specific components of the suspended phase, such as particulate mercury, concentrations were positively correlated to mean river velocity during both high and low water periods with a more pronounced response at 50% depth than the surface. Tidal variations also influenced the concentration of O2 and CO2 by altering the dynamic balance between photosynthesis, respiration, and gas transfer. CO2 was positively correlated and O2 and pH were negatively correlated with river velocity. The concentration of methane generally increased during low tide (i.e. when river water level was lowest) both in the mainstem and in small side channels. In side channels concentrations increased by several orders of magnitude during low tide with visible bubbling from the sediment, presumably due to a release of hydrostatic pressure. These results suggest that biogeochemical processes are highly dynamic in tidal rivers, and these dynamic variations need to be quantified to better constrain global and regional scale budgets. Understanding these rapid processes may also provide insight into the long-term response of aquatic systems to change.

Enhanced phenol-photodegradation by particulate semiconductor mixtures: interparticle electron-jump.

PubMed

Karunakaran, C; Dhanalakshmi, R; Gomathisankar, P; Manikandan, G

2010-04-15

Degradation of phenol on suspended TiO(2), ZnO, CdO, Fe(2)O(3), CuO, ZnS and Nb(2)O(5) particles under UV-A light exhibit identical photokinetic behavior; follow first-order kinetics, display linear dependence on the photon flux and slowdown with increase of pH. All the semiconductors show sustainable photocatalytic activity. Dissolved O(2) is essential for the photodegradation and oxidizing agents like H(2)O(2), Na(2)BO(3), K(2)S(2)O(8), KBrO(3), KIO(3) and KIO(4), reducing agents such as NaNO(2) and Na(2)SO(3) and sacrificial electron donors like hydroquinone, diphenyl amine and trimethyl amine enhance the degradation. However, the photocatalysis is insensitive to pre-sonication. Two particulate semiconductors present together, under suspension and at continuous motion, enhance the photocatalytic degradation up to about four-fold revealing interparticle electron-jump. 2009 Elsevier B.V. All rights reserved.

The O2, pH and Ca2+ Microenvironment of Benthic Foraminifera in a High CO2 World

PubMed Central

Glas, Martin S.; Fabricius, Katharina E.; de Beer, Dirk; Uthicke, Sven

2012-01-01

Ocean acidification (OA) can have adverse effects on marine calcifiers. Yet, phototrophic marine calcifiers elevate their external oxygen and pH microenvironment in daylight, through the uptake of dissolved inorganic carbon (DIC) by photosynthesis. We studied to which extent pH elevation within their microenvironments in daylight can counteract ambient seawater pH reductions, i.e. OA conditions. We measured the O2 and pH microenvironment of four photosymbiotic and two symbiont-free benthic tropical foraminiferal species at three different OA treatments (∼432, 1141 and 2151 µatm pCO2). The O2 concentration difference between the seawater and the test surface (ΔO2) was taken as a measure for the photosynthetic rate. Our results showed that O2 and pH levels were significantly higher on photosymbiotic foraminiferal surfaces in light than in dark conditions, and than on surfaces of symbiont-free foraminifera. Rates of photosynthesis at saturated light conditions did not change significantly between OA treatments (except in individuals that exhibited symbiont loss, i.e. bleaching, at elevated pCO2). The pH at the cell surface decreased during incubations at elevated pCO2, also during light incubations. Photosynthesis increased the surface pH but this increase was insufficient to compensate for ambient seawater pH decreases. We thus conclude that photosynthesis does only partly protect symbiont bearing foraminifera against OA. PMID:23166810

Influence of some technological parameters on the formation of dimethyl sulfide, 2-mercaptoethanol, methionol, and dimethyl sulfone in port wines.

PubMed

Silva Ferreira, António César; Rodrigues, Paula; Hogg, Timothy; Guedes De Pinho, Paula

2003-01-29

Volatile sulfur compounds of 15 young port wines and 12 old port wines were determined. As there is a great difference in the pool of sulfur compounds between the two groups of wines, an experimental protocol was performed to determine which technological parameter (dissolved O(2), free SO(2) levels, pH, and time/temperature) was related with the formation/consumption of these compounds. Four sulfur compounds were selected for this purpose: dimethyl sulfide, 2-mercaptoethanol, dimethyl sulfone, and methionol. The synergistic effects of increasing temperature and O(2) at lower pH had the largest impact. Dimethyl sulfide was formed during the experimental period in the presence of O(2). Dimethyl sulfone had the same behavior. Methionol decreased significantly in the presence of O(2), but no methional was formed. 2-Mercaptoethanol, considered to be an important "off-flavor" in dry wines, also decreased during the experimental period (54 days) in the presence of O(2), and the respective disulfide was formed. These results corroborate the fact that old port wine (barrel aged) never develops "off-flavors" associated with the presence of methionol (cauliflower), 2-mercaptoethanol (rubber/burnt), or methional (cooked potato). In fact, temperature and oxygen are the major factors in the consumption of these molecules. However, some notes of "quince" and "metallic" can appear during port wine aging, and these can be associated with the presence of dimethyl sulfide.

Neptunium(V) and neptunium(VI) solubilities in synthetic brines of interest to the Waste Isolation Pilot Plant (WIPP)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Novak, C.F.; Nitsche, H.; Silber, H.B.

1996-12-31

The solubility of Np(V) and Np(VI) has been measured in three synthetic Na-K-Mg-Cl brines in the presence of CO{sub 2}(g). Experiments were prepared from oversaturation by adding an excess of NpO{sub 2}{sup +} or NpO{sub 2}{sup 2+} to the brines and allowing the neptunium solids to precipitate. Vessels were maintained in contact with fixed CO{sub 2}(g) partial pressures at constant pH and 24 {+-} 1 C. Dissolved Np(V) concentrations decreased several orders of magnitude within the first 100 days of the experiment, while dissolved Np(VI) concentrations decreased initially but then remained relatively constant for more than 400 days. The solidmore » phases formed in all experiments were identified by X-ray powder diffraction as KNpO{sub 2}CO{sub 3}{center_dot}xH{sub 2}O(s). Steady state concentrations for Np(V) are similar to those observed for Pu(V) in the same brines under the same conditions, where Pu occurs predominantly as Pu(V). Similarly, steady state concentrations for Np(VI), which was not reduced over a two year period, compare well with measured Pu(VI) concentrations in the same brines before the Pu(VI) was reduced to Pu(V).« less

Single particle ICP-MS method development for the determination of plant uptake and accumulation of CeO2 nanoparticles.

PubMed

Dan, Yongbo; Ma, Xingmao; Zhang, Weilan; Liu, Kun; Stephan, Chady; Shi, Honglan

2016-07-01

Cerium dioxide nanoparticles (CeO2NPs) are among the most broadly used engineered nanoparticles that will be increasingly released into the environment. Thus, understanding their uptake, transportation, and transformation in plants, especially food crops, is critical because it represents a potential pathway for human consumption. One of the primary challenges for the endeavor is the inadequacy of current analytical methodologies to characterize and quantify the nanomaterial in complex biological samples at environmentally relevant concentrations. Herein, a method was developed using single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) technology to simultaneously detect the size and size distribution of particulate Ce, particle concentration, and dissolved cerium in the shoots of four plant species including cucumber, tomato, soybean, and pumpkin. An enzymatic digestion method with Macerozyme R-10 enzyme previously used for gold nanoparticle extraction from the tomato plant was adapted successfully for CeO2NP extraction from all four plant species. This study is the first to report and demonstrate the presence of dissolved cerium in plant seedling shoots exposed to CeO2NPs hydroponically. The extent of plant uptake and accumulation appears to be dependent on the plant species, requiring further systematic investigation of the mechanisms.

Alteration of rhyolite in CO{sub 2} charged water at 200 and 350{degree}C: The unreactivity of CO{sub 2} at higher temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bischoff, J.L.; Rosenbauer, R.J.

1996-10-01

Geochemical and hydrologic modeling indicates that geothermal waters in the T > 270{degrees}C reservoirs beneath Yellowstone National Park have HCO{sub 3} {much_lt} Cl and contrast with waters in reservoirs at lower temperatures which attain HCO{sub 3} about equal to Cl. Experiments reacting rhyolite with 0.5 molal solutions of CO{sub 2} at 200{degrees} and 350{degrees}C were carried out to test the hypothesis of Fournier to explain the chemistry of these springs: that CO{sub 2} is relatively unreactive with volcanic rocks at temperatures >270{degrees}C. The experimental results strongly support this hypothesis. Extent of alteration is twenty-seven times greater at 200{degrees}C than atmore » 350{degrees}C. The dominant process in the experiments appears to be the alteration of the albitic component of the rhyolite by dissolved CO{sub 2} to form a kaolinite-like alteration product plus quartz: 2NaAlSi{sub 3}O{sub 8} + 2CO{sub 2} + 3H{sub 2}O = 2Na{sup +} + 2HCO{sub 3}{sup -} + Al{sub 2}Si{sub 2}O{sub 5}(OH){sub 4} + 4SiO{sub 2}. CO{sub 2} reacts with water to form H{sub 2}CO{sub 3} which dissociates to H{sup +} and HCO{sub 3}{sup -}, more so at lower temperatures. Kinetic and thermodynamic considerations suggest that the reactivity of H{sub 2}CO{sub 3} with wallrocks is at its maximum between 150{degrees} and 200{degrees}C, consuming most of the H{sup +} and liberating equivalent amounts of cations and bicarbonate. Wallrocks in higher temperature reservoirs are relatively unreactive to dissolved CO{sub 2} which is eventually lost from the system by boiling. These observations also offer a possible explanation for the change in chemical sediments from chloride-dominated to bicarbonate-dominated salts found in the stratigraphic section at Searles Lake, California, the terminus of the Owens River which derives its dissolved load from hot springs of the Long Valley caldera. 21 refs., 5 figs., 2 tabs.« less

Silica removal from steamflood-produced water: South Texas tar sands pilot

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, S.A.; Yost, M.E.; Cathey, S.R.

1987-05-01

Steamflood-produced waters commonly contain suspended solids, oil, hardness-causing minerals, sulfide, and silica. Removal of these contaminants would make many of these waters suitable for recycling as steamer feedwater. Reuse of steamflood-produced waters increases steamer feedwater supplies and reduces water disposal requirements. This paper describes a field pilot study of silica removal from steamflood-produced water in the south Texas tar sands region. A hot-lime precipitation process was used to reduce dissolved silica (SiO/sub 2/) concentrations from 400 to less than 50 mg/L SiO/sub 2/ in Mary R. Saner Ranch produced water. Most water systems using hot-lime precipitation for silica removal requiremore » the addition of magnesium salt, as well as lime, to enhance silica removal. In this field study, however, addition of magnesium salt did not improve silica removal efficiency. Hydrated lime, CA(OH)/sub 2/, alone was sufficient to attain desired silica residual, 50 mg/L SiO/sub 2/. The dissolved silica adsorbed onto the CaCO/sub 3/ crystals formed by lime reacting with the alkalinity present in the produced water. Required lime dosage was approximately 900 mg/L Ca(OH)/sub 2/.« less

Evaluation of sunlight induced structural changes and their effect on the photocatalytic activity of V2O5 for the degradation of phenols.

PubMed

Aslam, M; Ismail, Iqbal M I; Salah, Numan; Chandrasekaran, S; Qamar, M Tariq; Hameed, A

2015-04-09

Despite knowing the fact that vanadium pentoxide is slightly soluble in aqueous medium, its photocatalytic activity was evaluated for the degradation of phenol and its derivatives (2-hydroxyphenol, 2-chlorophenol, 2-aminophenol and 2-nitrophenol) in natural sunlight exposure. The prime objective of the study was to differentiate between the homogeneous and heterogeneous photocatalysis incurred by dissolved and undissolved V2O5 in natural sunlight exposure. V2O5 was synthesized by chemical precipitation procedure using Triton X-100 as morphology mediator and characterized by DRS, PLS, Raman, FESEM and XRD. A lower solubility of ∼ 5% per 100ml of water at 23 °C was observed after calcination at 600 °C. The study revealed no contribution of the dissolved V2O5 in the photocatalytic process. In sunlight exposure, V2O5 powder exhibited substantial activity for the degradation, however, a low mineralization of phenolic substrates was observed. The initial low activity of V2O5 followed by a sharp increase both in degradation and mineralization in complete spectrum sunlight exposure, was further investigated that revealed the decrease in the bandgap and the reduction in the particle size with the interaction of UV photons (<420 nm) as this effect was not observable in the exposure of visible region of sunlight. The role of the chemically different substituents attached to an aromatic ring at 2-positions and the secondary interaction of released ions during the degradation process with the reactive oxygen species (ROS) was also explored. Copyright © 2014 Elsevier B.V. All rights reserved.

Dynamics of localized charges in dopamine-modified TiO{sub 2} and their effect on the formation of reactive oxygen species.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dimitrijevic, N.; Rozhkova, E.; Rajh, T.

Modification of TiO{sub 2} nanoparticles with dopamine enables harvesting of visible light and promotes spatial separation of charges. The formation of reactive oxygen species (OH, {sup 1}O{sub 2}, O{sub 2}{sup -}, HO{sub 2}, H{sub 2}O{sub 2}) upon illumination of TiO{sub 2}/dopamine was studied using complementary spin-trap EPR and radical-induced fluorescence techniques. The localization of holes on dopamine suppresses oxidation of adsorbed water molecules at the surface of nanoparticles, and thus formation of OH radicals. At the same time, dopamine does not affect electronic properties of photogenerated electrons and their reaction with dissolved oxygen to produce superoxide anions. Superoxide anions aremore » proposed to generate singlet oxygen through dismutation reaction, resulting in a low yield of {sup 1}O{sub 2} detected.« less

Assessment of the toxic potential of engineered metal oxide nanomaterials using an acellular model: citrated rat blood plasma.

