X-ray tomography studies on porosity and particle size distribution in cast in-situ Al-Cu-TiB{sub 2} semi-solid forged composites

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

Mathew, James; Mandal, Animesh

X-ray computed tomography (XCT) was used to characterise the internal microstructure and clustering behaviour of TiB{sub 2} particles in in-situ processed Al-Cu metal matrix composites prepared by casting method. Forging was used in semi-solid state to reduce the porosity and to uniformly disperse TiB{sub 2} particles in the composite. Quantification of porosity and clustering of TiB{sub 2} particles was evaluated for different forging reductions (30% and 50% reductions) and compared with an as-cast sample using XCT. Results show that the porosity content was decreased by about 40% due to semi-solid forging as compared to the as-cast condition. Further, XCT resultsmore » show that the 30% forging reduction resulted in greater uniformity in distribution of TiB{sub 2} particles within the composite compared to as-cast and the 50% forge reduction in semi-solid state. These results show that the application of forging in semi-solid state enhances particle distribution and reduces porosity formation in cast in-situ Al-Cu-TiB{sub 2} metal matrix composites. - Highlights: •XCT was used to visualise 3D internal structure of Al-Cu-TiB{sub 2} MMCs. •Al-Cu-TiB{sub 2} MMC was prepared by casting using flux assisted synthesis method. •TiB{sub 2} particles and porosity size distribution were evaluated. •Results show that forging in semi-solid condition decreases the porosity content and improve the particle dispersion in MMCs.« less

Large-Scale Parallel Simulations of Turbulent Combustion using Combined Dimension Reduction and Tabulation of Chemistry

DTIC Science & Technology

2012-05-22

tabulation of the reduced space is performed using the In Situ Adaptive Tabulation ( ISAT ) algorithm. In addition, we use x2f mpi – a Fortran library...for parallel vector-valued function evaluation (used with ISAT in this context) – to efficiently redistribute the chemistry workload among the...Constrained-Equilibrium (RCCE) method, and tabulation of the reduced space is performed using the In Situ Adaptive Tabulation ( ISAT ) algorithm. In addition

Phosphorus Amendment Efficacy for In Situ Remediation of Soil Lead Depends on the Bioaccessible Method

EPA Science Inventory

A validated method is needed to measure reductions of in vitro bioaccessible (IVBA) Pb in urban soil remediated with amendments. This study evaluated the effect of in vitro extraction solution pH and glycine buffer on bioaccesible Pb in P-treated soils. Two Pb-contaminated soils...

In-situ deposition of Pd nanoparticles on tubular halloysite template for initiation of metallization.

PubMed

Fu, Yubin; Zhang, Lide; Zheng, Jiyong

2005-04-01

Halloysite template has a tubular microstructure; its wall has a multi-layer aluminosilicate structure. A new catalytic method is adopted here, through the in-situ reduction of Pd ions on the surface of tubular halloysite by methanol to initiate electroless plating; the detailed deposition features of Pd nanoparticles are investigated for the first time. The results indicate that an in-situ reduction and deposition of Pd occurs at room temperature, in which the halloysite template plays an important role. Impurities in halloysite (such as ferric oxide) influence the formation and distribution of the Pd nanoparticles. The Pd nanoparticles are of a non-spherical shape in most cases, which would be caused by the irregular appearance of halloysite. No intercalation of the nanoparticles occurs between the aluminosilicate layers in the halloysite. The diameter of Pd nanoparticles increases with time; the average diameter ranges from 1 nm to 4 nm. Pd nanoparticles on a halloysite template can catalyze electroless deposition of Ni to prepare a novel nano-sized cermet at low cost. This practicable catalytic method could also be used on other clay substrates for the initiation of metallization.

Methods for tritium labeling

DOEpatents

Andres, Hendrik; Morimoto, Hiromi; Williams, Philip G.

1993-01-01

Reagents and processes for reductively introducing deuterium or tritium into organic molecules are described. The reagents are deuterium or tritium analogs of trialkyl boranes, borane or alkali metal aluminum hydrides. The process involves forming these reagents in situ from alkali metal tritides or deuterides.

Smart Solution Chemistry to Sn-Containing Intermetallic Compounds through a Self-Disproportionation Process.

PubMed

Zhang, Yuelan; Li, Liping; Li, Qi; Fan, Jianming; Zheng, Jing; Li, Guangshe

2016-09-26

Developing new methods to synthesize intermetallics is one of the most critical issues for the discovery and application of multifunctional metal materials; however, the synthesis of Sn-containing intermetallics is challenging. In this work, we demonstrated for the first time that a self-disproportionation-induced in situ process produces cavernous Sn-Cu intermetallics (Cu3 Sn and Cu6 Sn5 ). The successful synthesis is realized by introducing inorganic metal salts (SnCl2 ⋅2 H2 O) to NaOH aqueous solution to form an intermediate product of reductant (Na2 SnO2 ) and by employing steam pressures that enhance the reduction ability. Distinct from the traditional in situ reduction, the current reduction process avoided the uncontrolled phase composition and excessive use of organic regents. An insight into the mechanism was revealed for the Sn-Cu case. Moreover, this method could be extended to other Sn-containing materials (Sn-Co, Sn-Ni). All these intermetallics were attempted in the catalytic effect on thermal decompositions of ammonium perchlorate. It is demonstrated that Cu3 Sn showed an outstanding catalytic performance. The superior property might be primarily originated from the intrinsic chemical compositions and cavernous morphology as well. We supposed that this smart solution reduction methodology reported here would provide a new recognition for the reduction reaction, and its modified strategy may be applied to the synthesis of other metals, intermetallics as well as some unknown materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring dynamic electrochemical processes with in situ ptychography

NASA Astrophysics Data System (ADS)

Kourousias, George; Bozzini, Benedetto; Jones, Michael W. M.; Van Riessen, Grant A.; Dal Zilio, Simone; Billè, Fulvio; Kiskinova, Maya; Gianoncelli, Alessandra

2018-03-01

The present work reports novel soft X-ray Fresnel CDI ptychography results, demonstrating the potential of this method for dynamic in situ studies. Specifically, in situ ptychography experiments explored the electrochemical fabrication of Co-doped Mn-oxide/polypyrrole nanocomposites for sustainable and cost-effective fuel-cell air-electrodes. Oxygen-reduction catalysts based on Mn-oxides exhibit relatively high activity, but poor durability: doping with Co has been shown to improve both reduction rate and stability. In this study, we examine the chemical state distribution of the catalytically crucial Co dopant to elucidate details of the Co dopant incorporation into the Mn/polymer matrix. The measurements were performed using a custom-made three-electrode thin-layer microcell, developed at the TwinMic beamline of Elettra Synchrotron during a series of experiments that were continued at the SXRI beamline of the Australian Synchrotron. Our time-resolved ptychography-based investigation was carried out in situ after two representative growth steps, controlled by electrochemical bias. In addition to the observation of morphological changes, we retrieved the spectroscopic information, provided by multiple ptychographic energy scans across Co L3-edge, shedding light on the doping mechanism and demonstrating a general approach for the molecular-level investigation complex multimaterial electrodeposition processes.

In-situ IR spectroscopy as a probe of oxidation/reduction of Ce in nanostructured CeO2

NASA Astrophysics Data System (ADS)

Wu, Weiqiang; Savereide, Louisa Marie; Notestein, Justin; Weitz, Eric

2018-07-01

The redox properties of CeO2 are crucial in its applications in a wide range of catalytic processes. In the present research, in-situ IR spectroscopy is shown to be a viable and convenient method for the characterization of the oxidation state of Ce by monitoring the spin-orbit transition in Ce3+ (2F5/2 → 2F7/2) at ∼2147 cm-1. By monitoring this transition in CeO2 nanorods, the apparent activation energy for the production of oxygen vacancies that accompany the formation of Ce3+ has been determined and is shown to be lower for reduction with cyclohexene than with hydrogen. The bi-exponential kinetics for the formation of oxygen vacancies in CeO2 nanorods is discussed. An application of this method to real time monitoring of the oxidation state of Ce in the oxidation of cyclohexene on vanadia supported on ceria is presented as an example of how this method can be used as an operando probe of reaction mechanisms.

In Situ Rates of Sulfate Reduction in Response to Geochemical Perturbations

USGS Publications Warehouse

Kneeshaw, T.A.; McGuire, J.T.; Cozzarelli, I.M.; Smith, E.W.