PubMed

Gormley, Patrick Thomas; Callaghan, Neal Ingraham; MacCormack, Tyson James; Dieni, Christopher Anthony

2016-10-01

Citrated Sprague-Dawley rat blood plasma was used as a biologically relevant exposure medium to assess the acellular toxic potential of two metal oxide engineered nanomaterials (ENMs), zinc oxide (nZnO), and cerium oxide (nCeO 2 ). Plasma was incubated at 37 °C for up to 48 h with ENM concentrations ranging between 0 and 200 mg/L. The degree of ENM-induced oxidation was assessed by assaying for reactive oxygen species (ROS) levels using dichlorofluorescein (DCF), pH, ferric reducing ability of plasma (FRAP), lipase activity, malondialdehyde (MDA), and protein carbonyls (PC). Whereas previous in vitro studies showed linear-positive correlations between ENM concentration and oxidative damage, our results suggested that low concentrations were generally pro-oxidant and higher concentrations appeared antioxidant or protective, as indicated by DCF fluorescence trends. nZnO and nCeO 2 also affected pH in a manner dependent on concentration and elemental composition; higher nZnO concentrations maintained a more alkaline pH, while nCeO 2 tended to decrease pH. No other biomarkers of oxidative damage (FRAP, MDA, PC, lipase activity) showed changes at any ENM concentration or time-point tested. Differential dissolution of the two ENMs was also observed, where as much as ∼31.3% of nZnO was instantaneously dissolved to Zn 2+  and only negligible nCeO 2 was degraded. The results suggest that the direct oxidative potential of nZnO and nCeO 2 in citrated rat blood plasma is low, and that a physiological or immune response is needed to generate appreciable damage biomarkers. The data also highlight the need for careful consideration when selecting a model for assessing ENM toxicity.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1991-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1988-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1989-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

Oxygen uptake and vertical transport during deep convection events

NASA Astrophysics Data System (ADS)

Sun, D.; Ito, T.; Bracco, A.

2016-02-01

Dissolved oxygen (O2) is essential for the chemistry and living organisms of the oceans. O2 is consumed in the interior ocean due to the respiration of organic matter, and must be replenished by physical ventilation with the O2-rich surface waters. The O2 supply to the deep waters happens only through the subduction and deep convection during cold seasons at high latitude oceans. The Labrador Sea is one of the few regions where deep ventilation occurs. According to observational and modeling studies, the intensity, duration and timing of deep convection events have varied significantly on the interannual and decadal timescales. In this study we develop a theoretical framework to understand the air-sea transfer of O2 during open-ocean deep convection events. The theory is tested against a suite of numerical integrations using MITgcm in non-hydrostatic configuration including the parameterization of diffusive and bubble mediated gas transfer. Forced with realistic air-sea buoyancy fluxes, the model can reproduce the evolution of temperature, salinity and dissolved O2 observed by ARGO floats in the Labrador Sea. Idealized sensitivity experiments are performed changing the intensity and duration of the buoyancy forcing as well as the wind speed for the gas exchange parameterizations. The downward transport of O2 results from the combination of vertical homogenization of existing O2 and the uptake from the air-sea flux. The intensity of the buoyancy forcing controls the vertical extent of convective mixing which brings O2 to the deep ocean. Integrated O2 uptake increases with the duration of convection even when the total buoyancy loss is held constant. The air-sea fluxes are highly sensitive to the wind speed especially for the bubble injection flux, which is a major addition to the diffusive flux under strong winds. However, the bubble injection flux can be partially compensated by the diffusive outgassing in response to the elevated saturation state. Under strong buoyancy forcing, this compensation is suppressed by the entrainment of relatively O2-poor deep waters. These results imply and allow to quantify the direct link between variability of deep convection and the supply of O2 in the North Atlantic.

Chemical and stable isotopic evidence for water/rock interaction and biogenic origin of coalbed methane, Fort Union Formation, Powder River Basin, Wyoming and Montana U.S.A

USGS Publications Warehouse

Rice, C.A.; Flores, R.M.; Stricker, G.D.; Ellis, M.S.

2008-01-01

Significant amounts (> 36??million m3/day) of coalbed methane (CBM) are currently being extracted from coal beds in the Paleocene Fort Union Formation of the Powder River Basin of Wyoming and Montana. Information on processes that generate methane in these coalbed reservoirs is important for developing methods that will stimulate additional production. The chemical and isotopic compositions of gas and ground water from CBM wells throughout the basin reflect generation processes as well as those that affect water/rock interaction. Our study included analyses of water samples collected from 228 CBM wells. Major cations and anions were measured for all samples, ??DH2O and ??18OH2O were measured for 199 of the samples, and ??DCH4 of gas co-produced with water was measured for 100 of the samples. Results show that (1) water from Fort Union Formation coal beds is exclusively Na-HCO3-type water with low dissolved SO4 content (median < 1??mg/L) and little or no dissolved oxygen (< 0.15??mg/L), whereas shallow groundwater (depth generally < 120??m) is a mixed Ca-Mg-Na-SO4-HCO3 type; (2) water/rock interactions, such as cation exchange on clay minerals and precipitation/dissolution of CaCO3 and SO4 minerals, account for the accumulation of dissolved Na and depletion of Ca and Mg; (3) bacterially-mediated oxidation-reduction reactions account for high HCO3 (270-3310??mg/L) and low SO4 (median < 0.15??mg/L) values; (4) fractionation between ??DCH4 (- 283 to - 328 per mil) and ??DH2O (- 121 to - 167 per mil) indicates that the production of methane is primarily by biogenic CO2 reduction; and (5) values of ??DH2O and ??18OH2O (- 16 to - 22 per mil) have a wide range of values and plot near or above the global meteoric water line, indicating that the original meteoric water has been influenced by methanogenesis and by being mixed with surface and shallow groundwater.

Greenhouse gases emissions in rivers of the Tibetan Plateau.

PubMed

Qu, Bin; Aho, Kelly Sue; Li, Chaoliu; Kang, Shichang; Sillanpää, Mika; Yan, Fangping; Raymond, Peter A

2017-11-29

Greenhouse gases (GHGs) emissions from streams are important to regional biogeochemical budgets. This study is one of the first to incorporate stream GHGs (CO 2 , CH 4 and N 2 O) concentrations and emissions in rivers of the Tibetan Plateau. With one-time sampling from 32 sites in rivers of the plateau, we found that most of the rivers were supersaturated with CO 2 , CH 4 and N 2 O during the study period. Medians of partial pressures of CO 2 (pCO 2 ), pCH 4 and pN 2 O were presented 864 μatm, 6.3 μatm, and 0.25 μatm respectively. Based on a scaling model of the flux of gas, the calculated fluxes of CO 2 , CH 4 and N 2 O (3,452 mg-C m 2 d -1 , 26.7 mg-C m 2 d -1 and 0.18 mg-N m 2 d -1 , respectively) in rivers of the Tibetan Plateau were found comparable with most other rivers in the world; and it was revealed that the evasion rates of CO 2 and CH 4 in tributaries of the rivers of the plateau were higher than those in the mainstream despite its high altitude. Furthermore, concentrations of GHGs in the studied rivers were related to dissolved carbon and nitrogen, indicating that riverine dissolved components could be used to scale GHGs envision in rivers of the Tibetan Plateau.

[Using Raman spectrum analysis to research corrosive productions occurring in alloy of ancient bronze wares].

PubMed

Jia, La-jiang; Jin, Pu-jun

2015-01-01

The present paper analyzes the interior rust that occurred in bronze alloy sample from 24 pieces of Early Qin bronze wares. Firstly, samples were processed by grinding, polishing and ultrasonic cleaning-to make a mirror surface. Then, a confocal micro-Raman spectrometer was employed to carry out spectroscopic study on the inclusions in samples. The conclusion indicated that corrosive phases are PbCO3 , PbO and Cu2O, which are common rusting production on bronze alloy. The light-colored circular or massive irregular areas in metallographic structure of samples are proved as Cu2O, showing that bronze wares are not only easy to be covered with red Cu2O rusting layer, but also their alloy is easy to be eroded by atomic oxygen. In other words, the rust Cu2O takes place in both the interior and exterior parts of the bronze alloy. In addition, Raman spectrum analysis shows that the dark grey materials are lead corrosive products--PbCO3 and PbO, showing the corroding process of lead element as Pb -->PbO-->PbCO3. In the texture of cast state of bronze alloy, lead is usually distributed as independent particles between the different alloy phases. The lead particles in bronze alloy would have oxidation reaction and generate PbO when buried in the soil, and then have chemical reaction with CO3(2-) dissolved in the underground water to generate PbCO3, which is a rather stable lead corrosive production. A conclusion can be drawn that the external corrosive factors (water, dissolved oxygen and carbonate, etc) can enter the bronze ware interior through the passageway between different phases and make the alloy to corrode gradually.

Formation of organobromine and organoiodine compounds by engineered TiO2 nanoparticle-induced photohalogenation of dissolved organic matter in environmental waters.

PubMed

Hao, Zhineng; Yin, Yongguang; Wang, Juan; Cao, Dong; Liu, Jingfu

2018-08-01

There are increasing concerns about the adverse effects of released engineered nanoparticles and photochemically formed organohalogen compounds (OHCs) on human health and the environment. Herein, we report that titanium dioxide nanoparticles (TiO 2 NPs) can photocatalytically halogenate dissolved organic matter (DOM) to form a large number of organobromine compounds (OBCs) and organoiodine compounds (OICs), as characterized by negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry. Compared with no OHCs produced in control samples in darkness and/or without TiO 2 NPs under sunlight irradiation, various OBCs and OICs were detected in freshwater and seawater under sunlight irradiation for 12h and 24h even in the presence of 1mgL -1 TiO 2 NPs, indicating the photocatalytic roles TiO 2 NPs played in DOM halogenation. Furthermore, TiO 2 NPs could result in the photodegradation of newly formed OHCs, as evidenced by the intensity and the number of some OHCs decreased with reaction time. In addition, many TiO 2 NP-induced OBCs contained two or three bromine atoms, and/or nitrogen and sulfur elements, belonging to lignin-like, tannin-like, unsaturated hydrocarbon and aliphatic compounds. While the OICs were primarily contained one iodine, and very few consisted of nitrogen and sulfur elements, most were lignin-like and tannin-like compounds. Finally, the OBCs in freshwater were found to be formed mainly via a substitution reaction or addition reaction and were accompanied by other reactions such as photooxidation, while the OBCs in seawater and OICs were formed primarily via substitution reactions. Given the abundance of produced OHCs and their toxicity, our findings call for further studies on the exact structure and toxicity of the formed OHCs, taking account the TiO 2 NP-induced DOM photohalogenation in aquatic environments during the evaluation of the environmental effects of engineered TiO 2 NPs. Copyright © 2018 Elsevier B.V. All rights reserved.

Formation of Si grains from a NaSi melt prepared by reaction of SiO2 and Na

NASA Astrophysics Data System (ADS)

Yamane, Hisanori; Morito, Haruhiko; Uchikoshi, Masahito

2013-08-01

A mixture of Na2SiO3 and NaSi was found to be formed by reaction of SiO2 and Na at 650 °C as follows: 5Na+3SiO2→2Na2SiO3+NaSi. Single crystals of NaSi were grown by cooling the mixture of Na2SiO3 and NaSi with an excess amount of Na from 850 °C, and polycrystalline Si was obtained by vaporization of Na from the crystals. Coarse grains of Si were also crystallized by Na evaporation after the formation of Na2SiO3 and Si-dissolved liquid Na at 830 °C. The Si grains were collected by washing the product with water. The yield of the Si grains was 85% of the ideal amount expected from the reaction.

Total dissolved gas, barometric pressure, and water temperature data, lower Columbia River, Oregon and Washington, 1996

USGS Publications Warehouse

Tanner, Dwight Q.; Harrison, Howard E.; McKenzie, Stuart W.

1996-01-01

Increased levels of total dissolved gas pressure can cause gas-bubble trauma in fish downstream from dams on the Columbia River. In cooperation with the U.S. Army Corps of Engineers, the U.S. Geological Survey collected data on total dissolved gas pressure, barometric pressure, water temperature, and dissolved oxygen pressure at 11 stations on the lower Columbia River from the John Day forebay (river mile 215.6) to Wauna Mill (river mile 41.9) from March to September 1996. Methods of data collection, review, and processing are described in this report. Summaries of daily minimum, maximum, and mean hourly values are presented for total dissolved gas pressure, barometric pressure, and water temperature. Hourly values for these parameters are presented graphically. Dissolved oxygen data are not presented in this report because the quality-control data show that the data have poor precision and high bias. Suggested changes to monitoring procedures for future studies include (1) improved calibration procedures for total dissolved gas and dissolved oxygen to better define accuracy at elevated levels of supersaturation and (2) equipping dissolved oxygen sensors with stirrers because river velocities at the shoreline monitoring stations probably cannot maintain an adequate flow of water across the membrane surface of the dissolved oxygen sensor.

Algal productivity and nitrate assimilation in an effluent dominated concrete lined stream

USGS Publications Warehouse

Kent, Robert; Belitz, Kenneth; Burton, Carmen

2005-01-01

This study examined algal productivity and nitrate assimilation in a 2.85 km reach of Cucamonga Creek, California, a concrete lined channel receiving treated municipal wastewater. Stream nitrate concentrations observed at two stations indicated nearly continuous loss throughout the diel study. Nitrate loss in the reach was approximately 11 mg/L/d or 1.0 g/m2/d as N, most of which occurred during daylight. The peak rate of nitrate loss (1.13 mg/l/hr) occurred just prior to an afternoon total CO2 depletion. Gross primary productivity, as estimated by a model using the observed differences in dissolved oxygen between the two stations, was 228 mg/L/d, or 21 g/m2/d as O2. The observed diel variations in productivity, nitrate loss, pH, dissolved oxygen, and CO2indicate that nitrate loss was primarily due to algal assimilation. The observed levels of productivity and nitrate assimilation were exceptionally high on a mass per volume basis compared to studies on other streams; these rates occurred because of the shallow stream depth. This study suggests that concrete‐lined channels can provide an important environmental service: lowering of nitrate concentrations similar to rates observed in biological treatment systems.

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

PubMed

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies

DOE PAGES

Zehnder, Ralph A.; Jenkins, James; Zeller, Matthias; ...