2011-01-01

Rates of in situ microbial sulfate reduction in response to geochemical perturbations were determined using Native Organism Geochemical Experimentation Enclosures (NOGEEs), a new in situ technique developed to facilitate evaluation of controls on microbial reaction rates. NOGEEs function by first trapping a native microbial community in situ and then subjecting it to geochemical perturbations through the introduction of various test solutions. On three occasions, NOGEEs were used at the Norman Landfill research site in Norman, Oklahoma, to evaluate sulfate-reduction rates in wetland sediments impacted by landfill leachate. The initial experiment, in May 2007, consisted of five introductions of a sulfate test solution over 11 d. Each test stimulated sulfate reduction with rates increasing until an apparent maximum was achieved. Two subsequent experiments, conducted in October 2007 and February 2008, evaluated the effects of concentration on sulfate-reduction rates. Results from these experiments showed that faster sulfate-reduction rates were associated with increased sulfate concentrations. Understanding variability in sulfate-reduction rates in response to perturbations may be an important factor in predicting rates of natural attenuation and bioremediation of contaminants in systems not at biogeochemical equilibrium. Copyright ?? 2011 The Author(s). Journal compilation ?? 2011 National Ground Water Association.

Improved data reduction algorithm for the needle probe method applied to in-situ thermal conductivity measurements of lunar and planetary regoliths

NASA Astrophysics Data System (ADS)

Nagihara, Seiichi; Hedlund, Magnus; Zacny, Kris; Taylor, Patrick T.

2014-03-01

The needle probe method (also known as the ‘hot wire’ or ‘line heat source’ method) is widely used for in-situ thermal conductivity measurements on terrestrial soils and marine sediments. Variants of this method have also been used (or planned) for measuring regolith on the surfaces of extra-terrestrial bodies (e.g., the Moon, Mars, and comets). In the near-vacuum condition on the lunar and planetary surfaces, the measurement method used on the earth cannot be simply duplicated, because thermal conductivity of the regolith can be ~2 orders of magnitude lower. In addition, the planetary probes have much greater diameters, due to engineering requirements associated with the robotic deployment on extra-terrestrial bodies. All of these factors contribute to the planetary probes requiring a much longer time of measurement, several tens of (if not over a hundred) hours, while a conventional terrestrial needle probe needs only 1 to 2 min. The long measurement time complicates the surface operation logistics of the lander. It also negatively affects accuracy of the thermal conductivity measurement, because the cumulative heat loss along the probe is no longer negligible. The present study improves the data reduction algorithm of the needle probe method by shortening the measurement time on planetary surfaces by an order of magnitude. The main difference between the new scheme and the conventional one is that the former uses the exact mathematical solution to the thermal model on which the needle probe measurement theory is based, while the latter uses an approximate solution that is valid only for large times. The present study demonstrates the benefit of the new data reduction technique by applying it to data from a series of needle probe experiments carried out in a vacuum chamber on a lunar regolith simulant, JSC-1A. The use of the exact solution has some disadvantage, however, in requiring three additional parameters, but two of them (the diameter and the volumetric heat capacity of the probe) can be measured and the other (the volumetric heat capacity of the regolith/stimulant) may be estimated from the surface geologic observation and temperature measurements. Therefore, overall, the new data reduction scheme would make in-situ thermal conductivity measurement more practical on planetary missions.

Improved Data Reduction Algorithm for the Needle Probe Method Applied to In-Situ Thermal Conductivity Measurements of Lunar and Planetary Regoliths

NASA Technical Reports Server (NTRS)

Nagihara, S.; Hedlund, M.; Zacny, K.; Taylor, P. T.

2013-01-01

The needle probe method (also known as the' hot wire' or 'line heat source' method) is widely used for in-situ thermal conductivity measurements on soils and marine sediments on the earth. Variants of this method have also been used (or planned) for measuring regolith on the surfaces of extra-terrestrial bodies (e.g., the Moon, Mars, and comets). In the near-vacuum condition on the lunar and planetary surfaces, the measurement method used on the earth cannot be simply duplicated, because thermal conductivity of the regolith can be approximately 2 orders of magnitude lower. In addition, the planetary probes have much greater diameters, due to engineering requirements associated with the robotic deployment on extra-terrestrial bodies. All of these factors contribute to the planetary probes requiring much longer time of measurement, several tens of (if not over a hundred) hours, while a conventional terrestrial needle probe needs only 1 to 2 minutes. The long measurement time complicates the surface operation logistics of the lander. It also negatively affects accuracy of the thermal conductivity measurement, because the cumulative heat loss along the probe is no longer negligible. The present study improves the data reduction algorithm of the needle probe method by shortening the measurement time on planetary surfaces by an order of magnitude. The main difference between the new scheme and the conventional one is that the former uses the exact mathematical solution to the thermal model on which the needle probe measurement theory is based, while the latter uses an approximate solution that is valid only for large times. The present study demonstrates the benefit of the new data reduction technique by applying it to data from a series of needle probe experiments carried out in a vacuum chamber on JSC-1A lunar regolith stimulant. The use of the exact solution has some disadvantage, however, in requiring three additional parameters, but two of them (the diameter and the volumetric heat capacity of the probe) can be measured and the other (the volumetric heat capacity of the regolith/stimulant) may be estimated from the surface geologic observation and temperature measurements. Therefore, overall, the new data reduction scheme would make in-situ thermal conductivity measurement more practical on planetary missions.

Construction of Au@Pt core—satellite nanoparticles based on in-situ reduction of polymeric ionic liquid protected gold nanoparticles

NASA Astrophysics Data System (ADS)

Wu, Wenlan; Li, Junbo; Zou, Sheng; Guo, Jinwu; Zhou, Huiyun

2017-03-01

A method of in-situ reduction to prepare Au@Pt core-satellite nanoparticles (NPs) is described by using Au NPs coating poly[1-methyl 3-(2-methacryloyloxy propylimidazolium bromine)] (PMMPImB-@-Au NPs) as the template. After electrostatic complex chloroplatinic acid with PMMPImB shell, the composite NP was directly reduced with N2H4 to produce Au@Pt core-satellite NPs. The characterization of composite and core-satellite NPs under different amounts of chloroplatinic acid were studied by DLS, UV-vis absorption spectrum and TEM. The satellite Pt NPs with a small size ( 2 nm) dotted around Au core, and the resulting Au@Pt core-satellite NPs showed a red-shift surface plasmon resonance (SPR) and a good dispersion due to effectively electrostatic repulsion providing by the polymeric ionic liquid (PIL) shell. Finally, Au@Pt core-satellite NPs exhibit an enhanced catalytic activity and cycled catalytic capability for the reduction of p-nitrophenol with NaBH4.

IN SITU DESTRUCTION OF CHLORINATED HYDROCARBON COMPOUNDS IN GROUNDWATER USING CATALYTIC REDUCTIVE REDUCTIVE DEHALOGENATION IN A REACTIVE WELL: TESTING AND OPERATIONAL EXPERIENCES. (R825421)

EPA Science Inventory

A groundwater treatment technology based on catalytic reductive
dehalogenation has been developed to efficiently destroy chlorinated
hydrocarbons in situ using a reactive well approach. The treatment process
utilizes dissolved H₂ as an electron donor, in...

In situ supported MnOx-CeOx on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Zhang, Dengsong; Zhang, Lei; Shi, Liyi; Fang, Cheng; Li, Hongrui; Gao, Ruihua; Huang, Lei; Zhang, Jianping

2013-01-01

The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods.The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods. Electronic supplementary information (ESI) available: SEM images and EDS analysis, TEM images, and XPS spectrum of samples. See DOI: 10.1039/c2nr33006g

Optical in situ monitoring of plasma-enhanced atomic layer deposition process

NASA Astrophysics Data System (ADS)

Zeeshan Arshad, Muhammad; Jo, Kyung Jae; Kim, Hyun Gi; Jeen Hong, Sang

2018-06-01

An optical in situ process monitoring method for the early detection of anomalies in plasma process equipment is presented. Cyclic process steps of precursor treatment and plasma reaction for the deposition of an angstrom-scale film increase their complexity to ensure the process quality. However, a small deviation in process parameters, for instance, gas flow rate, process temperature, or RF power, may jeopardize the deposited film quality. As a test vehicle for the process monitoring, we have investigated the aluminum-oxide (Al2O3) encapsulation process in plasma-enhanced atomic layer deposition (PEALD) to form a moisture and oxygen diffusion barrier in organic-light emitting diodes (OLEDs). By optical in situ monitoring, we successfully identified the reduction in oxygen flow rates in the reaction steps, which resulted in a 2.67 times increase in the water vapor transmission ratio (WVTR) of the deposited Al2O3 films. Therefore, we are convinced that the suggested in situ monitoring method is useful for the detection of process shifts or drifts that adversely affect PEALD film quality.

The treatment of an unstable slipped capital femoral epiphysis by either intracapsular cuneiform osteotomy or pinning in situ: a comparative study.