2017-11-26

Here, using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln 2(Glut) 2Cl 2(H 2O) 8]·2H 2O·THF, with Ln = La , Ce, Pr, Nd. They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO 10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln 2(Glut) 3(H 2O) 3]·5H 2O, withmore » Ln = La, Ce, Pr, and [Nd 2(Glut) 3(H 2O) 2]·3.5H 2O.« less

Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zehnder, Ralph A.; Jenkins, James; Zeller, Matthias

Here, using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln 2(Glut) 2Cl 2(H 2O) 8]·2H 2O·THF, with Ln = La , Ce, Pr, Nd. They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO 10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln 2(Glut) 3(H 2O) 3]·5H 2O, withmore » Ln = La, Ce, Pr, and [Nd 2(Glut) 3(H 2O) 2]·3.5H 2O.« less

Fractionation of sulfur and oxygen isotopes in sulfate by soil sorption

NASA Astrophysics Data System (ADS)

Van Stempvoort, D. R.; Reardon, E. J.; Fritz, P.

1990-10-01

Both field and laboratory data indicate that there is no significant isotope fractionation of sulfate during sorption in upland forest Podzols. The dominant sulfate sorption process in these soils is adsorption onto mineral surfaces. In the Plastic Lake watershed, Dorset, Ontario, Canada, fractions of sulfate from Podzol B-horizons have the following mean isotope (%.) compositions: water soluble sulfate, δ34S = +6.4; δ18O = -5.3; bicarbonate-exchanged sulfate by two methods, δ34S = + 4.5 and + 3.4; δ18O =-6.2 and -5.6; dissolved sulfate in B-horizon soilwater seepage, δ34S = + 4.8; δ18O = -5.4. These data indicate that soil sorption enriches dissolved sulfate in 34S by approximately 1 ± 1%. and in 18O by 0 +- 1 %. relative to sorbed sulfate. Similar results were obtained by laboratory sorption of sulfate by prepared goethite, which is a mineral representative of soil sorption sites in acidic Podzols like the one at Plastic Lake. The mean fractionation between sorbed and dissolved sulfate was found to be - 0.3%. for 34S and 0.1 %. for 18O. Earlier literature has confused the term adsorption; in many cases the more general term sorption, or retention, should be used. Pronounced fractionation of S and O isotopes in sulfate by lake and ocean sediments has been attributed to "adsorption" or "retention" but is more likely the result of sulfate reduction. Apparently, at Earth-surface conditions the only substantial isotope shifts in sulfate occur during microbial processes.

Groundwater nitrate reduction versus dissolved gas production: A tale of two catchments.

PubMed

McAleer, E B; Coxon, C E; Richards, K G; Jahangir, M M R; Grant, J; Mellander, Per E

2017-05-15

At the catchment scale, a complex mosaic of environmental, hydrogeological and physicochemical characteristics combine to regulate the distribution of groundwater and stream nitrate (NO 3 - ). The efficiency of NO 3 - removal (via denitrification) versus the ratio of accumulated reaction products, dinitrogen (excess N 2 ) & nitrous oxide (N 2 O), remains poorly understood. Groundwater was investigated in two well drained agricultural catchments (10km 2 ) in Ireland with contrasting subsurface lithologies (sandstone vs. slate) and landuse. Denitrification capacity was assessed by measuring concentration and distribution patterns of nitrogen (N) species, aquifer hydrogeochemistry, stable isotope signatures and aquifer hydraulic properties. A hierarchy of scale whereby physical factors including agronomy, water table elevation and permeability determined the hydrogeochemical signature of the aquifers was observed. This hydrogeochemical signature acted as the dominant control on denitrification reaction progress. High permeability, aerobic conditions and a lack of bacterial energy sources in the slate catchment resulted in low denitrification reaction progress (0-32%), high NO 3 - and comparatively low N 2 O emission factors (EF 5g 1). In the sandstone catchment denitrification progress ranged from 4 to 94% and was highly dependent on permeability, water table elevation, dissolved oxygen concentration solid phase bacterial energy sources. Denitrification of NO 3 - to N 2 occurred in anaerobic conditions, while at intermediate dissolved oxygen; N 2 O was the dominant reaction product. EF 5g 1 (mean: 0.0018) in the denitrifying sandstone catchment was 32% less than the IPCC default. The denitrification observations across catchments were supported by stable isotope signatures. Stream NO 3 - occurrence was 32% lower in the sandstone catchment even though N loading was substantially higher than the slate catchment. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Aqueous speciation is likely to control the stable isotopic fractionation of cerium at varying pH

NASA Astrophysics Data System (ADS)

Nakada, Ryoichi; Tanaka, Masato; Tanimizu, Masaharu; Takahashi, Yoshio

2017-12-01

Cerium (Ce) can be used as a plaeoredox proxy as shown by a recent study of stable isotopic fractionation of Ce during adsorption and precipitation. However, the experiments in that study were performed at pH conditions lower than that of natural seawater. In the current study, adsorption and precipitation experiments were performed at pH 6.80, 8.20, and 11.00 with 2.25 mM dissolved carbonate to simulate Ce isotopic fractionation in the natural environment and examine the relationship between isotopic fractionation and Ce speciation in the liquid phase. Mean isotopic fractionation factors between liquid and solid phases (αLq-So) of Ce adsorbed on ferrihydrite did not depend on pH conditions or dissolved Ce species. In the Ce/δ-MnO2 system,αLq-So values decreased from 1.000411 (±0.000079) to 1.000194 (±0.000067) with increasing pH or number of carbonate ions, from Ce3+ to Ce(CO3)2-. In the Ce/precipitation system at pH 8.20 and 11.00 where Ce(CO3)2- is present in solution, the αLq-So values were 0.999821 (±0.000071) and 0.999589 (±0.000074), respectively, meaning that lighter isotope enrichment was observed in the liquid phase, which is the contrary to those of the other systems. Extended X-ray absorption fine structure (EXAFS) analyses were also performed to investigate the coordination structure of the adsorbed or precipitated Ce species that control the isotopic fractionation during adsorption. Even at higher pH, where Ce(CO3)+ or Ce(CO3)2- are the dominant dissolved species, the first coordination sphere of Ce in the solid phase in the Ce/ferrihydrite and Ce/precipitation systems was similar to that observed at pH 5.00 where Ce3+ was the main species in solution. A slight elongation in the Cesbnd O bond length in the solid phase at pH 11.00, where negatively charged dissolved species are dominant in the liquid phase, may cause a decrease in isotopic fractionation in the Ce/δ-MnO2 system. The coordination environment of Ce may not change significantly during the adsorption onto ferrihydrite, because Ce binds to the neutral surface OH group on ferrihydrite at pH below 8.5-8.8 (i.e. the pH of the point of zero charge (PZC) for ferrihydrite), similar to other cations when the metal-O distance was similar in hydrated and adsorbed species. At pH above PZC, Ce bonds to the negatively charged surface OH group, while Ce also bonds with CO32- in dissolved species. The reduced partition functions (ln β) for dissolved species (ln βLq) and adsorbed species (ln βSo) with the same trends canceled each other, because ln β of hydrated cation was reduced by the binding anion, resulting in small isotope fractionations. Thus, isotope fractionations for Ce/ferrihydrite may be quite small at the entire pH conditions in this study. The direction of the isotopic fractionation was estimated based on density functional theory (DFT) calculations, which confirmed that lighter Ce is enriched in the liquid phase when Ce forms a complex with carbonate ions. Therefore, this study indicates that the dissolved species can control stable Ce isotopic fractionation during precipitation reactions.

Availability of O(2) and H(2)O(2) on pre-photosynthetic Earth.

PubMed

Haqq-Misra, Jacob; Kasting, James F; Lee, Sukyoung

2011-05-01

Old arguments that free O(2) must have been available at Earth's surface prior to the origin of photosynthesis have been revived by a new study that shows that aerobic respiration can occur at dissolved oxygen concentrations much lower than had previously been thought, perhaps as low as 0.05 nM, which corresponds to a partial pressure for O(2) of about 4 × 10(-8) bar. We used numerical models to study whether such O(2) concentrations might have been provided by atmospheric photochemistry. Results show that disproportionation of H(2)O(2) near the surface might have yielded enough O(2) to satisfy this constraint. Alternatively, poleward transport of O(2) from the equatorial stratosphere into the polar night region, followed by downward transport in the polar vortex, may have brought O(2) directly to the surface. Thus, our calculations indicate that this "early respiration" hypothesis might be physically reasonable.

Dissolved Oxygen Data for Coos Estuary (Oregon)

EPA Science Inventory

The purpose of this product is the transmittal of dissolved oxygen data collected in the Coos Estuary, Oregon to Ms. Molly O'Neill (University of Oregon), for use in her studies on the factors influencing spatial and temporal patterns in dissolved oxygen in this estuary. These d...

Experimental Determination of the H2O-undersaturated Peridotite Solidus

NASA Astrophysics Data System (ADS)

Sarafian, E. K.; Gaetani, G. A.; Hauri, E.; Sarafian, A.

2015-12-01

Knowledge of the H2O-undersaturated lherzolite solidus places important constraints on the process of melt generation beneath oceanic spreading centers. While it is generally accepted that the small concentration of H2O (~50-200 ug/g) dissolved in the oceanic upper mantle has a strong influence on the peridotite solidus, but this effect has not been directly determined through experiments. This is because (1) precisely controlling low concentrations of H2O in high-pressure melting experiments is thought to be difficult, (2) small amounts of melt are difficult to identify, and (3) the size of mineral grains that grow in near-solidus experiments is too small to be analyzed for H2O by either Fourier transform infrared (FTIR) spectroscopy or secondary ion mass spectrometry (SIMS). We have developed an experimental approach for determining the peridotite solidus as a function of H2O content that overcomes these difficulties. Our approach utilizes large (~300 um diameter) spheres of San Carlos olivine to monitor the concentration and behavior of H2O in our experiments.. The spheres are mixed in 5:95 proportions with a synthetic peridotite that has the composition of the depleted MORB mantle of Workman and Hart (2005). Partial melting experiments are conducted in is a piston cylinder device using pre-conditioned Au80Pd20 capsules. During an experiment, the H2O content of the San Carlos olivine spheres diffusively equilibrates with the peridotite matrix. After each experiment, the concentration of H2O dissolved in the olivine spheres is determined by secondary ion mass spectrometry. By analyzing the H2O content of the San Carlos olivine spheres and performing a simple mass balance, we can then calculate the amount of H2O in the capsule. The spheres also provides a means to determine the solidus temperature due to the strong partitioning of H2O into silicate melt compared to olivine, pyroxene, and spinel. When a small amount of melt is present the H2O partitions into the melt and the H2O content of the spheres drops in a predictable fashion. The H2O-undersaturated solidus indicated by our experimental results is in agreement with previous experimental determinations of the nominally anhydrous solidus. This suggests that the potential temperature of the oceanic upper mantle is higher than existing petrologic estimates.

Carbonate Mineralization of Volcanic Province Basalts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

2010-03-31

Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO2, with studies underway in the United States, India, Iceland, and Canada. As an extension of our previous experiments with Columbia River basalt, basalts from the eastern United States, India, and South Africa were reacted with aqueous dissolved CO2 and aqueous dissolved CO2-H2S mixtures under supercritical CO2 (scCO2) conditions to study the geochemical reactions resulting from injection of CO2 in such formations. The results of these studies are consistent with cation release behavior measured in our previous experiments (in press) for basalt samples tested inmore » single pass flow through dissolution experiments under dilute solution and mildly acidic conditions. Despite the basalt samples having similar bulk chemistry, mineralogy and apparent dissolution kinetics, long-term static experiments show significant differences in rates of mineralization as well as compositions and morphologies of precipitates that form when the basalts are reacted with CO2-saturated water. For example, basalt from the Newark Basin in the United States was by far the most reactive of any basalt tested to date. Carbonate reaction products for the Newark Basin basalt were globular in form and contained significantly more Fe than the secondary carbonates that precipitated on the other basalt samples. In comparison, the post-reacted samples associated with the Columbia River basalts from the United States contained calcite grains with classic dogtooth spar morphology and trace cation substitution (Mg and Mn). Carbonation of the other basalts produced precipitates with compositions that varied chemically throughout the entire testing period. Examination of polished cross sections of the reacted grains by scanning electron microscopy and energy dispersive x-ray spectroscopy show precipitate overgrowths with varying chemical compositions. Compositional differences in the precipitates suggest changes in fluid chemistry unique to the dissolution behavior of each basalt sample reacted with CO2-saturated water. The Karoo basalt from South Africa appeared the least reactive, with very limited mineralization occurring during the testing with CO2-saturated water. The relative reactivity of different basalt samples were unexpectedly different in the experiments conducted using aqueous dissolved CO2-H2S mixtures versus those reacted with aqueous dissolved CO2 mixtures. For example, the Karoo basalt was highly reactive in the presence of aqueous dissolved CO2-H2S, as evident by small nodules of carbonate coating the basalt grains after 181 days of testing. However the most reactive basalt in CO2-H2O, Newark Basin, formed limited amounts of carbonate precipitates in the presence of aqueous dissolved CO2-H2S mixture. Basalt reactivity in CO2-H2O mixtures appears to be controlled by the composition of the glassy mesostasis, which is the most reactive component in the basalt rock. With the addition of H2S to the CO2-H2O system, basalt reactivity appears to be controlled by precipitation of coatings of insoluble Fe sulfides.« less

Novel insights into anoxic/aerobic(1)/aerobic(2) biological fluidized-bed system for coke wastewater treatment by fluorescence excitation-emission matrix spectra coupled with parallel factor analysis.