PubMed

Walton, R D M; Martin, E; Wright, D; Garg, N K; Perry, D; Bass, A; Bruce, C

2015-03-01

We undertook a retrospective comparative study of all patients with an unstable slipped capital femoral epiphysis presenting to a single centre between 1998 and 2011. There were 45 patients (46 hips; mean age 12.6 years; 9 to 14); 16 hips underwent intracapsular cuneiform osteotomy and 30 underwent pinning in situ, with varying degrees of serendipitous reduction. No patient in the osteotomy group was lost to follow-up, which was undertaken at a mean of 28 months (11 to 48); four patients in the pinning in situ group were lost to follow-up, which occurred at a mean of 30 months (10 to 50). Avascular necrosis (AVN) occurred in four hips (25%) following osteotomy and in 11 (42%) following pinning in situ. AVN was not seen in five hips for which osteotomy was undertaken > 13 days after presentation. AVN occurred in four of ten (40%) hips undergoing emergency pinning in situ, compared with four of 15 (47%) undergoing non-emergency pinning. The rate of AVN was 67% (four of six) in those undergoing pinning on the second or third day after presentation. Pinning in situ following complete reduction led to AVN in four out of five cases (80%). In comparison, pinning in situ following incomplete reduction led to AVN in 7 of 21 cases (33%). The rate of development of AVN was significantly higher following pinning in situ with complete reduction than following intracapsular osteotomy (p = 0.048). Complete reduction was more frequent in those treated by emergency pinning and was strongly associated with AVN (p = 0.005). Non-emergency intracapsular osteotomy may have a protective effect on the epiphyseal vasculature and should be undertaken with a delay of at least two weeks. The place of emergency pinning in situ in these patients needs to be re-evaluated, possibly in favour of an emergency open procedure or delayed intracapsular osteotomy. Non-emergency pinning in situ should be undertaken after a delay of at least five days, with the greatest risk at two and three days after presentation. Intracapsular osteotomy should be undertaken after a delay of at least 14 days. In our experience, closed epiphyseal reduction is harmful. Cite this article: Bone Joint J 2015;97-B:412-19. ©2015 The British Editorial Society of Bone & Joint Surgery.

Graphitic carbon stabilized silver nanoparticles synthesized by a simple chemical precursor method

NASA Astrophysics Data System (ADS)

Soni, Bhasker; Biswas, Somnath

2018-04-01

Monodispersed graphitic carbon stabilized silver nanoparticles (AgNPs) were synthesized following a simple chemical precursor method. The precursor was obtained by a controlled reduction of Ag+ in aqueous solution of poly-vinyl alcohol (PVA) and sucrose. The process allows precise control over the morphology of the AgNPs along with in situ formation of a surface stabilization layer of graphitic carbon.

Combined In-Situ XRD and In-Situ XANES Studies on the Reduction Behavior of a Rhenium Promoted Cobalt Catalyst

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

Kumar, Nitin; Payzant, E Andrew; Jothimurugesan, K

2011-01-01

A 10% Co 4% Re/(2% Zr/SiO2) catalyst was prepared by co-impregnation using a silica support modified by 2% Zr. The catalyst was characterized by temperature programmed reduction (TPR), in situ XRD and in situ XANES analysis where it was simultaneously exposed to H2 using a temperature programmed ramp. The results showed the two step reduction of large crystalline Co3O4 with CoO as an intermediate. TPR results showed that the reduction of highly dispersed Co3O4 was facilitated by reduced rhenium by a H2-spillover mechanism. In situ XRD results showed the presence of both, Co-hcp and Co-fcc phases in the reduced catalystmore » at 400 C. However, the Co-hcp phase was more abundant, which is thought to be the more active phase as compared to the Co-fcc phase for CO hydrogenation. CO hydrogenation at 270 C and 5 bar pressure produces no detectable change in the phases during the time of experiment. In situ XANES results showed a decrease in the metallic cobalt in the presence of H2/CO, which can be attributed due to oxidation of the catalyst by reaction under these conditions.« less

In situ spectroscopic monitoring of CO2 reduction at copper oxide electrode.

PubMed

Wang, Liying; Gupta, Kalyani; Goodall, Josephine B M; Darr, Jawwad A; Holt, Katherine B

2017-04-28

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO 3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(i) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO 2 saturated KHCO 3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO 2 . On cycling to negative potentials, larger reduction currents were observed in the presence of CO 2 ; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO 2 CuO underwent reduction to Cu 2 O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials.

In-Situ Resource Utilization (ISRU) Development Program

NASA Technical Reports Server (NTRS)

Sanders, Jerry

1998-01-01

The question "Why In-Situ Resource Utilization (ISRU)?" is addressed in this presentation. The reasons given concentrate on Cost reduction, Mass reduction, Risk reduction, the expansion of human exploration and presence and the enabling of industrial exploitation. A review of the Martian and Lunar resources available for ISRU is presented. Other ISRU concepts (i.e., In-Situ Consumable production (ISCP) and In-Situ Propellant Production (ISPP)) are introduced and further explained. The objectives of a Mars ISRU System Technology (MIST) include (1) the characterization of technology and subsystem performance for mission modeling and technology funding planning, (2) reduce risk and concerns arising from sample return and human missions utilizing ISRU, and (3) demonstrate the environmental suitability of ISRU components/processes and systems. A proof of concept demonstration schedule and a facility overview for MIST is presented.

Polypyrrole-MWCNT-Ag composites for electromagnetic shielding: Comparison between chemical deposition and UV-reduction approaches

NASA Astrophysics Data System (ADS)

Ebrahimi, Izadyar; Gashti, Mazeyar Parvinzadeh

2018-07-01

In this study, we focused on the synthesis of polypyrrole-MWCNT-Ag composites and we evaluated their electrical properties to determine the electromagnetic interference shielding performance. We reduced silver nanoparticles in composites using two different in situ methods: UV-reduction and chemical deposition. Composites were characterized using spectroscopic and microscopic tools for evaluation of the chemical, morphological, electrical conductivity and electromagnetic shielding effectiveness. Results from Fourier transform infrared spectroscopy and dispersive Raman microscope showed chemical interactions between silver and the polypyrrole-MWCNT composite due to the charge-transfer within the structure. X-ray diffraction confirmed appearance of two new peaks for silver nanoparticles embedded in polypyrrole-MWCNT independent to reduction method. According to microscopy images, silver nanoparticles were homogenously distributed at the PPy-MWCNTs interfaces by UV reduction, while, chemical reduction resulted to deposition of silver within the PPy matrix. Finally, our results revealed that the polypyrrole-MWCNT-Ag composite produced via UV-reduction has higher electrical conductivity and shielding effectiveness in comparison to chemically reduced one.

Reduction reactions and densification during in situ TEM heating of iron oxide nanochains

NASA Astrophysics Data System (ADS)

Bonifacio, Cecile S.; Das, Gautom; Kennedy, Ian M.; van Benthem, Klaus

2017-12-01

The reduction reactions and densification of nanochains assembled from γ-Fe2O3 nanoparticles were investigated using in situ transmission electron microscopy (TEM). Morphological changes and reduction of the metal oxide nanochains were observed during in situ TEM annealing through simultaneous imaging and quantitative analysis of the near-edge fine structures of Fe L2,3 absorption edges acquired by spatially resolved electron energy loss spectroscopy. A change in the oxidation states during annealing of the iron oxide nanochains was observed with phase transformations due to continuous reduction from Fe2O3 over Fe3O4, FeO to metallic Fe. Phase transitions during the in situ heating experiments were accompanied with morphological changes in the nanochains, specifically rough-to-smooth surface transitions below 500 °C, neck formation between adjacent particles around 500 °C, and subsequent neck growth. At higher temperatures, coalescence of FeO particles was observed, representing densification.

Dielectric Properties of Reduced Graphene Oxide/Copper Phthalocyanine Nanocomposites Fabricated Through π- π Interaction

NASA Astrophysics Data System (ADS)

Wang, Zicheng; Wei, Renbo; Liu, Xiaobo

2017-01-01

Reduced graphene oxide/copper phthalocyanine nanocomposites are successfully prepared through a simple and effective two-step method, involving preferential reduction of graphene oxide and followed by self-assembly with copper phthalocyanine. The results of photographs, ultraviolet visible, x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy show that the in situ blending method can effectively facilitate graphene sheets to disperse homogenously in the copper phthalocyanine matrix through π- π interactions. As a result, the reduction of graphene oxide and restoration of the sp 2 carbon sites in graphene can enhance the dielectric properties and alternating current conductivity of copper phthalocyanine effectively.

Immobilization of Iron Nanoparticles on Multi Substrates and Its Reduction Removal of Chromium (VI) from Waste Streams

EPA Science Inventory

This article describes the in-situ synthesis and immobilization of iron nanoparticles on several substrates at room temperature using NaBH4 as a reducing agent and ascorbic acid as capping agent. The method is very effective in protecting iron nanoparticles from air oxidation for...

Reduction of stresses on buried rigid highway structures using the imperfect ditch method and expanded polysterene : geofoam.