PubMed

Ou, Hua-Se; Wei, Chao-Hai; Mo, Ce-Hui; Wu, Hai-Zhen; Ren, Yuan; Feng, Chun-Hua

2014-10-01

Fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC) was applied to investigate the contaminant removal efficiency and fluorescent characteristic variations in a full scale coke wastewater (CWW) treatment plant with a novel anoxic/aerobic(1)/aerobic(2) (A/O(1)/O(2)) process, which combined with internal-loop fluidized-bed reactor. Routine monitoring results indicated that primary contaminants in CWW, such as phenols and free cyanide, were removed efficiently in A/O(1)/O(2) process (removal efficiency reached 99% and 95%, respectively). Three-dimensional excitation-emission matrix fluorescence spectroscopy and PARAFAC identified three fluorescent components, including two humic-like fluorescence components (C1 and C3) and one protein-like component (C2). Principal component analysis revealed that C1 and C2 correlated with COD (correlation coefficient (r)=0.782, p<0.01 and r=0.921, p<0.01), respectively) and phenols (r=0.796, p<0.01 and r=0.914, p<0.01, respectively), suggesting that C1 and C2 might be associated with the predominating aromatic contaminants in CWW. C3 correlated with mixed liquor suspended solids (r=0.863, p<0.01) in fluidized-bed reactors, suggesting that it might represent the biological dissolved organic matter. In A/O(1)/O(2) process, the fluorescence intensities of C1 and C2 consecutively decreased, indicating the degradation of aromatic contaminants. Correspondingly, the fluorescence intensity of C3 increased in aerobic(1) stage, suggesting an increase of biological dissolved organic matter. Copyright © 2014 Elsevier Ltd. All rights reserved.

Salt transport extraction of transuranium elements from lwr fuel

DOEpatents

Pierce, R. Dean; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a Cu--Mg alloy containing not less than about 25% by weight Mg at a temperature in the range of from about 750.degree. C. to about 850.degree. C. to precipitate uranium metal and some of the noble metal fission products leaving the Cu--Mg alloy having transuranium actinide metals and rare earth fission product metals and some of the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The Cu--Mg alloy having transuranium metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with a transport salt including Mg Cl.sub.2 to transfer Mg values from the transport salt to the Cu--Mg alloy while transuranium actinide and rare earth fission product metals transfer from the Cu--Mg alloy to the transport salt. Then the transport salt is mixed with a Mg--Zn alloy to transfer Mg values from the alloy to the transport salt while the transuranium actinide and rare earth fission product values dissolved in the salt are reduced and transferred to the Mg--Zn alloy.

Impact of the excess sludge modification with selected chemical reagents on the increase of dissolved organic substances concentration compounds transformations in activated sludge.

PubMed

Zawieja, Iwona; Lidia, Wolny; Marta, Próba

2017-07-01

Submission of excess sludge initial disintegration process significantly affects the efficiency of anaerobic stabilization process. Expression of increasing the concentration of organic matter in dissolved form is to increase sludge disintegration. As a result of chemical modification is an increase of the chemical oxygen demand and the concentration of volatile fatty acids. The aim of this study was to determine the impact of the disintegration process with selected chemical reagents to increase the concentration of organic substances in dissolved form. The process of chemical disintegration of excess sludge was treated using the following reagents: Mg(OH) 2 , Ca(OH) 2 , HCl, H 2 SO 4 , H 2 O 2 . The modification was carried out at ambient temperature for 2, 6 and 24h. During sludge disintegration it was noticed the growth of indicators values that confirmed the susceptibility of prepared sludge to biodegradation. Copyright © 2017 Elsevier Inc. All rights reserved.

Colorimetric detection of catalytic reactivity of nanoparticles in complex matrices.

PubMed

Corredor, Charlie; Borysiak, Mark D; Wolfer, Jay; Westerhoff, Paul; Posner, Jonathan D

2015-03-17

There is a need for new methodologies to quickly assess the presence and reactivity of nanoparticles (NPs) in commercial, environmental, and biological samples since current detection techniques require expensive and complex analytical instrumentation. Here, we investigate a simple and portable colorimetric detection assay that assesses the surface reactivity of NPs, which can be used to detect the presence of NPs, in complex matrices (e.g., environmental waters, serum, urine, and in dissolved organic matter) at as low as part per billion (ppb) or ng/mL concentration levels. Surface redox reactivity is a key emerging property related to potential toxicity of NPs with living cells, and is used in our assays as a key surrogate for the presence of NPs and a first tier analytical strategy toward assessing NP exposures. We detect a wide range of metal (e.g., Ag and Au) and oxide (e.g., CeO2, SiO2, VO2) NPs with a diameter range of 5 to 400 nm and multiple capping agents (tannic acid (TA), polyvinylpyrrolidone (PVP), branched polyethylenimine (BPEI), polyethylene glycol (PEG)). This method is sufficiently sensitive (ppb levels) to measure concentrations typically used in toxicological studies, and uses inexpensive, commercially available reagents.

The role of iron and reactive oxygen species in the production of CO2 in arctic soil waters

NASA Astrophysics Data System (ADS)

Trusiak, Adrianna; Treibergs, Lija A.; Kling, George W.; Cory, Rose M.

2018-03-01

Hydroxyl radical (radOH) is a highly reactive oxidant of dissolved organic carbon (DOC) in the environment. radOH production in the dark was observed through iron and DOC mediated Fenton reactions in natural environments. Specifically, when dissolved oxygen (O2) was added to low oxygen and anoxic soil waters in arctic Alaska, radOH was produced in proportion to the concentrations of reduced iron (Fe(II)) and DOC. Here we demonstrate that Fe(II) was the main electron donor to O2 to produce radOH. In addition to quantifying radOH production, hydrogen peroxide (H2O2) was detected in soil waters as a likely intermediate in radOH production from oxidation of Fe(II). For the first time in natural systems we detected carbon dioxide (CO2) production from radOH oxidation of DOC. More than half of the arctic soil waters tested showed production of CO2 under conditions conducive for production of radOH. Findings from this study strongly suggest that DOC is the main sink for radOH, and that radOH can oxidize DOC to yield CO2. Thus, this iron-mediated, dark chemical oxidation of DOC may be an important component of the arctic carbon cycle.

Carbon dioxide-assisted fabrication of highly uniform submicron-sized colloidal carbon spheres via hydrothermal carbonization using soft drink

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moon, Gun-Hee; Shin, Yongsoon; Arey, Bruce W.

An eco-friendly and economical method for the formation of uniform-sized carbon spheres by hydrothermal dehydration/condensation of a commercial carbonated beverage at 200 oC is reported. CO2 dissolved in the beverage accelerates the dehydration kinetics of the dissolved sugar molecules leading to production of homogeneous carbon spheres having a diameter less than 850 nm. In the presence of CO2, the rough surface of these carbon spheres likely results from continuous Ostwald ripening of constituent microscopic carbon-containing spheres that are formed by subsequent polymerization of intermediate HMF molecules.

Modeling the Losses of Dissolved CO(2) from Laser-Etched Champagne Glasses.

PubMed

Liger-Belair, Gérard

2016-04-21

Under standard champagne tasting conditions, the complex interplay between the level of dissolved CO2 found in champagne, its temperature, the glass shape, and the bubbling rate definitely impacts champagne tasting by modifying the neuro-physicochemical mechanisms responsible for aroma release and flavor perception. On the basis of theoretical principles combining heterogeneous bubble nucleation, ascending bubble dynamics, and mass transfer equations, a global model is proposed, depending on various parameters of both the wine and the glass itself, which quantitatively provides the progressive losses of dissolved CO2 from laser-etched champagne glasses. The question of champagne temperature was closely examined, and its role on the modeled losses of dissolved CO2 was corroborated by a set of experimental data.

Rates of 1O 2 ( 1Δ g) production upon direct excitation of molecular oxygen by 1270 nm laser radiation in air-saturated alcohols and micellar aqueous dispersions

NASA Astrophysics Data System (ADS)

Krasnovsky, A. A.; Rоumbal, Ya. V.; Strizhakov, A. A.

2008-06-01

The oxygenation rates of the 1O2 trap, 1,3-diphenylisobenzofuran were measured in air-saturated H2O-sodium dodecyl sulfate dispersions, ethanol, methanol and benzene upon direct excitation of dissolved oxygen by infrared (1269 ± 1 nm) laser radiation. In aqueous dispersions, variation of the detergent concentration from 0.1 to 1 M resulted in the 2.5-time increase of the photooxygenation rate. The absorbance and molar absorption coefficients of oxygen were estimated in all tested systems, water and the micellar phase of detergent dispersions and compared with the rate constants of 1O2 radiative deactivation obtained from the measurement of the quantum yields of photosensitized 1O2 phosphorescence.

Steam Oxidation Behavior of Alloy 617 at 900 °C to 1100 °C

NASA Astrophysics Data System (ADS)

Liang, Zhiyuan; Wang, Yungang; Zhao, Qinxin

2018-07-01

The steam oxidation behavior of solid solution strengthened alloy 617 at 900 °C-1100 °C was investigated. The oxidation products were characterized by scanning electron microscopy, X-ray diffraction, and energy-dispersive spectroscopy. The results show that the oxidation kinetics of alloy 617 in steam followed the parabolic oxidation law. The calculated activity energy of alloy 617 was 223.47 kJ/mol. The oxidation products were mainly composed of external and internal scales and prior oxides at grain boundaries. External oxide scales were MnCr2O4, TiO2, and Cr2O3. Internal oxidation scales and prior oxides were Al2O3 and some Cr2O3 dissolved into Al2O3. The growth mechanism of oxide scales on alloy 617 is proposed.

Steam Oxidation Behavior of Alloy 617 at 900 °C to 1100 °C

NASA Astrophysics Data System (ADS)

Liang, Zhiyuan; Wang, Yungang; Zhao, Qinxin

2018-05-01

The steam oxidation behavior of solid solution strengthened alloy 617 at 900 °C-1100 °C was investigated. The oxidation products were characterized by scanning electron microscopy, X-ray diffraction, and energy-dispersive spectroscopy. The results show that the oxidation kinetics of alloy 617 in steam followed the parabolic oxidation law. The calculated activity energy of alloy 617 was 223.47 kJ/mol. The oxidation products were mainly composed of external and internal scales and prior oxides at grain boundaries. External oxide scales were MnCr2O4, TiO2, and Cr2O3. Internal oxidation scales and prior oxides were Al2O3 and some Cr2O3 dissolved into Al2O3. The growth mechanism of oxide scales on alloy 617 is proposed.

AFS-2 FLOWSHEET MODIFICATIONS TO ADDRESS THE INGROWTH OF PU(VI) DURING METAL DISSOLUTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crapse, K.; Rudisill, T.; O'Rourke, P.

2014-07-02

In support of the Alternate Feed Stock Two (AFS-2) PuO{sub 2} production campaign, Savannah River National Laboratory (SRNL) conducted a series of experiments concluding that dissolving Pu metal at 95°C using a 6–10 M HNO{sub 3} solution containing 0.05–0.2 M KF and 0–2 g/L B could reduce the oxidation of Pu(IV) to Pu(VI) as compared to dissolving Pu metal under the same conditions but at or near the boiling temperature. This flowsheet was demonstrated by conducting Pu metal dissolutions at 95°C to ensure that PuO{sub 2} solids were not formed during the dissolution. These dissolution parameters can be used formore » dissolving both Aqueous Polishing (AP) and MOX Process (MP) specification materials. Preceding the studies reported herein, two batches of Pu metal were dissolved in the H-Canyon 6.1D dissolver to prepare feed solution for the AFS-2 PuO{sub 2} production campaign. While in storage, UV-visible spectra obtained from an at-line spectrophotometer indicated the presence of Pu(VI). Analysis of the solutions also showed the presence of Fe, Ni, and Cr. Oxidation of Pu(IV) produced during metal dissolution to Pu(VI) is a concern for anion exchange purification. Anion exchange requires Pu in the +4 oxidation state for formation of the anionic plutonium(IV) hexanitrato complex which absorbs onto the resin. The presence of Pu(VI) in the anion feed solution would require a valence adjustment step to prevent losses. In addition, the presence of Cr(VI) would result in absorption of chromate ion onto the resin and could limit the purification of Pu from Cr which may challenge the purity specification of the final PuO{sub 2} product. Initial experiments were performed to quantify the rate of oxidation of Pu(IV) to Pu(VI) (presumed to be facilitated by Cr(VI)) as functions of the HNO{sub 3} concentration and temperature in simulated dissolution solutions containing Cr, Fe, and Ni. In these simulated Pu dissolutions studies, lowering the temperature from near boiling to 95 °C reduced the oxidation rate of Pu(IV) to Pu(VI). For 8.1 M HNO{sub 3} simulated dissolution solutions, at near boiling conditions >35% Pu(VI) was present in 50 h while at 95 °C <10% Pu(VI) was present at 50 h. At near boiling temperatures, eliminating the presence of Cr and varying the HNO{sub 3} concentration in the range of 7–8.5 M had little effect on the rate of conversion of Pu(IV) to Pu(VI). HNO{sub 3} oxidation of Pu(IV) to Pu(VI) in a pure solution has been reported previously. Based on simulated dissolution experiments, this study concluded that dissolving Pu metal at 95°C using a 6 to 10 M HNO{sub 3} solution 0.05–0.2 M KF and 0–2 g/L B could reduce the rate of oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. To demonstrate this flowsheet, two small-scale experiments were performed dissolving Pu metal up to 6.75 g/L. No Pu-containing residues were observed in the solutions after cooling. Using Pu metal dissolution rates measured during the experiments and a correlation developed by Holcomb, the time required to completely dissolve a batch of Pu metal in an H-Canyon dissolver using this flowsheet was estimated to require nearly 5 days (120 h). This value is reasonably consistent with an estimate based on the Batch 2 and 3 dissolution times in the 6.1D dissolver and Pu metal dissolution rates measured in this study and by Rudisill et al. Data from the present and previous studies show that the Pu metal dissolution rate decreases by a factor of approximately two when the temperature decreased from boiling (112 to 116°C) to 95°C. Therefore, the time required to dissolve a batch of Pu metal in an H-Canyon dissolver at 95°C would likely double (from 36 to 54 h) and require 72 to 108 h depending on the surface area of the Pu metal. Based on the experimental studies, a Pu metal dissolution flowsheet utilizing 6–10 M HNO{sub 3} containing 0.05–0.2 M KF (with 0–2 g/L B) at 95°C is recommended to reduce the oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. The time required to completely dissolve a batch of Pu metal will increase, however, by approximately a factor of two as compared to initial dissolutions at near boiling (assuming the KF concentration is maintained at nominally 0.1 M). By lowering the temperature to 95°C under otherwise the same operating parameters as previous dissolutions, the Pu(VI) concentration should not exceed 15% after a 120 h heating cycle. Increasing the HNO{sub 3} concentration and lowering Pu concentration are expected to further limit the amount of Pu(VI) formed.« less

Inside Story of Gas Processes within Stormwater Biofilters: Does Greenhouse Gas Production Tarnish the Benefits of Nitrogen Removal?

PubMed

Payne, Emily G I; Pham, Tracey; Cook, Perran L M; Deletic, Ana; Hatt, Belinda E; Fletcher, Tim D

2017-04-04

Stormwater biofilters are dynamic environments, supporting diverse processes that act to capture and transform incoming pollutants. However, beneficial water treatment processes can be accompanied by undesirable greenhouse gas production. This study investigated the potential for nitrous oxide (N 2 O) and methane (CH 4 ) generation in dissolved form at the base of laboratory-scale stormwater biofilter columns. The influence of plant presence, species, inflow frequency, and inclusion of a saturated zone and carbon source were studied. Free-draining biofilters remained aerobic with negligible greenhouse gas production during storm events. Designs with a saturated zone were oxygenated at their base by incoming stormwater before anaerobic conditions rapidly re-established, although extended dry periods allowed the reintroduction of oxygen by evapotranspiration. Production of CH 4 and N 2 O in the saturated zone varied significantly in response to plant presence, species, and wetting and drying. Concentrations of N 2 O typically peaked rapidly following stormwater inundation, associated with limited plant root systems and poorer nitrogen removal from biofilter effluent. Production of CH 4 also commenced quickly but continued throughout the anaerobic interevent period and lacked clear relationships with plant characteristics or nitrogen removal performance. Dissolved greenhouse gas concentrations were highly variable, but peak concentrations of N 2 O accounted for <1.5% of the incoming total nitrogen load. While further work is required to measure surface emissions, the potential for substantial release of N 2 O or CH 4 in biofilter effluent appears relatively low.

Effects of crystallization and bubble nucleation on the elastic properties of magmas

NASA Astrophysics Data System (ADS)

Tripoli, B. A.; Ulmer, P.; Eric, R.; Cordonnier, B.; Burg, J.

2012-12-01

Seismic tomography of potentially hazardous volcanoes is a prime tool to assess the physical state of magma reservoirs. Processes occurring in the conduit or in the chamber, such as crystallization and bubble exsolution, control the magma rheology, hence the style of volcanic eruption. Elastic parameters of vapor-saturated, partially molten systems are thus providing fundamental information for the identification of such reservoirs under active and seemingly dormant volcanoes. This knowledge will potentially serve to assess their risk. We present preliminary data on compression and shear wave propagation velocities of a chemically simplified melt analogous to andesite and trachyte, in the system CaO-Na2O-Al2O3-SiO2-H2O-CO2. These ultrasonic velocities are measured simultaneously in a Paterson-type internally-heated gas pressure apparatus at confining pressures up to 300 MPa and temperatures up to 1000°C. Using the pulse transmission technique, the experiments are performed at frequencies ranging from 0.1 to 3 MHz. Variations in the elastic parameters induced by the presence of bubbles or dissolved water in glassy samples are discussed for various pressures and temperatures. As the investigated melt undergoes plagioclase crystallization, a thermal plateau is maintained over specific time duration in order to measure the changes in seismic properties of in-situ crystallizing magmas. This maintained temperature varies between 800° and 1000°C depending on the amount of dissolved water in the system.

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectramore » of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.« less

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

NASA Astrophysics Data System (ADS)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57 · 10-10 vs. 1.28 · 10-13 mol m-2 s-1 [log R = -9.81 and -12.89] and 5.79 · 10-10 vs. 3.71 · 10-13 mol m-2 s-1 [log R = -9.24 and -12.43] for K- and Na-compreignacite, respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for U mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. This study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE PAGES

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; ...

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

PubMed

Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

2013-05-14

A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

Monitoring of urban and rural basins: water quality of Mourão basin.

PubMed

Passig, F H; Lima, S B; Carvalho, K Q; Halmeman, M C R; Souza, P C; Gusmão, L K

2015-12-01

The Mourão River basin is located on the central western region of the Paraná State - Brazil, between coordinates 23º 44' - 24º 25 South latitude and 52º 12' - 52º 30' West longitude, between 270 and 820 m above sea level, and 1,648.21 km2 drainage area. Water quality was evaluated by monitoring physical, chemical and microbiological parameters. Monthly samplings were performed for a year at five sites in the basin for analysis of: pH, temperature, dissolved oxygen, biochemical oxygen demand, total nitrogen, ammoniacal nitrogen, nitrite, nitrate, total phosphorus, turbidity, total solids, volatile solids and fecal coliforms. The results of the evaluated parameters showed higher values than the limits set by CONAMA Resolution 357 from 2005 for Class 2 in some samples. The Water Quality Index (WQI) indicated that 72% of samples had average quality and 28% had good quality for the Mourão River basin. Higher values of WQI were observed after rainfall period with median of 75 compared to the dry period with median of 62. The source of the Mourão River is contaminated with fecal coliforms, evidencing the real need to treat sewage in rural areas.

Determination of the δ15N and δ18O of nitrate in solids; RSIL lab code 2897

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping; Revesz, Kinga; Casciotti, Karen; Hannon, Janet E.

2007-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2897 is to determine the δ15N and δ18O of nitrate (NO3-) in solids. The NO3- fraction of the nitrogen species is dissolved by water (called leaching) and can be analyzed by the bacterial method covered in RSIL lab code 2900. After leaching, the δ15N and δ18O of the dissolved NO3- is analyzed by conversion of the NO3- to nitrous oxide (N2O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of NO3- to N2O, which follows the pathway shown in equation 1: NO3- → NO2- → NO → 1/2 N2O (1) Because the bacteria Pseudomonas aureofaciens lack N2O reductive activity, the reaction stops at N2O, unlike the typical denitrification reaction that goes to N2. After several hours, the conversion is complete, and the N2O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO4)2), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N2O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge (m/z) of the N2O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N2O = 14N14N16O; m/z = 45 = N2O = 14N15N16O or 14N14N17O; m/z = 46 = N2O = 14N14N18O. The 17O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ15N values are reported.

JPRS Report, Science & Technology, Japan

DTIC Science & Technology

1988-03-03

formation of deoxi- dized products in composite-deoxidized steel ingots M-6 Production of particle-dispersed alloy M-7 Structure and...densities of the OH radicals and C03 2" in the glass as low as possible, while prevent- ing bubble formation . 3. Sound-Wave Floating Furnace The...001 3 March 1988 21 ADVANCED MATERIALS 50. 60 80 ~CaO (mol%) 90 100 unit : ppm nnount oF plitinud dissolved i 2g Dissolution

Monitoring induced denitrification in an artificial aquifer recharge system.

NASA Astrophysics Data System (ADS)

Grau-Martinez, Alba; Torrentó, Clara; Folch, Albert; Domènech, Cristina; Otero, Neus; Soler, Albert

2014-05-01

As demands on groundwater increase, artificial recharge is becoming a common method for enhancing groundwater supply. The Llobregat River is a strategic water supply resource to the Barcelona metropolitan area (Catalonia, NE Spain). Aquifer overexploitation has leaded to both a decrease of groundwater level and seawater intrusion, with the consequent deterioration of water quality. In the middle section of the aquifer, in Sant Vicenç del Horts, decantation and infiltration ponds recharged by water from the Llobregat River (highly affected from wastewater treatment plant effluents), were installed in 2007, in the framework of the ENSAT Life+ project. At the bottom of the infiltration pond, a vegetal compost layer was installed to promote the growth of bacteria, to induce denitrification and to create favourable conditions for contaminant biodegradation. This layer consists on a mixture of compost, aquifer material, clay and iron oxide. Understanding the fate of contaminants, such as nitrate, during artificial aquifer recharge is required to evaluate the impact of artificial recharge in groundwater quality. In order to distinguish the source of nitrate and to evaluate the capability of the organic reactive layer to induce denitrification, a multi-isotopic approach coupled with hydrogeochemical data was performed. Groundwater samples, as well as river samples, were sampled during artificial and natural recharge periods. The isotopic analysis included: δ15N and δ18O of dissolved nitrate, δ34S and δ18O of dissolved sulphate, δ13C of dissolved inorganic carbon, and δ2H and δ18O of water. Dissolved nitrate isotopic composition (δ15NNO3 from +9 to +21 o and δ18ONO3 from +3 to +16 ) demonstrated that heterotrophic denitrification induced by the reactive layer was taking place during the artificial recharge periods. An approximation to the extent of nitrate attenuation was calculated, showing a range between 95 and 99% or between 35 and 45%, by using the extreme literature ɛN values of -4o and -22o respectively (Aravena and Robertson, 1998; Pauwels et al., 2000). Ongoing denitrification batch experiments will allow us to determine the specific nitrogen and oxygen isotopic fractionation induced by the organic reactive layer, in order to estimate more precisely the extent of denitrification during artificial aquifer recharge. These results confirmed that the reactive layer induces denitrification in the recharge ponds area, proving the usefulness of an isotopic approach to characterize water quality improvement occurring during artificial aquifer recharge. References 1. Aravena, R., Robertson, W.D., 1998. Use of multiple isotope tracers to evaluate denitrification in ground water: Study of nitrate from a large-flux septic system plume. Ground Water, 36(6): 975-982. 2. Pauwels, H., J.C., Kloppmann, W., 2000. Denitrification and mixing in a schist aquifer: Influence on water chemistry and isotopes. Chemical Geology, 168(3-4): 307-324. Acknowledgment This study was supported by the projects CGL2011-29975-C04-01 from the Spanish Government, 2009SGR-00103 from the Catalan Government and ENPI/2011/280-008 from the European Commission. Please fill in your abstract text.

Aerobic sulfate reduction in microbial mats

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Des Marais, David J.

1991-01-01

Measurements of bacterial sulfate reduction and dissolved oxygen (O2) in hypersaline bacterial mats from Baja California, Mexico, revealed that sulfate reduction occurred consistently within the well-oxygenated photosynthetic zone of the mats. This evidence that dissimilatory sulfate reduction can occur in the presence of O2 challenges the conventional view that sulfate reduction is a strictly anaerobic process. At constant temperature, the rates of sulfate reduction in oxygenated mats during daytime were similar to rates in anoxic mats at night: thus, during a 24-hour cycle, variations in light and O2 have little effect on rates of sulfate reduction in these mats.

Formation of a hybrid-type proto-atmosphere on Mars accreting in the solar nebula

NASA Astrophysics Data System (ADS)

Saito, Hiroaki; Kuramoto, Kiyoshi

2018-03-01

Recent studies of the chronology of Martian meteorites suggest that the growth of Mars was almost complete within a few Myr after the birth of the Solar system. During such rapid accretion, proto-Mars likely gravitationally maintained both the solar nebula component and the impact degassing component, containing H2O vapour and reduced gas species, as a proto-atmosphere to be called a hybrid-type proto-atmosphere. Here we numerically analyse the mass and composition of the degassed component and the atmospheric thermal structure sustained by accretional heating. Our results predict that a growing Mars possibly acquired a massive and hot hybrid-type proto-atmosphere with surface pressure and temperature greater than several kbar and 2000 K, respectively, which is sufficient to produce a deep magma ocean. In such a high-temperature and high-pressure environment, a significant amount of H2O, CH4, CO, and H2 is expected to be partitioned into the planetary interior, although this would strongly depend on the dynamics of the magma ocean and mantle solidification. The dissolved H2O may explain the wet Martian mantle implied from basaltic Martian meteorites. Along with the remnant reduced atmosphere after the hydrodynamic atmospheric escape, dissolved reduced gas species may have maintained an earliest Martian surface environment that allowed prebiotic chemical evolution and liquid H2O activities.

A simple high-performance matrix-free biomass molten carbonate fuel cell without CO2 recirculation

PubMed Central

Lan, Rong; Tao, Shanwen

2016-01-01

In previous reports, flowing CO2 at the cathode is essential for either conventional molten carbonate fuel cells (MCFCs) based on molten carbonate/LiAlO2 electrolytes or matrix-free MCFCs. For the first time, we demonstrate a high-performance matrix-free MCFC without CO2 recirculation. At 800°C, power densities of 430 and 410 mW/cm2 are achieved when biomass—bamboo charcoal and wood, respectively–is used as fuel. At 600°C, a stable performance is observed during the measured 90 hours after the initial degradation. In this MCFC, CO2 is produced at the anode when carbon-containing fuels are used. The produced CO2 then dissolves and diffuses to the cathode to react with oxygen in open air, forming the required CO32− or CO42− ions for continuous operation. The dissolved O2− ions may also take part in the cell reactions. This provides a simple new fuel cell technology to directly convert carbon-containing fuels such as carbon and biomass into electricity with high efficiency. PMID:27540588

Differences in soil solution chemistry between soils amended with nanosized CuO or Cu reference materials: implications for nanotoxicity tests.

PubMed

McShane, Heather V A; Sunahara, Geoffrey I; Whalen, Joann K; Hendershot, William H

2014-07-15

Soil toxicity tests for metal oxide nanoparticles often include micrometer-sized oxide and metal salt treatments to distinguish between toxicity from nanometer-sized particles, non-nanometer-sized particles, and dissolved ions. Test result will be confounded if each chemical form has different effects on soil solution chemistry. We report on changes in soil solution chemistry over 56 days-the duration of some standard soil toxicity tests-in three soils amended with 500 mg/kg Cu as nanometer-sized CuO (nano), micrometer-sized CuO (micrometer), or Cu(NO3)2 (salt). In the CuO-amended soils, the log Cu2+ activity was initially low (minimum -9.48) and increased with time (maximum -5.20), whereas in the salt-amended soils it was initially high (maximum -4.80) and decreased with time (minimum -6.10). The Cu2+ activity in the nano-amended soils was higher than in the micrometer-amended soils for at least the first 11 days, and lower than in the salt-amended soils for at least 28 d. The pH, and dissolved Ca and Mg concentrations in the CuO-amended soils were similar, but the salt-amended soils had lower pH for at least 14 d, and higher Ca and Mg concentrations throughout the test. Soil pretreatments such as leaching and aging prior to toxicity tests are suggested.