DOT National Transportation Integrated Search

2009-01-01

This study provides strong evidences from both numerical model analysis and in-situ test data to indicate that geofoam is an ideal elasto-plastic material to reduce vertical load on top of rigid culvert resting on a rigid foundation. The load on the ...

Surgical management of macroglossia secondary to amyloidosis.

PubMed

Gadiwalla, Yusuf; Burnham, Richard; Warfield, Adrian; Praveen, Prav

2016-04-11

The authors report a case of amyloidosis-induced macroglossia treated with surgical reduction of the tongue using a keyhole to inverted T method with particular emphasis on the postoperative sequelae. Significant tongue swelling persisted for longer than anticipated requiring tracheostomy to remain in situ for 14 days. 2016 BMJ Publishing Group Ltd.

Direct patterning of silver particles on porous silicon by inkjet printing of a silver salt via in-situ reduction

PubMed Central

2012-01-01

We have developed a method for obtaining a direct pattern of silver nanoparticles (NPs) on porous silicon (p-Si) by means of inkjet printing (IjP) of a silver salt. Silver NPs were obtained by p-Si mediated in-situ reduction of Ag+ cations using solutions based on AgNO3 which were directly printed on p-Si according to specific geometries and process parameters. The main difference with respect to existing literature is that normally, inkjet printing is applied to silver (metal) NP suspensions, while in our experiment the NPs are formed after jetting the solution on the reactive substrate. We performed both optical and scanning electron microscopes on the NPs traces, correlating the morphology features with the IjP parameters, giving an insight on the synthesis kinetics. The patterned NPs show good performances as SERS substrates. PMID:22953722

Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt-Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy

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

Flynn, Brendan T.; Oleksak, Richard P.; Thevuthasan, Suntharampillai

A method to modulate the Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. The interfacial chemistries that modulate barrier heights for the Pt/a-IGZO system were investigated using in-situ X-ray photoelectron spectroscopy. A significant reduction of indium, from In3+ to In0, occurs during deposition of Pt on to the a-IGZO surface in ultra-high vacuum. Post-annealing and controlling the background ambient O2 pressure allows tuning the degree of indium reduction and the corresponding Schottky barrier height between 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries atmore » Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metalsemiconductor field-effect transistors.« less

Removal of water contaminants by nanoscale zero-valent iron immobilized in PAN-based oxidized membrane

NASA Astrophysics Data System (ADS)

Liu, Chunyi; Li, Xiang; Ma, Bomou; Qin, Aiwen; He, Chunju

2014-12-01

The functionalizing nanoporous polyacrylonitrile-based oxidized membrane (PAN-OM) firmly immobilized with highly reactive nanoscale zero-valent iron (NZVI) are successfully prepared via an innovative in situ synthesis method. Due to the formation of ladder structure, the PAN-OM present excellent thermal and chemical stabilities as a new carrier for the in-situ growth of NZVI via firm chelation and reduction action, respectively, which prevent the aggregation and release of NZVI. The developed NZVI-immobilized membrane present effective decolorizing efficiency to both anionic methyl blue and cationic methylene blue with a pseudo-first-order decay and degrading efficiency to trichloroethylene (TCE). The regeneration and stability results show that NZVI-immobilized membrane system can be regenerated without obvious performance reduction, which remain the reactivity after half a year storage period. These results suggest that PAN-based oxidized membrane immobilized with NZVI exhibit significant potential for environmental applications.

Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt–Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy

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

Flynn, Brendan T.; Oleksak, Richard P.; Thevuthasan, Suntharampillai

A method to modulate the Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. The interfacial chemistries that modulate barrier heights for the Pt/a-IGZO system were investigated using in-situ X-ray photoelectron spectroscopy. A significant reduction of indium, from In 3+ to In 0, occurs during deposition of Pt on to the a-IGZO surface in ultra-high vacuum. Post-annealing and controlling the background ambient O 2 pressure allows tuning the degree of indium reduction and the corresponding Schottky barrier height between 0.17 to 0.77 eV. Understanding the detailedmore » interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metalsemiconductor field-effect transistors.« less

A practical and catalyst-free trifluoroethylation reaction of amines using trifluoroacetic acid

NASA Astrophysics Data System (ADS)

Andrews, Keith G.; Faizova, Radmila; Denton, Ross M.

2017-06-01

Amines are a fundamentally important class of biologically active compounds and the ability to manipulate their physicochemical properties through the introduction of fluorine is of paramount importance in medicinal chemistry. Current synthesis methods for the construction of fluorinated amines rely on air and moisture sensitive reagents that require special handling or harsh reductants that limit functionality. Here we report practical, catalyst-free, reductive trifluoroethylation reactions of free amines exhibiting remarkable functional group tolerance. The reactions proceed in conventional glassware without rigorous exclusion of either moisture or oxygen, and use trifluoroacetic acid as a stable and inexpensive fluorine source. The new methods provide access to a wide range of medicinally relevant functionalized tertiary β-fluoroalkylamine cores, either through direct trifluoroethylation of secondary amines or via a three-component coupling of primary amines, aldehydes and trifluoroacetic acid. A reduction of in situ-generated silyl ester species is proposed to account for the reductive selectivity observed.

INJECTION OF A FERROUS SULFATE/SODIUM DITHIONITE REDUCTANT FOR IN-SITU TREATMENT OF HEXAVALENT CHROMIUM

EPA Science Inventory

An in situ pilot study was conducted to evaluate the performance of a ferrous iron-based reductant solution in treating hexavalent chromium within a saturated zone source area at a former industrial site in Charleston, South Carolina (USA). The hexavalent source area, consisting...

Enhanced performance of microbial fuel cell with in situ preparing dual graphene modified bioelectrode.

PubMed

Chen, Junfeng; Hu, Yongyou; Tan, Xiaojun; Zhang, Lihua; Huang, Wantang; Sun, Jian

2017-10-01

This study proposed a three-step method to prepare dual graphene modified bioelectrode (D-GM-BE) by in situ microbial-induced reduction of GO and polarity reversion in microbial fuel cell (MFC). Both graphene modified bioanode (GM-BA) and biocathode (GM-BC) were of 3D graphene/biofilm architectures; the viability and thickness of microbial biofilm decreased compared with control bioelectrode (C-BE). The coulombic efficiency (CE) of GM-BA was 2.1 times of the control bioanode (C-BA), which demonstrated higher rate of substrates oxidation; the relationship between peak current and scan rates data meant that GM-BC was of higher efficiency of catalyzing oxygen reduction than the control biocathode (C-BC). The maximum power density obtained in D-GM-BE MFC was 122.4±6.9mWm -2 , the interfacial charge transfer resistance of GM-BA and GM-BC were decreased by 79% and 75.7%. The excellent electrochemical performance of D-GM-BE MFC was attributed to the enhanced extracellular electron transfer (EET) process and catalyzing oxygen reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques

DOE PAGES

Durham, Jessica L.; Brady, Alexander B.; Cama, Christina A.; ...

2017-08-02

Here, the structure of pristine AgFeO 2 and phase makeup of Ag 0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2O 3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2FeO 1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe 2O 3 component in the Ag 0.2FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2FeO 1.6 composites demonstrated differences in the structuralmore » evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+yFe IIIFe IIyO 2 phase. The Li 1+yFe IIIFe IIyO 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2FeO 1.6 composite, a substantial amorphous γ-Fe 2O 3 component is observed which discharges to rock salt LiFe 2O 3 and Fe 0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.« less

Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques

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

Durham, Jessica L.; Brady, Alexander B.; Cama, Christina A.

Here, the structure of pristine AgFeO 2 and phase makeup of Ag 0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2O 3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2FeO 1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe 2O 3 component in the Ag 0.2FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2FeO 1.6 composites demonstrated differences in the structuralmore » evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+yFe IIIFe IIyO 2 phase. The Li 1+yFe IIIFe IIyO 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2FeO 1.6 composite, a substantial amorphous γ-Fe 2O 3 component is observed which discharges to rock salt LiFe 2O 3 and Fe 0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.« less

Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques.

PubMed

Durham, Jessica L; Brady, Alexander B; Cama, Christina A; Bock, David C; Pelliccione, Christopher J; Zhang, Qing; Ge, Mingyuan; Li, Yue Ru; Zhang, Yiman; Yan, Hanfei; Huang, Xiaojing; Chu, Yong; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2017-08-23

The structure of pristine AgFeO 2 and phase makeup of Ag 0.2 FeO 1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2 O 3 phases) was investigated using synchrotron X-ray diffraction. A new stacking-fault model was proposed for AgFeO 2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2 FeO 1.6 were investigated using ex situ, in situ, and operando characterization techniques. An amorphous γ-Fe 2 O 3 component in the Ag 0.2 FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2 FeO 1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex situ X-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in situ high energy X-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag 0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+y Fe III Fe II y O 2 phase. The Li 1+y Fe III Fe II y O 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2 FeO 1.6 composite, a substantial amorphous γ-Fe 2 O 3 component is observed which discharges to rock salt LiFe 2 O 3 and Fe 0 metal phase in the 3.5-1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.