The effects of total dissolved gas on chum salmon fry survival, growth, gas bubble disease, and seawater tolerance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geist, David R.; Linley, Timothy J.; Cullinan, Valerie I.

2013-02-01

Chum salmon Oncorhynchus keta alevin developing in gravel habitats downstream of Bonneville Dam on the Columbia River are exposed to elevated levels of total dissolved gas (TDG) when water is spilled at the dam to move migrating salmon smolts downstream to the Pacific Ocean. Current water quality criteria for the management of dissolved gas in dam tailwaters were developed primarily to protect salmonid smolts and are assumed to be protective of alevin if adequate depth compensation is provided. We studied whether chum salmon alevin exposed to six levels of dissolved gas ranging from 100% to 130% TDG at three developmentmore » periods between hatch and emergence (hereafter early, middle, and late stage) suffered differential mortality, growth, gas bubble disease, or seawater tolerance. Each life stage was exposed for 50 d (early stage), 29 d (middle stage), or 16 d (late stage) beginning at 13, 34, and 37 d post-hatch, respectively, through 50% emergence. The mortality for all stages from exposure to emergence was estimated to be 8% (95% confidence interval (CI) of 4% to 12%) when dissolved gas levels were between 100% and 117% TDG. Mortality significantly increased as dissolved gas levels rose above 117% TDG,; with the lethal concentration that produced 50% mortality (LC50 ) was estimated to be 128.7% TDG (95% CI of 127.2% to 130.2% TDG) in the early and middle stages. By contrast, there was no evidence that dissolved gas level significantly affected growth in any life stage except that the mean wet weight at emergence of early stage fish exposed to 130% TDG was significantly less than the modeled growth of unexposed fish. The proportion of fish afflicted with gas bubble disease increased with increasing gas concentrations and occurred most commonly in the nares and gastrointestinal tract. Early stage fish exhibited higher ratios of filament to lamellar gill chloride cells than late stage fish, and these ratios increased and decreased for early and late stage fish, respectively, as gas levels increased; however, there were no significant differences in mortality between life stages after 96 h in seawater. The study results suggest that current water quality guidelines for the management of dissolved gas appear to offer a conservative level of protection to chum salmon alevin incubating in gravel habitat downstream of Bonneville Dam.« less

Correlative Light-Electron Microscopy Shows RGD-Targeted ZnO Nanoparticles Dissolve in the Intracellular Environment of Triple Negative Breast Cancer Cells and Cause Apoptosis with Intratumor Heterogeneity.

PubMed

Othman, Basmah A; Greenwood, Christina; Abuelela, Ayman F; Bharath, Anil A; Chen, Shu; Theodorou, Ioannis; Douglas, Trevor; Uchida, Maskai; Ryan, Mary; Merzaban, Jasmeen S; Porter, Alexandra E

2016-06-01

ZnO nanoparticles (NPs) are reported to show a high degree of cancer cell selectivity with potential use in cancer imaging and therapy. Questions remain about the mode by which the ZnO NPs cause cell death, whether they exert an intra- or extracellular effect, and the resistance among different cancer cell types to ZnO NP exposure. The present study quantifies the variability between the cellular toxicity, dynamics of cellular uptake, and dissolution of bare and RGD (Arg-Gly-Asp)-targeted ZnO NPs by MDA-MB-231 cells. Compared to bare ZnO NPs, RGD-targeting of the ZnO NPs to integrin αvβ3 receptors expressed on MDA-MB-231 cells appears to increase the toxicity of the ZnO NPs to breast cancer cells at lower doses. Confocal microscopy of live MDA-MB-231 cells confirms uptake of both classes of ZnO NPs with a commensurate rise in intracellular Zn(2+) concentration prior to cell death. The response of the cells within the population to intracellular Zn(2+) is highly heterogeneous. In addition, the results emphasize the utility of dynamic and quantitative imaging in understanding cell uptake and processing of targeted therapeutic ZnO NPs at the cellular level by heterogeneous cancer cell populations, which can be crucial for the development of optimized treatment strategies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mimicking floodplain reconnection and disconnection using 15N mesocosm incubations

NASA Astrophysics Data System (ADS)

Welti, N.; Bondar-Kunze, E.; Mair, M.; Bonin, P.; Wanek, W.; Pinay, G.; Hein, T.

2012-11-01

Floodplain restoration changes the nitrate delivery pattern and dissolved organic matter pool in backwaters, though the effects these changes have are not yet well known. We performed two mesocosm experiments on floodplain sediments to quantify the nitrate metabolism in two types of floodplains. Rates of denitrification, dissimilatory nitrate reduction to ammonium (DNRA) and anammox were measured using 15N-NO3 tracer additions in mesocosms of undisturbed floodplain sediments originating from (1) restored and (2) disconnected sites in the Alluvial Zone National Park on the Danube River downstream of Vienna, Austria. DNRA rates were an order of magnitude lower than denitrification and neither rate was affected by changes in nitrate delivery pattern or organic matter quality. Anammox was not detected at any of the sites. Denitrification was out-competed by assimilation, which was estimated to use up to 70% of the available nitrate. Overall, denitrification was higher in the restored sites, with mean rates of 5.7 ± 2.8 mmol N m-2 h-1 compared to the disconnected site (0.6 ± 0.5 mmol N m-2 h-1). In addition, ratios of N2O : N2 were lower in the restored site indicating a more complete denitrification. Nitrate addition had neither an effect on denitrification, nor on the N2O : N2 ratio. However, DOM (dissolved organic matter) quality significantly changed the N2O : N2 ratio in both sites. Addition of riverine-derived organic matter lowered the N2O : N2 ratio in the disconnected site, whereas addition of floodplain-derived organic matter increased the N2O : N2 ratio in the restored site. These results demonstrate that increasing floodplains hydrological connection to the main river channel increases nitrogen retention and decreases nitrous oxide emissions.

Experimental constraints on the damp peridotite solidus and oceanic mantle potential temperature

NASA Astrophysics Data System (ADS)

Sarafian, Emily; Gaetani, Glenn A.; Hauri, Erik H.; Sarafian, Adam R.

2017-03-01

Decompression of hot mantle rock upwelling beneath oceanic spreading centers causes it to exceed the melting point (solidus), producing magmas that ascend to form basaltic crust ~6 to 7 kilometers thick. The oceanic upper mantle contains ~50 to 200 micrograms per gram of water (H2O) dissolved in nominally anhydrous minerals, which—relative to its low concentration—has a disproportionate effect on the solidus that has not been quantified experimentally. Here, we present results from an experimental determination of the peridotite solidus containing known amounts of dissolved hydrogen. Our data reveal that the H2O-undersaturated peridotite solidus is hotter than previously thought. Reconciling geophysical observations of the melting regime beneath the East Pacific Rise with our experimental results requires that existing estimates for the oceanic upper mantle potential temperature be adjusted upward by about 60°C.

Effect of chemical composition of man-made vitreous fibers on the rate of dissolution in vitro at different pHs.

PubMed

Christensen, V R; Jensen, S L; Guldberg, M; Kamstrup, O

1994-10-01

Measurements of rates of dissolution of typical insulation wool fibers (glasswool and basalt based stonewool) and an experimental fiber were made using a flow-through equipment. The liquids used were a modified Gamble's solution, adjusted to pH 4.8 and 7.7 +/- 0.2, respectively. The dissolution of SiO2 and CaO was determined over periods of up to three months. The rate of dissolution of stonewool fibers was lower than that of glasswool fibers at pH 7.7, whereas the opposite was true at pH 4.8. The stonewool fibers dissolve congruently, but glasswool fibers tend to dissolve with leaching. The rates of dissolution of fibers of different compositions, including insulation wool (glasswool, basalt-based stonewool, slagwool) and experimental fibers were screened using a stationary set-up. Both the chemical composition and pH influenced the rates of dissolution. At pH 7.7 alumina was a determining component and at pH 4.8 the content of SiO2 and CaO was determinant. One experimental fiber with a high content of alumina was an exception having a fairly high rate of dissolution both at pH 4.8 and 7.7.

Effect of chemical composition of man-made vitreous fibers on the rate of dissolution in vitro at different pHs.

PubMed Central

Christensen, V R; Jensen, S L; Guldberg, M; Kamstrup, O

1994-01-01

Measurements of rates of dissolution of typical insulation wool fibers (glasswool and basalt based stonewool) and an experimental fiber were made using a flow-through equipment. The liquids used were a modified Gamble's solution, adjusted to pH 4.8 and 7.7 +/- 0.2, respectively. The dissolution of SiO2 and CaO was determined over periods of up to three months. The rate of dissolution of stonewool fibers was lower than that of glasswool fibers at pH 7.7, whereas the opposite was true at pH 4.8. The stonewool fibers dissolve congruently, but glasswool fibers tend to dissolve with leaching. The rates of dissolution of fibers of different compositions, including insulation wool (glasswool, basalt-based stonewool, slagwool) and experimental fibers were screened using a stationary set-up. Both the chemical composition and pH influenced the rates of dissolution. At pH 7.7 alumina was a determining component and at pH 4.8 the content of SiO2 and CaO was determinant. One experimental fiber with a high content of alumina was an exception having a fairly high rate of dissolution both at pH 4.8 and 7.7. PMID:7882962

Electrochemical Deposition of High Purity Silicon from Molten Salts

NASA Astrophysics Data System (ADS)

Haarberg, Geir Martin

Several approaches were tried in order to develop an electrochemical route for producing high purity silicon from molten salts. SiO2, K2SiF6 and metallurgical silicon were used as the source of silicon. Molten electrolytes based on chloride (CaCl2-NaCl) and fluoride (LiF-KF) at temperatures from 550 - 900 oC were used. Transient electrochemical techniques were used to study the electrochemical behaviour of dissolved silicon species. Electrolysis experiments were carried out to deposit silicon.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehta, Vrajesh; Maillot, Fabien; Wang, Zheming

Uranyl phosphate solids are often found with uranium ores, and their low solubility makes them promising target phases for in situ remediation of uranium-contaminated subsurface environments. The products and solubility of uranium(VI) precipitated with phosphate can be affected by the pH, dissolved inorganic carbon (DIC) concentration, and co-solute composition (e.g. Na+/Ca2+) of the groundwater. Batch experiments were performed to study the effect of these parameters on the products and extent of uranium precipitation induced by phosphate addition. In the absence of co-solute cations, chernikovite [H3O(UO2)(PO4)•3H2O] precipitated despite uranyl orthophosphate [(UO2)3(PO4)2•4H2O] being thermodynamically more favorable under certain conditions. As determined usingmore » X-ray diffraction, electron microscopy, and laser induced fluorescence spectroscopy, the presence of Na+ or Ca2+ as a co-solute led to the precipitation of sodium autunite ([Na2(UO2)2(PO4)2] and autunite [Ca(UO2)2(PO4)2]), which are structurally similar to chernikovite. In the presence of sodium, the dissolved U(VI) concentrations were generally in agreement with equilibrium predictions of sodium autunite solubility. However, in the calcium-containing systems, the observed concentrations were below the predicted solubility of autunite, suggesting the possibility of uranium adsorption to or incorporation in a calcium phosphate precipitate in addition to the precipitation of autunite.« less

Scavenging of ammonia by raindrops in Saturn's great storm clouds

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Baines, Kevin

2016-10-01

Observations of the great Saturn storms of 2010-2011 by Cassini instruments showed a very large depletion in atmospheric ammonia. While dynamics will play a role, the very high solubility of ammonia in water may be another important contributor to ammonia depletion in storms. Ammonia exists in Earth's atmosphere and rainstorms dissolve ammonia to a great degree, leaving almost no NH3 in the atmosphere. Studies by Elperin et al (2011, 2013) show that scavenging of ammonia is greatest as a rainstorm starts and lessens as raindrops fall, tapering off to almost zero by the time the rain reaches the ground (Elperin et al 2009). Ammonia is reaching saturation as it dissolves in the aqueous solution. As concentration increases, NH3 is then converted to aqueous species (NH3)x.(H2O)y (Max and Chapados 2013).Ammonia has the highest solubility in water compared to all other gases in the Saturn atmosphere. The Henry's Law constant for NH3 in water is 60 M/atm at 25 C. For H2S, it is 0.001 M/atm. In Saturn storms, it is "raining UP": As water-laden storm clouds convectively rise, ammonia gas will be scavenged and go into solution to a great degree, whilst all the other gases remain mostly in the gas phase. Aqueous ammonia acts as an antifreeze: if ammonia is dissolved in water cloud droplets to the limit of its solubility, as water droplets rise, they can stay liquid (and continue to scavenge NH3) to well below their normal freezing point of 0 Celsius (273 K). The freezing point for a 30 wt % water-ammonia solution is ~189 K. The pressure level where T = 189 K is at 2.8 bars. The normal freezing point of water occurs at the 9 bar pressure level in Saturn's atmosphere. 2.8 bars occurs at the -51 km altitude (below the 1 bar level). 9 bars is at the -130 km level: a difference of 79 km. A water droplet containing 30 wt% NH3 can move upwards from 9 bars to 2.8 bars (79 km) and still remain liquid, only freezing above that altitude. Calculations by the E-AIM model show that ammonia becomes the dominant species as the water droplets rise and cool. Ammonia will be effectively depleted as it is scavenged into water droplets in Saturn's storms.

Omeprazole increases the efficacy of a soluble epoxide hydrolase inhibitor in a PGE2 induced pain model

PubMed Central

Goswami, Sumanta Kumar; Inceoglu, Bora; Yang, Jun; Wan, Debin; Kodani, Sean D.; da Silva, Carlos Antonio Trindade; Morisseau, Christophe; Hammock, Bruce D.

2015-01-01

Epoxyeicosatrienoic acids (EETs) are potent endogenous analgesic metabolites produced from arachidonic acid by cytochrome P450s (P450s). Metabolism of EETs by soluble epoxide hydrolase (sEH) reduces their activity, while their stabilization by sEH inhibition decreases both inflammatory and neuropathic pain. Here, we tested the complementary hypothesis that increasing the level of EETs through induction of P450s by omeprazole (OME), can influence pain related signaling by itself, and potentiate the anti-hyperalgesic effect of sEH inhibitor. Rats were treated with OME (100 mg/kg/day, p.o., 7 days), sEH inhibitor TPPU (3 mg/kg/day, p.o.) and OME (100 mg/kg/day, p.o., 7 days) + TPPU (3 mg/kg/day, p.o., last 3 days of OME dose) dissolved in vehicle PEG400, and their effect on hyperalgesia (increased sensitivity to pain) induced by PGE2 was monitored. While OME treatment by itself exhibited variable effects on PGE2 induced hyperalgesia, it strongly potentiated the effect of TPPU in the same assay. The significant decrease in pain with OME + TPPU treatment correlated with the increased levels of EETs in plasma and increased activities of P450 1A1 and P450 1A2 in liver microsomes. The results show that reducing catabolism of EETs with a sEH inhibitor yielded a stronger analgesic effect than increasing generation of EETs by OME, and combination of both yielded the strongest pain reducing effect under the condition of this study. PMID:26522832

Dissolved and colloidal copper in the tropical South Pacific

NASA Astrophysics Data System (ADS)

Roshan, Saeed; Wu, Jingfeng

2018-07-01

Copper (Cu) as a bioactive trace metal in the ocean has widely been studied in the context of chemical speciation. However, this trace metal is extremely understudied in the context of physical speciation (i.e., size- or molecular weight-partitioning), which may help in characterizing dissolved Cu species. In this study, we determine total dissolved Cu (<0.2 μm) distribution and its physical speciation along the US GEOTRACES 2013 cruise, a 4300-km east-west transect in the tropical South Pacific. The distribution of dissolved Cu is rather uniform horizontally and exhibits a linear increase with depth from surface to 2500-3000 m, below which it varies less significantly both vertically and horizontally. Dissolved Cu shows a strong correlation with silicate (SiO44-) in the upper 1500 m, which is in agreement with previous studies in other regions. This correlation is weaker but with higher slope at depths below 1500 m, which supports the sedimentary source hypothesis. Although hydrothermal activity at the East Pacific Rise (EPR) does not show a readily evident impact on the dissolved Cu distribution, high-quality data at 2300-2800 m allow for diagnosing a subtle westward decrease in the background-subtracted dissolved Cu component. This component of dissolved Cu poorly correlates with mantle-derived 3He (R2 = 0.41), indicating a possible hydrothermal source for dissolved Cu, in contrast to previous studies. For the first time in a major basin, we also determined the physical speciation of dissolved Cu, which shows that Cu species lighter than 10 kDa (Da = 1 g mol-1) dominate the pool of dissolved Cu (<0.2 μm) below 1000 m with a contribution of 61 ± 6% (fraction of total dissolved). 39 ± 6% of dissolved Cu at depths below 1000 m, thus, occurs in the pool of colloidal matter (10 kDa-0.2 μm). Moreover, using a suite of molecular weight cutoffs indicate that Cu species are distributed between two distinct molecular weight classes: the lighter than 5 kDa and heavier than 300 kDa classes, which form 53 ± 6% and 37 ± 7% of dissolved Cu at 2200-2800 m, respectively. The Cu species with molecular weight between 5 kDa and 300 kDa contribute only to 10 ± 12% of the pool at 2200-2800 m. These results offer new insights into structure, reactivity and bioavailability of oceanic Cu compounds. As an organic-dominating metal, Cu physical speciation may also shed light on size-reactivity spectrum of dissolved organic matter (DOM) in the deep ocean.

The isotopic imprint of fixed nitrogen elimination in the redox transition zone of Lake Lugano, Switzerland

NASA Astrophysics Data System (ADS)

Wenk, Christine; Blees, Jan; Niemann, Helge; Zopfi, Jakob; Schubert, Carsten J.; Veronesi, Mauro; Simona, Marco; Koba, Keisuke; Lehmann, Moritz F.

2010-05-01

Nitrogen (N) loading in lakes from natural and anthropogenic sources is partially mitigated by microbially mediated processes that take place in redox transition zones (RTZ) in the water column and in sediments. However, the role of lakes as a terrestrial sink of fixed N is still poorly constrained. Furthermore, modes of suboxic N2 (and N2O) production other than canonical denitrification (e.g. anaerobic ammonium oxidation, or anammox) have barely been investigated in lakes, and the microbial communities involved in N transformations in lacustrine RTZ are mostly unknown. The isotopic composition of dissolved nitrogen species can serve as a reliable indicator of N-transformations in aquatic environments. However, the successful application of N (and O) isotope measurements in natural systems requires a solid understanding of the various N-transformation-specific isotope effects. The deep, south-alpine Lake Lugano, with a permanent chemocline in its North Basin, is an excellent model system for a biogeochemically dynamic lake, in which to study N isotope ratio variations associated with fixed N elimination and regeneration processes. We present the first comprehensive dataset of hydrochemical parameters (including N2/Ar and dissolved N2O concentrations), natural abundance stable isotope ratios of dissolved inorganic nitrogen (DIN) compounds (nitrate, nitrite, ammonium, dinitrogen, nitrous oxide), and the isotopomeric composition of water column N2O for the North Basin of Lake Lugano. Isotopic data will be integrated with molecular microbiological phylogenetic analyses and results from incubation experiments with 15N-labeled N-substrates. Strong gradients in DIN concentrations, as well as in the N and O isotope (and isotopomeric) compositions of nitrate and N2O towards the redox-transition zone indicate nitrate reduction, occurring with a high community N-fractionation. The site preference of N2O isotopomers above the chemocline indicates that the N2O is not only produced by denitrification. Furthermore, the ratio of nitrate N versus O isotope enrichment is 0.6, significantly lower than the ratio expected for sole water column denitrification. Ammonium concentrations in the hypolimnion constantly decrease to 0µM at about 20m below the oxycline, suggesting that anammox, the anaerobic oxidation of ammonium, takes place below the RTZ. First results from 16S rDNA analysis confirmed the presence of anammox bacteria (Candidatus ‘Kuenenia') in the water column. Further phylogenetic and isotope-labeling experiments will provide more information on the spatial and seasonal distribution of anammox bacteria in the water column, on the quantitative partitioning between the candidate N elimination processes, and thus likely on the N isotope fractionation of single N transformation pathways.

Experimental investigation and modelling approach of the impact of urban wastewater on a tropical river; a case study of the Nhue River, Hanoi, Viet Nam

NASA Astrophysics Data System (ADS)

Duc, Trinh Anh; Vachaud, Georges; Bonnet, Marie Paule; Prieur, Nicolas; Loi, Vu Duc; Anh, Le Lan

2007-02-01

SummaryAnalyses of water quality and flow regime in combination with laboratory studies and ecological modelling were used to assess the water quality impact of pollution from to To Lich River that drains through Hanoi City and greatly contaminates the Nhue River. With an average discharge of 26.2 m 3/s, the Nhue River receives about 5.8 m 3/s of untreated domestic water from the city's main open-air-sewer - the To Lich River. The studies during 2002-2003 showed high concentrations of BOD (70 mg O 2/l), DOC (15 mg C/l), coliform (2.4e 6 MNP/100 ml), total phosphorus (3.5 mg P/l), and total nitrogen (31.6 mg N/l) in the To Lich, while DO level was less than 1 mg O 2/l. Such high loads of untreated wastewater impacted water quality in the Nhue River where DO decreased at times to as low as 1 mg O 2/l. The accumulation of particulate organic matter and micro-organisms in the sediments of the Nhue represented substantial sources of nutrients and sinks for DO. They are also considerable production of dissolved carbon dioxide at concentrations up to two orders of magnitude higher than pressure. Such pressures ( EpCO 2) are expected in polluted environments, but the results presented here are new for Vietnam and much of developing countries. A number of factors linked to field monitoring and laboratory measurements clearly indicate the importance of autotrophic over heterotrophic biological processes and sediments. An ecological model for management purposes has been developed that reliably estimates of the pollutant loads. An opportunity was taken to examine the changing impacts and processes when the To Lich was diverted from the Nhue. The monitoring and modelling of this opportunity showed low dissolved oxygen levels even if the impact from the To Lich was lessened. Alternatives are proposed to alleviate problems of water quality in the Nhue. It is concluded that the treatment of the To Lich River's water is highly recommended; otherwise a reduction to one third of current wastewater discharge is needed to bring water quality back to the environmental standard.

Dissolution flowsheet for high flux isotope reactor fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foster, T.

2016-09-27

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3O 8) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2. The HFIR fuel cores will be dissolved and the recovered U will be down-blendedmore » into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H 2) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H 2 and other permanent gases in the dissolution offgas allowing the development of H 2 generation rate profiles. The H 2 generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the calculated lower flammability limit (LFL) for H 2 at a given Hg concentration.« less

Comparative evaluation of human pulp tissue dissolution by different concentrations of chlorine dioxide, calcium hypochlorite and sodium hypochlorite: An in vitro study

PubMed Central

Taneja, Sonali; Mishra, Neha; Malik, Shubhra

2014-01-01

Introduction: Irrigation plays an indispensable role in removal of tissue remnants and debris from the complicated root canal system. This study compared the human pulp tissue dissolution by different concentrations of chlorine dioxide, calcium hypochlorite and sodium hypochlorite. Materials and Methods: Pulp tissue was standardized to a weight of 9 mg for each sample. In all,60 samples obtained were divided into 6 groups according to the irrigating solution used- 2.5% sodium hypochlorite (NaOCl), 5.25% NaOCl, 5% calcium hypochlorite (Ca(OCl)2), 10% Ca(OCl)2, 5%chlorine dioxide (ClO2) and 13% ClO2. Pulp tissue was placed in each test tube carrying irrigants of measured volume (5ml) according to their specified subgroup time interval: 30 minutes (Subgroup A) and 60 minutes (Subgroup B). The solution from each sample test tube was filtered and was left for drying overnight. The residual weight was calculated by filtration method. Results: Mean tissue dissolution increases with increase in time period. Results showed 5.25% NaOCl to be most effective at both time intervals followed by 2.5% NaOCl at 60 minutes, 10%Ca(OCl)2 and 13% ClO2 at 60 minutes. Least amount of tissue dissolving ability was demonstrated by 5% Ca(OCl)2 and 5% ClO2 at 30 minutes. Distilled water showed no pulp tissue dissolution. Conclusion: Withinthe limitations of the study, NaOCl most efficiently dissolved the pulp tissue at both concentrations and at both time intervals. Mean tissue dissolution by Ca(OCl)2 and ClO2 gradually increased with time and with their increase in concentration. PMID:25506141

Brain tissue oxygen tension is more indicative of oxygen diffusion than oxygen delivery and metabolism in patients with traumatic brain injury.

PubMed

Rosenthal, Guy; Hemphill, J Claude; Sorani, Marco; Martin, Christine; Morabito, Diane; Obrist, Walter D; Manley, Geoffrey T

2008-06-01

Despite the growing clinical use of brain tissue oxygen monitoring, the specific determinants of low brain tissue oxygen tension (P(bt)O2) following severe traumatic brain injury (TBI) remain poorly defined. The objective of this study was to evaluate whether P(bt)O2 more closely reflects variables related to cerebral oxygen diffusion or reflects cerebral oxygen delivery and metabolism. Prospective observational study. Level I trauma center. Fourteen TBI patients with advanced neuromonitoring underwent an oxygen challenge (increase in FiO2 to 1.0) to assess tissue oxygen reactivity, pressure challenge (increase in mean arterial pressure) to assess autoregulation, and CO2 challenge (hyperventilation) to assess cerebral vasoreactivity. None. P(bt)O2 was measured directly with a parenchymal probe in the least-injured hemisphere. Local cerebral blood flow (CBF) was measured with a parenchymal thermal diffusion probe. Cerebral venous blood gases were drawn from a jugular bulb venous catheter. We performed 119 measurements of PaO2, arterial oxygen content (CaO2), jugular bulb venous oxygen tension (PVO2), venous oxygen content (CVO2), arteriovenous oxygen content difference (AVDO2), and local cerebral metabolic rate of oxygen (locCMRO2). In multivariable analysis adjusting for various variables of cerebral oxygen delivery and metabolism, the only statistically significant relationship was that between P(bt)O2 and the product of CBF and cerebral arteriovenous oxygen tension difference (AVTO2), suggesting a strong association between brain tissue oxygen tension and diffusion of dissolved plasma oxygen across the blood-brain barrier. Measurements of P(bt)O2 represent the product of CBF and the cerebral AVTO2 rather than a direct measurement of total oxygen delivery or cerebral oxygen metabolism. This improved understanding of the cerebral physiology of P(bt)O2 should enhance the clinical utility of brain tissue oxygen monitoring in patients with TBI.

TRIS buffer in simulated body fluid distorts the assessment of glass-ceramic scaffold bioactivity.

PubMed

Rohanová, Dana; Boccaccini, Aldo Roberto; Yunos, Darmawati Mohamad; Horkavcová, Diana; Březovská, Iva; Helebrant, Aleš

2011-06-01

The paper deals with the characterisation of the bioactive phenomena of glass-ceramic scaffold derived from Bioglass® (containing 77 wt.% of crystalline phases Na(2)O·2CaO·3SiO(2) and CaO·SiO(2) and 23 wt.% of residual glass phase) using simulated body fluid (SBF) buffered with tris-(hydroxymethyl) aminomethane (TRIS). A significant effect of the TRIS buffer on glass-ceramic scaffold dissolution in SBF was detected. To better understand the influence of the buffer, the glass-ceramic scaffold was exposed to a series of in vitro tests using different media as follows: (i) a fresh liquid flow of SBF containing tris (hydroxymethyl) aminomethane; (ii) SBF solution without TRIS buffer; (iii) TRIS buffer alone; and (iv) demineralised water. The in vitro tests were provided under static and dynamic arrangements. SBF buffered with TRIS dissolved both the crystalline and residual glass phases of the scaffold and a crystalline form of hydroxyapatite (HAp) developed on the scaffold surface. In contrast, when TRIS buffer was not present in the solutions only the residual glassy phase dissolved and an amorphous calcium phosphate (Ca-P) phase formed on the scaffold surface. It was confirmed that the TRIS buffer primarily dissolved the crystalline phase of the glass-ceramic, doubled the dissolving rate of the scaffold and moreover supported the formation of crystalline HAp. This significant effect of the buffer TRIS on bioactive glass-ceramic scaffold degradation in SBF has not been demonstrated previously and should be considered when analysing the results of SBF immersion bioactivity tests of such systems. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A review of the contrasting behavior of two magmatic volatiles: Chlorine and carbon dioxide

USGS Publications Warehouse

Lowenstern, J. B.