In situ synthesis of silver nanoparticles uniformly distributed on polydopamine-coated silk fibers for antibacterial application.

PubMed

Lu, Zhisong; Xiao, Jing; Wang, Ying; Meng, Mei

2015-08-15

Fabrication of silver nanoparticles (AgNPs)-modified silk for antibacterial application is one of the hottest topics in the textile material research. However, the utilization of a polymer as both 3-dimensional matrix and reductant for the in-situ synthesis of AgNPs on silk fibers has not been realized. In this work, a facile, efficient and green approach was developed to in-situ grow AgNPs on the polydopamine (PDA)-functionalized silk. AgNPs with the size of 30-90 nm were uniformly deposited on the silk fiber surface with the PDA coating layer as a reduction reagent. The AgNPs exhibit excellent face-centered cubic crystalline structures. The bacterial growth curve and inhibition zone assays clearly demonstrate the antibacterial properties of the functionalized silk. Both high Ag(+) release level and long-time release profile were observed for the as-prepared AgNPs-PDA-coated silk, indicating the high-density loading of AgNPs and the possible long-term antibacterial effects. This work may provide a new method for the preparation of AgNPs-functionalized silk with antibacterial activity for the clothing and textile industry. Copyright © 2015 Elsevier Inc. All rights reserved.

In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

PubMed

Zhang, Kaige; Li, Gongke; Hu, Yuling

2015-10-28

The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

In-Situ Chemical Reduction and Oxidation of VOCs in Groundwater: Groundwater Treatability Studies

NASA Technical Reports Server (NTRS)

Keith, Amy; Glasgow, Jason; McCaleh, Rececca C. (Technical Monitor)

2001-01-01

This paper presents NASA Marshall Space Flight Center's treatability studies for volatile organic compounds in groundwater. In-Situ groundwater treatment technologies include: 1) Chemical Reduction(Ferox); 2) Chemical Oxidation (Fenton Reagents, Permanganate, and Persulfate); and 3) Thermal (Dynamic Underground Stripping, Six-Phase Heating). This paper is presented in viewgraph form.

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2012 CFR

2012-07-01

...) The concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent...). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source...

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2011 CFR

2011-07-01

... concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent characteristic... provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source subject to...

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) The concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent...). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source...

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2010 CFR

2010-07-01

... concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent characteristic... provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source subject to...

Secondary amine formation from reductive amination of carbonyl compounds promoted by Lewis acid using the InCl3/Et3SiH system.

PubMed

Lee, On-Yi; Law, Ka-Lun; Yang, Dan

2009-08-06

A robust and reliable method has been developed for reductive amination of primary amines with various aldehydes and ketones using Zn(ClO(4))(2) x 6 H(2)O as a catalyst. [In-H] generated in situ via a combination of InCl(3) and Et(3)SiH is employed as an effective reducing system. A variety of secondary amines can be synthesized in a one-pot procedure in excellent yields.

Combination of Fluorescence In Situ Hybridization with Staining Techniques for Cell Viability and Accumulation of PHA and polyP in Microorganisms in Complex Microbial Systems

NASA Astrophysics Data System (ADS)

Nielsen, Jeppe Lund; Kragelund, Caroline; Nielsen, Per Halkjær

Fluorescence in situ hybridization (FISH) can be combined with a number of staining techniques to reveal the relationships between the microorganisms and their function in complex microbial systems with a single-cell resolution. In this chapter, we have focused on staining methods for intracellular storage compounds (polyhydroxyalkanoates, polyphosphate) and a measure for cell viability, reduction of the tetrazolium-based redox stain CTC. These protocols are optimized for the study of microorganisms in waste-water treatment (activated sludge and biofilms), but they may also be used with minor modifications in many other ecosystems.

In-situ photoluminescence imaging for passivation-layer etching process control for photovoltaics

NASA Astrophysics Data System (ADS)

Lee, J. Z.; Michaelson, L.; Munoz, K.; Tyson, T.; Gallegos, A.; Sullivan, J. T.; Buonassisi, T.

2014-07-01

Light-induced plating (LIP) of solar-cell metal contacts is a scalable alternative to silver paste. However, LIP requires an additional patterning step to create openings in the silicon nitride (SiNx) antireflection coating (ARC) layer prior to metallization. One approach to pattern the SiNx is masking and wet chemical etching. In-situ real-time photoluminescence imaging (PLI) is demonstrated as a process-monitoring method to determine when SiNx has been fully removed during etching. We demonstrate that the change in PLI signal intensity during etching is caused by a combination of (1) decreasing light absorption from the reduction in SiNx ARC layer thickness and (2) decreasing surface lifetime as the SiNx/Si interface transitions to an etch-solution/Si. Using in-situ PLI to guide the etching process, we demonstrate a full-area plated single-crystalline silicon device. In-situ PLI has the potential to be integrated into a commercial processing line to improve process control and reliability.

Analytical method for optimal source reduction with monitored natural attenuation in contaminated aquifers

USGS Publications Warehouse

Widdowson, M.A.; Chapelle, F.H.; Brauner, J.S.; ,

2003-01-01

A method is developed for optimizing monitored natural attenuation (MNA) and the reduction in the aqueous source zone concentration (??C) required to meet a site-specific regulatory target concentration. The mathematical model consists of two one-dimensional equations of mass balance for the aqueous phase contaminant, to coincide with up to two distinct zones of transformation, and appropriate boundary and intermediate conditions. The solution is written in terms of zone-dependent Peclet and Damko??hler numbers. The model is illustrated at a chlorinated solvent site where MNA was implemented following source treatment using in-situ chemical oxidation. The results demonstrate that by not taking into account a variable natural attenuation capacity (NAC), a lower target ??C is predicted, resulting in unnecessary source concentration reduction and cost with little benefit to achieving site-specific remediation goals.

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

Neelgund, Gururaj M.; Oki, Aderemi, E-mail: aroki@pvamu.edu; Luo, Zhiping

Graphical abstract: A facile chemical precipitation method is reported for effective in situ deposition of hydroxyapatite on graphene nanosheets. Prior to grafting of hydroxyapatite, chemically modified graphene nanosheets were obtained by the reduction of graphene oxide in presence of ethylenediamine. Display Omitted Highlights: ► It is a facile and effective method for deposition of HA on GR nanosheets. ► It avoids the use of harmful reducing agents like hydrazine, NaBH{sub 4} etc. ► GR nanosheets were produced using bio-compatible, ethylenediamine. ► The graphitic structure of synthesized GR nanosheets was high ordered. ► The ratio of Ca to P in HAmore » was 1.64, which is close to ratio in natural bone. -- Abstract: Graphene nanosheets were effectively functionalized by in situ deposition of hydroxyapatite through a facile chemical precipitation method. Prior to grafting of hydroxyapatite, chemically modified graphene nanosheets were obtained by the reduction of graphene oxide in presence of ethylenediamine. The resulting hydroxyapatite functionalized graphene nanosheets were characterized by attenuated total reflection IR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, Raman spectroscopy and thermogravimetric analysis. These characterization techniques revealed the successful grafting of hydroxyapatite over well exfoliated graphene nanosheets without destroying their structure.« less

Biochar Addition Increases the Rates of Dissimilatory Iron Reduction and Methanogenesis in Ferrihydrite Enrichments

PubMed Central

Zhou, Guo-Wei; Yang, Xiao-Ru; Marshall, Christopher W.; Li, Hu; Zheng, Bang-Xiao; Yan, Yu; Su, Jian-Qiang; Zhu, Yong-Guan

2017-01-01

Biochar contains quinones and aromatic structures that facilitate extracellular electron transfer between microbial cells and insoluble minerals. In this study, granulated biochar (1.2–2 mm) and powdered biochar (<0.15 mm) were amended to two ferrihydrite (in situ ferrihydrite and ex situ ferrihydrite) enrichments to investigate the effect of biochar with different particle sizes on dissimilatory iron(III)-reducing bacteria (DIRB) and methanogens. Biochar addition significantly stimulated the reduction of both in situ ferrihydrite and ex situ ferrihydrite and the production of methane. Powdered biochar amendments increased iron reduction compared to granulated biochar amendment in both the in situ ferrihydrite and ex situ ferrihydrite enrichments. However, no significant difference was observed in methane production between the powdered biochar and granulated biochar amendments in the two ferrihydrite enrichments. Analysis of 16S rRNA gene sequences showed that both DIRB and methanogens were enriched after biochar amendments in the in situ ferrihydrite and ex situ ferrihydrite enrichments. Taxa belonging to the Geobacteraceae and methanogenic genus affiliated to Methanosarcina were detected with significantly higher relative abundances in powdered biochar amendments than those in granulated biochar amendments in both the ferrihydrite enrichments. X-ray diffraction analysis indicated green rust [Fe2(CO3) (OH)] and vivianite [Fe3(PO4)2 8(H2O)] formed in the ex situ ferrihydrite and in situ ferrihydrite enrichments without biochar addition, respectively. After granulated biochar amendment, the mineral phase changed from the green rust to vivianite in the ex situ ferrihydrite enrichment, while crystalline vivianite and iron oxide (γ-Fe2O3) were detected simultaneously in the in situ ferrihydrite enrichment. No crystalline iron compound was found in the powdered biochar amendments in both ferrihydrite enrichments. Overall, our study illustrated that the addition of biochar affected iron-reducing and methane-generating microbial communities to some extent. PMID:28428774

Microbial links between sulfate reduction and metal retention in uranium- and heavy metal-contaminated soil.

PubMed

Sitte, Jana; Akob, Denise M; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E; Scheinost, Andreas C; Büchel, Georg; Küsel, Kirsten

2010-05-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the (35)SO(4)(2-) radiotracer method, was restricted to reduced soil horizons with rates of < or =142 +/- 20 nmol cm(-3) day(-1). Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that approximately 80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [(13)C]acetate- and [(13)C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined < or =100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching < or =1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems.

Microbial Links between Sulfate Reduction and Metal Retention in Uranium- and Heavy Metal-Contaminated Soil▿

PubMed Central

Sitte, Jana; Akob, Denise M.; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E.; Scheinost, Andreas C.; Büchel, Georg; Küsel, Kirsten

2010-01-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the 35SO42− radiotracer method, was restricted to reduced soil horizons with rates of ≤142 ± 20 nmol cm−3 day−1. Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that ∼80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [13C]acetate- and [13C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined ≤100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching ≤1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems. PMID:20363796

40 CFR 440.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2010 CFR

2010-07-01

..., radium and vanadium including mill-mine facilities and mines using in-situ leach methods shall not exceed...). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source... available (BPT): (a) The concentration of pollutants discharged in mine drainage from mines, either open-pit...

40 CFR 440.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2011 CFR

2011-07-01

..., radium and vanadium including mill-mine facilities and mines using in-situ leach methods shall not exceed...). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source... available (BPT): (a) The concentration of pollutants discharged in mine drainage from mines, either open-pit...

Microbiological effectiveness of household water treatment technologies under field use conditions in rural Tanzania.

PubMed

Mohamed, Hussein; Clasen, Thomas; Njee, Robert Mussa; Malebo, Hamisi M; Mbuligwe, Stephen; Brown, Joe

2016-01-01

To assess the microbiological effectiveness of several household water treatment and safe storage (HWTS) options in situ in Tanzania, before consideration for national scale-up of HWTS. Participating households received supplies and instructions for practicing six HWTS methods on a rotating 5-week basis. We analysed 1202 paired samples (source and treated) of drinking water from 390 households, across all technologies. Samples were analysed for thermotolerant (TTC) coliforms, an indicator of faecal contamination, to measure effectiveness of treatment in situ. All HWTS methods improved microbial water quality, with reductions in TTC of 99.3% for boiling, 99.4% for Waterguard ™ brand sodium hypochlorite solution, 99.5% for a ceramic pot filter, 99.5% for Aquatab ® sodium dichloroisocyanurate (NaDCC) tablets, 99.6% for P&G Purifier of Water ™ flocculent/disinfectant sachets, and 99.7% for a ceramic siphon filter. Microbiological performance was relatively high compared with other field studies and differences in microbial reductions between technologies were not statistically significant. Given that microbiological performance across technologies was comparable, decisions regarding scale-up should be based on other factors, including uptake in the target population and correct, consistent, and sustained use over time. © 2015 John Wiley & Sons Ltd.

Heterogeneous enantioselective hydrogenation of beta-keto esters using chirally modified supported Ni nanoparticles

NASA Astrophysics Data System (ADS)

Acharya, Sushma

Enantioselective heterogeneous catalysis is an important and rapidly expanding research area. The two most heavily researched examples of this type of catalysis are the enantioselective hydrogenation of α-keto-esters over Pt-based catalysts and the enantioselective hydrogenation of β-keto-esters over Ni-based catalysts. These enantioselective surface reactions are controlled by the presence of adsorbed chiral molecules i.e. tartaric acid on the surface of the metal component of the catalyst. The work presented in this thesis focuses on two parts, the synthesis of pure nickel nanoparticles and enantioselective behavior of the modified nickel nanoparticles. The works on the synthesis of pure nickel nanoparticles were carried out using two methods, the reverse microemulsion and the reduction method. It was discovered that the reverse microemulsion method produced nickel oxide nanoparticles, whereas the reduction method produced pure nickel nanoparticles. Chiral modifications of Raney nickel (RNi) and C-supported catalysts were studied. The catalysts were employed in enantioselective hydrogenation of methyl acetoacetate (MAA) to (R) - and (S)-enantiomers of methyl 3-hydroxybutyrate (MHB). The effects of modification and hydrogenation parameters such as concentration of modifier temperature, pressure and solvent on the enantioselectivity of MAA hydrogenation were discussed. For RNi methanol was found to be the best solvent, with tartaric acid concentration 0.2 mol/L for achieving the highest enantiomeric excess under 8 bar at 70 oC. Characteristic features of the in-situ modification of Raney nickel and C-supported Ni were also evaluated and the results obtained were compared with the conventional (pre-modification) approach. Parameters for the conventional and in-situ methods were optimised in a series of experiments for both types of catalysts. The in-situ modified catalyst was found more active for both RNi and C-supported catalysts with 98 % and 42% enantiomeric excess, respectively.

Voltage-induced reduction of graphene oxide

NASA Astrophysics Data System (ADS)

Faucett, Austin C.

Graphene Oxide (GO) is being widely researched as a precursor for the mass production of graphene, and as a versatile material in its own right for flexible electronics, chemical sensors, and energy harvesting applications. Reduction of GO, an electrically insulating material, into reduced graphene oxide (rGO) restores electrical conductivity via removal of oxygen-containing functional groups. Here, a reduction method using an applied electrical bias, known as voltage-induced reduction, is explored. Voltage-induced reduction can be performed under ambient conditions and avoids the use of hazardous chemicals or high temperatures common with standard methods, but little is known about the reduction mechanisms and the quality of rGO produced with this method. This work performs extensive structural and electrical characterization of voltage-reduced GO (V-rGO) and shows that it is competitive with standard methods. Beyond its potential use as a facile and eco-friendly processing approach, V-rGO reduction also offers record high-resolution patterning capabilities. In this work, the spatial resolution limits of voltage-induced reduction, performed using a conductive atomic force microscope probe, are explored. It is shown that arbitrary V-rGO conductive features can be patterned into insulating GO with nanoscale resolution. The localization of voltage-induced reduction to length scales < 10 nm allows studies of reduction reaction kinetics, using electrical current obtained in-situ, with statistical robustness. Methods for patterning V-rGO nanoribbons are then developed. After presenting sub-10nm patterning of V-rGO nanoribbons in GO single sheets and films, the performance of V-rGO nanoribbon field effect transistors (FETs) are demonstrated. Preliminary measurements show an increase in electrical current on/off ratios as compared to large-area rGO FETs, indicating transport gap modulation that is possibly due to quantum confinement effects.

Salinity Responses of Benthic Microbial Communities in a Solar Saltern (Eilat, Israel)

PubMed Central

Sørensen, Ketil Bernt; Canfield, Donald E.; Oren, Aharon

2004-01-01

The salinity responses of cyanobacteria, anoxygenic phototrophs, sulfate reducers, and methanogens from the laminated endoevaporitic community in the solar salterns of Eilat, Israel, were studied in situ with oxygen microelectrodes and in the laboratory in slurries. The optimum salinity for the sulfate reduction rate in sediment slurries was between 100 and 120‰, and sulfate reduction was strongly inhibited at an in situ salinity of 215‰. Nevertheless, sulfate reduction was an important respiratory process in the crust, and reoxidation of formed sulfide accounted for a major part of the oxygen budget. Methanogens were well adapted to the in situ salinity but contributed little to the anaerobic mineralization in the crust. In slurries with a salinity of 180‰ or less, methanogens were inhibited by increased activity of sulfate-reducing bacteria. Unicellular and filamentous cyanobacteria metabolized at near-optimum rates at the in situ salinity, whereas the optimum salinity for anoxygenic phototrophs was between 100 and 120‰. PMID:15006785

Availability and assessment of fixing additives for the in situ remediation of heavy metal contaminated soils: a review.