2000-01-01

Chlorine (Cl) and carbon dioxide (CO2) are common magmatic volatiles with contrasting behaviors. CO2 solubility increases with pressure whereas Cl solubility shows relatively little pressure or temperature effect. CO2 speciation changes with silicate melt composition, dissolving as carbonate in basaltic magmas and molecular CO2 in more silicic compositions. In H2O-bearing systems, the strongly non-ideal behavior of alkali chlorides causes unmixing of the volatile phase to form a H2O-rich vapor and a hydrosaline phase with important implications for the maximum concentration of Cl in magmas. Addition of CO2 to magma hastens immiscibility at crustal pressures (<500 MPa), inducing the formation of CO2-rich vapors and Cl-rich hydrosaline melts. (C) 2000 Elsevier Science B.V. All rights reserved.Chlorine (Cl) and carbon dioxide (CO2) are common magmatic volatiles with contrasting behaviors. CO2 solubility increases with pressure whereas Cl solubility shows relatively little pressure or temperature effect. CO2 speciation changes with silicate melt composition, dissolving as carbonate in basaltic magmas and molecular CO2 in more silicic compositions. In H2O-bearing systems, the strongly non-ideal behavior of alkali chlorides causes unmixing of the volatile phase to form a H2O-rich vapor and a hydrosaline phase with important implications for the maximum concentration of Cl in magmas. Addition of CO2 to magma hastens immiscibility at crustal pressures (<500 MPa), inducing the formation of CO2-rich vapors and Cl-rich hydrosaline melts.

Effects of Low-Molecular-Weight Organic Acids on the Dissolution of Hydroxyapatite Nanoparticles in Batch and Column Experiments: A Perspective from Phosphate Oxygen Isotope Fractionation

NASA Astrophysics Data System (ADS)

Wang, D.; Jaisi, D. P.; Jin, Y.

2015-12-01

Hydroxyapatite nanoparticles (HANPs) are increasingly being advocated as an efficient and environment-friendly "green" phosphorus nanofertilizer attributed to their nanoscale dimension, large reactive surface area, and low leaching potential. However, knowledge of how naturally occurring low-molecular-weight organic acids (LMWOAs) that are secreted by plant roots mediate the dissolution of HANPs (releasing PO43- ion for plant growth) is nonexistent. Here three most commonly encountered LMWOAs (acetic acid, oxalic acid, and citric acid) at environmentally relevant concentration (1 mM) were evaluated for their effects on HANPs' dissolution in static batch and dynamic column systems. Particularly, phosphate oxygen isotope fractionation of HANPs during dissolution was examined to disentangle mechanisms controlling the evolution of O-isotopic composition of dissolved PO43- ion. Our results reveal that in batch experiments the dissolution of HANPs was fast but the overall dissolution efficiency of HANPs was limited (≤30%). In contrast, ~100% HANPs were dissolved in columns where LMWOAs were continuously injected. The limited dissolution of HANPs in static batch systems was due primarily to pH buffer effect (pH increased sharply when LMWOA was added in HANPs suspension), whereas in dynamic column systems the HANPs were continuously dissolved by low pH LMWOAs and leached away. Regardless of LMWOA type and experimental system, the isotopically light phosphate (P16O4) was preferentially released during dissolution and the O-isotopic composition of dissolved PO43- ion increased gradually with increasing dissolution due to equilibrium isotope effect between dissolved PO43- ion and HANPs. However, the overall magnitude of O-isotopic fractionation of dissolved PO43- ion was less in batch than in column systems, due to less mass transfer between dissolved PO43- ions and HANPs in batch relative to column experiments. Our findings provide new insights into bioavailability, transformation, and evolution of O-isotopic signatures of phosphate-based nanoparticles in agricultural soils particularly in the rhizosphere where such LMWOAs are ubiquitous.

Dissolved organic matter reduces CuO nanoparticle toxicity to duckweed in simulated natural systems.

PubMed

Rippner, Devin A; Green, Peter G; Young, Thomas M; Parikh, Sanjai J

2018-03-01

With increasing demand for recycled wastewater for irrigation purposes, there is a need to evaluate the potential for manufactured nanomaterials in waste water to impact crop production and agroecosystems. Copper oxide nanoparticles (CuO NPs) have previously been shown to negatively impact the growth of duckweed (Landoltia punctata) a model aquatic plant consumed by water fowl and widely found in agricultural runoff ditches in temperate climates. However, prior studies involving CuO NP toxicity to duckweed have focused on systems without the presence of dissolved organic matter (DOM). In the current study, duckweed growth inhibition was shown to be a function of aqueous Cu 2+ concentration. Growth inhibition was greatest from aqueous CuCl 2 and, for particles, increased with decreasing CuO particle size. The dissolution of CuO NPs in ½ Hoagland's solution was measured to increase with decreasing particle size and in the presence of Suwannee river humic and fulvic acids (HA; FA). However, the current results suggest that HA, and to a lesser extent, FA, decrease the toxicity of both CuO NPs and free ionized Cu to duckweed, likely by inhibiting Cu availability through Cu-DOM complex formation. Such results are consistent with changes to Cu speciation as predicted by speciation modeling software and suggest that DOM changes Cu speciation and therefore toxicity in natural systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

Varanasi, Lathika; Coscarelli, Erica; Khaksari, Maryam; Mazzoleni, Lynn R; Minakata, Daisuke

2018-05-15

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/H 2 O 2 ), 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/H 2 O 2 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 SO 4 •- are the predominant pathways in the UV/persulfate system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Migration of Ag- and TiO2-(Nano)particles from textiles into artificial sweat under physical stress: experiments and exposure modeling.

PubMed

von Goetz, N; Lorenz, C; Windler, L; Nowack, B; Heuberger, M; Hungerbühler, K

2013-09-03

Engineered nanoparticles (ENP) are increasingly used to functionalize textiles taking advantage, e.g., of the antimicrobial activity of silver (Ag)-ENP or the UV-absorption of titania (TiO2)-ENP. Mobilization and migration of ENPs from the textile into human sweat can result in dermal exposure to these nanoobjects and their aggregates and agglomerates (NOAA). In this study we assessed exposure to NOAA migrating from commercially available textiles to artificial sweat by an experimental setup that simulates wear-and-tear during physical activity. By combining physical stress with incubation in alkaline and acidic artificial sweat solutions we experimentally realized a worst case scenario for wearing functionalized textiles during sports activities. This experimental approach is not limited to NOAA, but can be used for any other textile additive. Out of four investigated textiles, one T-shirt and one pair of trousers with claimed antimicrobial properties were found to release Ag <450 nm in detectable amounts (23-74 μg/g/L). Textiles containing TiO2 for UV protection did not release significant amounts of TiO2 <450 nm, but the antimicrobial T-shirt released both TiO2 and Ag <450 nm. The silver was present in dissolved and particulate form, whereas TiO2 was mainly found as particulate. On the basis of our experimental results we calculated external dermal exposure to Ag and TiO2 for male and female adults per use. For silver, maximal amounts of 17.1 and 8.2 μg/kg body weight were calculated for total and particulate Ag <450 nm, respectively. For TiO2, the exposure levels amount to maximal 11.6 μg/kg body weight for total (mainly particulate) TiO2. In comparison with other human exposure pathways, dermal exposure to NOAA from textiles can be considered comparably minor for TiO2-NOAA, but not for Ag-NOAA.

Evaluation of Titanium Dioxide as a Binding Phase for the Passive Sampling of Glyphosate and Aminomethyl Phosphonic Acid in an Aquatic Environment.

PubMed

Fauvelle, Vincent; Nhu-Trang, Tran-Thi; Feret, Thibaut; Madarassou, Karine; Randon, Jérôme; Mazzella, Nicolas

2015-06-16

Glyphosate is the most widely used herbicide on a world scale for the last 40 years, for both urban and agricultural uses. Here we describe the first passive sampling method for estimating the concentration of glyphosate and AMPA (aminomethyl phosphonic acid, one of its major degradation products) in surface water. The sampling method is based on a newly developed configuration of the diffusive gradient in thin-film (DGT) technique, which includes a TiO2 binding phase, already in use for a wide range of anions. Glyphosate and AMPA were retained well on a TiO2 binding phase, and elution in a 1 mL of 1 M NaOH led to recoveries greater than 65%. We found no influence of pH or flow velocity on the diffusion coefficients through 0.8 mm polyacrylamide gels, although they did increase with temperature. TiO2 binding gels were able to accumulate up to 1167 ng of P for both glyphosate and AMPA, and linear accumulation was expected over several weeks, depending on environmental conditions. DGT sampling rates were close to 10 mL day(-1) in ultrapure water, while they were less than 1 mL day(-1) in the presence of naturally occurring ions (e.g., copper, iron, calcium, magnesium). These last results highlighted (i) the ability of DGT to measure only the freely dissolved fraction of glyphosate and AMPA in water and (ii) the needs to determine which fraction (total, particulate, dissolved, freely dissolved) is indeed bioactive.

Method 366.0 Determination of Dissolved Silicate in Estuarine and Coastal Watersby Gas Segmented Continuous Flow Colorimetric Analysis

EPA Science Inventory

This method provides a procedure for the determination of dissolved silicate concentration in estuarine and coastal waters. The dissolved silicate is mainly in the form of silicic acid, H SiO , in estuarine and 4 4 coastal waters. All soluble silicate, including colloidal silici...

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1991-06-18

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figures.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1989-11-07

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figs.

Pd nanoparticle assemblies--as the substitute of HRP, in their biosensing applications for H2O2 and glucose.

PubMed

Han, Min; Liu, Suli; Bao, Jianchun; Dai, Zhihui

2012-01-15

The spherical porous Pd nanoparticle assemblies (NPAs) have been successfully synthesized by starch-assisted chemical reduction of Pd(II) species at room temperature. Such Pd NPAs are not simply used to enlarge the surface area and to promote the electron transfer. They also catalyze the reduction of H(2)O(2) which are regarded as horseradish peroxidase (HRP) substitutes in electron transfer process. By using them as electrocatalysts, as low as 6.8×10(-7) M H(2)O(2) can be detected with a linear range from 1.0×10(-6) to 8.2×10(-4) M. Moreover, through co-immobilization of such Pd NPAs and glucose oxidase (GOx), a sensitive and selective glucose biosensor is developed. The detection principle lies on measuring the increase of cathodic current by co-reduction of dissolved oxygen and the in situ generated H(2)O(2) during the enzymatic reaction. Under optimal conditions, the detection limit is down to 6.1×10(-6) M with a very wide linear range from 4.0×10(-5) to 2.2×10(-2) M. The proposed biosensor shows a fast response, good stability, high selectivity and reproducibility of serum glucose level. It provides a promising strategy to construct fast, sensitive, stable and anti-interferential amperometric biosensors for early diagnosis and prevention of diabetes. Copyright © 2011 Elsevier B.V. All rights reserved.

In situ denitrification and DNRA rates in soils and underlying groundwater of an integrated constructed wetland

NASA Astrophysics Data System (ADS)

Mofizur Rahman Jahangir, Mohammad; Fenton, Owen; McAleer, Eoin; Carroll, Paul; Harrington, Rory; Johnston, Paul; Müller, Christoph; Richards, Karl

2015-04-01

Nitrogen (N) removal efficiency in constructed wetlands (CW) is low and again it does not in itself explain whether the removed N species are reactive or benign. Evaluation of environmental benefits of CW necessitates knowing N removal mechanisms and the fate of the removed N in such system. In situ denitrification and DNRA (dissimilatory nitrate reduction to ammonium) rates were measured in an earthen lined 5-cell integrated CW using 15N-enriched nitrate (NO3--N) push-pull method. Measurements were conducted in 2 groundwater depths (shallow- soils in CW bed; and deep- 4 m below CW soils) in 2 contrasting cells (high vs. low nutrient loads) of the CW. Denitrification (N¬2O-N + N2-N) and DNRA were the major NO3--N removal processes accounting together for 54-79% of the total biochemical removal of the applied NO3--N. Of which 14-17 and 40-68% were removed by denitrification and DNRA, respectively. Both the processes significantly differed with CW cells indicating that N transformations depend on the rate of nutrient loads in different cells. They were significantly higher in shallow than deep groundwater. Environmental conditions were favourable for both the processes (i.e. low dissolved oxygen and low redox potential, high dissolved organic carbon, high total carbon and high dissolved organic N) but DNRA rate was favoured over denitrification by high ambient NH4+ concentrations, reduced sulphide and low pH (5.9 - 7.0). Low pH might have limited denitrification to some extent to an incomplete state, being evident by a high N2O-N/(N2O-N+N2-N) ratio (0.35 ± 0.17, SE). Relatively higher N2O-N/(N2O-N+N2-N) ratio and higher DNRA rate over denitrification suggest that the end products of N transformations are reactive. This N2O can be consumed to N2 and/or emit to atmosphere directly and indirectly. The DNRA rate and accumulation of NH4+ indicated that CW is a net source of NH4+ in groundwater. Ammonium produced by DNRA can be fixed in soils and, when exchange sites are saturated, can flow to ground and surface waters. These results suggest that conventional input - output balance for N removal is misleading unless the removal mechanisms are fully understood and the fate of the removed N are known.