PubMed

Guo, Guanlin; Zhou, Qixing; Ma, Lene Q

2006-05-01

The use of low-cost and environmental safety amendments for the in situ immobilization of heavy metals has been investigated as a promising method for contaminated soil remediation. Natural materials and waste products from certain industries with high captive capacity of heavy metals can be obtained and employed. Reduction of extractable metal concentration and phytotoxicity could be evaluated and demonstrated by the feasibility of various amendments in fixing remediation. In this review, an extensive list of references has been compiled to provide a summary of information on a wide range of potentially amendment resources, including organic, inorganic and combined organic-inorganic materials. The assessment based on the economic efficiency and environmental risks brought forth the potential application values and future development directions of this method on solving the soil contamination.

Highly transparent carbon counter electrode prepared via an in situ carbonization method for bifacial dye-sensitized solar cells.

PubMed

Bu, Chenghao; Liu, Yumin; Yu, Zhenhua; You, Sujian; Huang, Niu; Liang, Liangliang; Zhao, Xing-Zhong

2013-08-14

A facile in situ carbonization method was demonstrated to prepare the highly transparent carbon counter electrode (CE) with good mechanical stability for bifacial dye-sensitized solar cells (DSCs). The optical and electrochemical properties of carbon CEs were dramatically affected by the composition and concentration of the precursor. The well-optimized carbon CE exhibited high transparency and sufficient catalytic activity for I3(-) reduction. The bifacial DSC with obtained carbon CE achieved a high power conversion efficiency (PCE) of 5.04% under rear-side illumination, which approaches 85% that of front-side illumination (6.07%). Moreover, the device shows excellent stability as confirmed by the aging test. These promising results reveal the enormous potential of this transparent carbon CE in scaling up and commercialization of low cost and effective bifacial DSCs.

An Efficient, Solvent-Free Process for Synthesizing Anhydrous MgCl 2

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

Motkuri, Radha K.; Vemuri, Venkata Rama S.; Barpaga, Dushyant

A new efficient and solvent-free method for the synthesis of anhydrous MgCl2 from its hexahydrate is proposed. Fluidized dehydration of MgCl 2·6H 2O feedstock at 200 °C in a porous bed reactor yields MgCl2·nH2O (0 < n < 1), which has a similar diffraction pattern as activated MgCl2. The MgCl 2·nH 2O is then ammoniated directly using liquefied NH 3 in the absence of solvent to form MgCl 2·6NH 3. Calcination of the hexammoniate complex at 300 °C then yields anhydrous MgCl 2. Both dehydration and deammoniation were thoroughly studied using in situ as well as ex situ characterization techniques.more » Specifically, a detailed understanding of the dehydration process was monitored by in situ PXRD and in situ FTIR techniques where formation of salt with nH 2O (n = 4, 2, 1, <1) was characterized. Given the reduction in thermal energy required to produce dehydrated feedstock with this method compared with current strategies, significant cost benefits are expected. Overall, the combined effect of activation, macroporosity, and coordinated water depletion allows the formation of hexammoniate without using solvent, thus minimizing waste formation.« less

Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

PubMed

Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

2017-06-20

An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

Solar Concentrator Demonstrator for Lunar Regolith Processing

NASA Technical Reports Server (NTRS)

Fikes, John C.; Howell, Joe T.; Gerrish, Harold P.; Patrick, Stephen L.

2008-01-01

NASA at the Marshall Space Flight Center (MSFC) is building a portable inflatable solar concentrator ground demonstrator for use in testing in-situ resource utilization (ISRU) lunar regolith processing methods. Of primary interest is the production of oxygen as a propellant oxidizer and for life support. There are various processes being proposed for the in-situ reduction of the lunar regolith, the leading processes are hydrogen reduction, carbothermal reduction and vapor phase pyrolysis. The concentrator system being built at MSFC could support demonstrations of all of these processes. The system consists of a light inflatable concentrator that will capture sunlight and focus it onto a receiver inside a vacuum chamber. Inflatable concentrators are good for space based applications due to their low weight and dense packaging at launch. The hexapod design allows the spot size to be increased to reduce the power density if needed for the process being demonstrated. In addition to the hardware development, a comprehensive simulation model is being developed and will be verified and validated using the system hardware. The model will allow for the evaluation of different lunar locations and operational scenarios for the lunar regolith processing with a high confidence in the predicted results.

In situ IR studies of Co and Ce doped Mn/TiO2 catalyst for low-temperature selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng

2015-12-01

The Mn-Co-Ce/TiO2 catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH3 in the presence of oxygen. The adsorption and co-adsorption of NH3, NO and O2 on catalysts were investigated by in situ FTIR spectroscopy. The results suggested that addition of cobalt and cerium oxides increased the numbers of acid and redox sites. Especially, the cobalt oxide produced lots of Brønsted acid sites, which favor to the adsorption of coordinated NH3 through NH3 migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn-Co-Ce/TiO2 was proposed. At low-temperature SCR reaction, coordinated NH3 reacted with NO2-, and amide reacted with NO (ad) or NO (g) to form N2. NO2 was related to the formation of nitrite on Co-contained catalysts and the generation of sbnd NH2- on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH3 and nitrate species, resulting in N2O yield increase.

Fabrication of biomembrane-like films on carbon electrodes using alkanethiol and diazonium salt and their application for direct electrochemistry of myoglobin.

PubMed

Anjum, Saima; Qi, Wenjing; Gao, Wenyue; Zhao, Jianming; Hanif, Saima; Aziz-Ur-Rehman; Xu, Guobao

2015-03-15

Alkanethiols generally form self-assembled monolayers on gold electrodes and the electrochemical reduction of aromatic diazonium salts is a popular method for the covalent modification of carbon. Based on the reaction of alkanethiol with aldehyde groups covalently bound on carbon surface by the electrochemical reduction of aromatic diazonium salts, a new strategy for the modification of carbon electrodes with alkanethiols has been developed. The modification of carbon surface with aldehyde groups is achieved by the electrochemical reduction of aromatic diazonium salts in situ electrogenerated from a nitro precursor, p-nitrophenylaldehyde, in the presence of nitrous acid. By this way, in situ electrogenerated p-aminophenyl aldehyde from p-nitrophenylaldehyde immediately reacts with nitrous acid, effectively minimizing the side reaction of amine groups and aldehyde groups. The as-prepared alkanethiol-modified glassy carbon electrode was further used to make biomembrane-like films by casting didodecyldimethylammonium bromide on its surface. The biomembrane-like films enable the direct electrochemistry of immobilized myoglobin for the detection of hydrogen peroxide. The response is linear over the range of 1-600μM with a detection limit of 0.3μM. Copyright © 2014 Elsevier B.V. All rights reserved.

Monitoring Physical and Biogeochemical Dynamics of Uranium Bioremediation at the Intermediate Scale

NASA Astrophysics Data System (ADS)

Tarrell, A. N.; Figueroa, L. A.; Rodriguez, D.; Haas, A.; Revil, A.

2011-12-01

Subsurface uranium above desired levels for aquifer use categories exists naturally and from historic mining and milling practices. In situ bioimmobilization offers a cost effective alternative to conventional pump and treat methods by stimulating growth of microorganisms that lead to the reduction and precipitation of uranium. Vital to the long-term success of in situ bioimmobilization is the ability to successfully predict and demonstrate treatment effectiveness to assure that regulatory goals are met. However, successfully monitoring the progress over time is difficult and requires long-term stewardship to ensure effective treatment due to complex physical and biogeochemical heterogeneity. In order to better understand these complexities and the resultant effect on uranium immobilization, innovative systematic monitoring approaches with multiple performance indicators must be investigated. A key issue for uranium bioremediation is the long term stability of solid-phase reduction products. It has been shown that a combination of data from electrode-based monitoring, self-potential monitoring, oxidation reduction potential (ORP), and water level sensors provides insight for identifying and localizing bioremediation activity and can provide better predictions of deleterious biogeochemical change such as pore clogging. In order to test the proof-of-concept of these sensing techniques and to deconvolve redox activity from other electric potential changing events, an intermediate scale 3D tank experiment has been developed. Well-characterized materials will be packed into the tank and an artificial groundwater will flow across the tank through a constant-head boundary. The experiment will utilize these sensing methods to image the electrical current produced by bacteria as well as indications of when and where electrical activity is occurring, such as with the reduction of radionuclides. This work will expand upon current knowledge by exploring the behavior of uranium bioremediation at an intermediate scale, as well as examining the effects from introducing a flow field in a laboratory setting. Data collected from this experiment will help further characterize which factors are contributing to current increases. Additional information concerning the effect of geochemical changes in porosity may also be observed. The results of this work will allow the creation of a new data set collected from a more comprehensive laboratory monitoring network and will allow stakeholders to develop effective decision-making tools on the long-term remediation management at uranium contaminated sites. The data will also aid in the long-term prediction abilities of a reactive transport models. As in situ bioremediation offers a low cost alternative to ex situ treatment methods, the results of this work will help to both reduce cost at existing sites and enable treatment of sites that otherwise have no clear solution.

Fabrication of selectively functionalized-graphene reinforced copper phthalocyanine nanocomposites with low dielectric loss and high dielectric constant

NASA Astrophysics Data System (ADS)

Wang, Zicheng; Wei, Renbo; Liu, Xiaobo

2017-01-01

A novel kind of selectively functionalized-graphene reinforced copper phthalocyanine (RGO-O-CuPc) nanocomposites was successfully fabricated through a facile and effective three-step method, involving preferential surficial modification and reduction of graphene oxide (GO) sheets, and followed by incorporating with CuPc via in situ polymerization. The results of SEM, AFM, XPS, FTIR, XRD and UV-vis confirmed that GO was effectively surficial functionalized by a ring-open covalent reaction between amino in 3-aminophenoxyphthalonitrile (3-APN) and epoxy groups on the GO sheets, and partly reduced back to graphene under solvothermal conditions. And the RGO-O-CuPc was successfully fabricated by self-assembling of CuPc molecule on graphene sheets via in situ polymerization. As a consequence, the selective surface functionalization and solvothermal reduction of GO facilitated the improvement in the dielectric constant and AC conductivity, and the decrease in the dielectric loss of the graphene/CuPc nanocomposites.

Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt-Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy.

PubMed

Flynn, Brendan T; Oleksak, Richard P; Thevuthasan, Suntharampillai; Herman, Gregory S

2018-01-31

A method to understand the role of interfacial chemistry on the modulation of Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. In situ X-ray photoelectron spectroscopy was used to characterize the interfacial chemistries that modulate barrier heights in this system. The primary changes were a significant chemical reduction of indium, from In 3+ to In 0 , that occurs during deposition of Pt on to the a-IGZO surface in ultrahigh vacuum. Postannealing and controlling the background ambient O 2 pressure allows further tuning of the reduction of indium and the corresponding Schottky barrier heights from 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metal-semiconductor field-effect transistors.

Bio-Based Artificial Nacre with Excellent Mechanical and Barrier Properties Realized by a Facile In Situ Reduction and Cross-Linking Reaction.

PubMed

Shahzadi, Kiran; Mohsin, Imran; Wu, Lin; Ge, Xuesong; Jiang, Yijun; Li, Hui; Mu, Xindong

2017-01-24

Demands for high strength integrated materials have substantially increased across various kinds of industries. Inspired by the relationship of excellent integration of mechanical properties and hierarchical nano/microscale structure of the natural nacre, a simple and facile method to fabricate high strength integrated artificial nacre based on sodium carboxymethylcellulose (CMC) and borate cross-linked graphene oxide (GO) sheets has been developed. The tensile strength and toughness of cellulose-based hybrid material reached 480.5 ± 13.1 MPa and 11.8 ± 0.4 MJm -3 by a facile in situ reduction and cross-linking reaction between CMC and GO (0.7%), which are 3.55 and 6.55 times that of natural nacre. This hybrid film exhibits better thermal stability and flame retardancy. More interestingly, the hybrid material showed good water stability compared to that in the original water-soluble CMC. This type of hybrid has great potential applications in aerospace, artificial muscle, and tissue engineering.

Asymmetric Volcano Trend in Oxygen Reduction Activity of Pt and Non-Pt Catalysts: In Situ Identification of the Site-Blocking Effect.

PubMed

Li, Jingkun; Alsudairi, Amell; Ma, Zi-Feng; Mukerjee, Sanjeev; Jia, Qingying

2017-02-01

Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR catalysts with a wide range of redox potential (E redox ) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the E redox of active sites; and the intrinsic activity of active sites with low E redox have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high E redox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low E redox side is limited by either the site-blocking effect and/or intrinsic activity depending on the E redox .

Highly Stretchable and Conductive Silver Nanoparticle Embedded Graphene Flake Electrode Prepared by In situ Dual Reduction Reaction.

PubMed

Yoon, Yeoheung; Samanta, Khokan; Lee, Hanleem; Lee, Keunsik; Tiwari, Anand P; Lee, JiHun; Yang, Junghee; Lee, Hyoyoung

2015-09-18

The emergence of stretchable devices that combine with conductive properties offers new exciting opportunities for wearable applications. Here, a novel, convenient and inexpensive solution process was demonstrated to prepare in situ silver (Ag) or platinum (Pt) nanoparticles (NPs)-embedded rGO hybrid materials using formic acid duality in the presence of AgNO3 or H2PtCl6 at low temperature. The reduction duality of the formic acid can convert graphene oxide (GO) to rGO and simultaneously deposit the positively charged metal ion to metal NP on rGO while the formic acid itself is converted to a CO2 evolving gas that is eco-friendly. The AgNP-embedded rGO hybrid electrode on an elastomeric substrate exhibited superior stretchable properties including a maximum conductivity of 3012 S cm(-1) (at 0 % strain) and 322.8 S cm(-1) (at 35 % strain). Its fabrication process using a printing method is scalable. Surprisingly, the electrode can survive even in continuous stretching cycles.

Combining Low-Energy Electrical Resistance Heating with Biotic and Abiotic Reactions for Treatment of Chlorinated Solvent DNAPL Source Areas

DTIC Science & Technology

2015-01-01

5 2.1.2 In Situ Bioremediation ...Technology Certification Program gpm gallons per minute ISB in situ bioremediation JBLM Joint Base Lewis-McChord mmol millimole MROD Mount...EXECUTIVE SUMMARY BACKGROUND The applicability of in situ groundwater remedies such as in situ bioremediation (ISB) or zero valent iron (ZVI) reduction

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

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac)2, to vanadium acetylacetonate, V(acac)3, is introduced. V(acac)3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac)2. In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H+), the reduction can take place between 2.25 and 1.5 V versus Na/Na+ via a one-electron-transfer reduction.more » This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na–Cs alloy as the anode. The in situ recovery of V(acac)3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V3+/V4+ and V2+/V3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac)3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future.« less

IN SITU SOURCE TREATMENT OF CR(VI) USING A FE(II)-BASED REDUCTANT BLEND: LONG-TERM MONITORING AND EVALUATION

EPA Science Inventory

The long-term effectiveness of a FeSO4 + Na2S2O4 reductant solution blend for in situ saturated zone treatment of dissolved and solid phase Cr(VI) in a high pH chromite ore processing solid waste (COPSW) fill material was investigated. Two field pilot injection studies were cond...

Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope.

PubMed

Abellan, Patricia; Parent, Lucas R; Al Hasan, Naila; Park, Chiwoo; Arslan, Ilke; Karim, Ayman M; Evans, James E; Browning, Nigel D

2016-02-16

Synthesizing nanomaterials of uniform shape and size is of critical importance to access and manipulate the novel structure-property relationships arising at the nanoscale, such as catalytic activity. In this work, we synthesize Pd nanoparticles with well-controlled size in the sub-3 nm range using scanning transmission electron microscopy (STEM) in combination with an in situ liquid stage. We use an aromatic hydrocarbon (toluene) as a solvent that is very resistant to high-energy electron irradiation, which creates a net reducing environment without the need for additives to scavenge oxidizing radicals. The primary reducing species is molecular hydrogen, which is a widely used reductant in the synthesis of supported metal catalysts. We propose a mechanism of particle formation based on the effect of tri-n-octylphosphine (TOP) on size stabilization, relatively low production of radicals, and autocatalytic reduction of Pd(II) compounds. We combine in situ STEM results with insights from in situ small-angle X-ray scattering (SAXS) from alcohol-based synthesis, having similar reduction potential, in a customized microfluidic device as well as ex situ bulk experiments. This has allowed us to develop a fundamental growth model for the synthesis of size-stabilized Pd nanoparticles and demonstrate the utility of correlating different in situ and ex situ characterization techniques to understand, and ultimately control, metal nanostructure synthesis.

INHIBITION OF REDUCTIVE DECHLORINATION BY SULFATE REDUCTION IN MICROCOSMS (ABSTRACT ONLY)

EPA Science Inventory

High sulfate (>1,000 mg/L) concentrations are potentially problematic for field implementation of in situ bioremediation of chlorinated ethenes because its reduction competes for electron donor with reductive dechlorination. As a result of this competition, reductive dechl...

Activated Biochars with Iron for In-Situ Sequestration of Organics, Metals and Carbon

DTIC Science & Technology

2012-04-30

Research Center. Total mercury analysis (EPA Method 1631) was performed following digestion , reduction, and gold-trapping. Methylmercury analysis...effective carbon at removing high Hg concentrations from solution in the pH edge study. Apart from having relatively high levels of sulfur, broiler ...Pyrolysis of Broiler Manure: Char and Product Gas Characterization. Industrial & Engineering Chemistry Research 48, 1292-1297. 48 Lohmann, R

In situ remediation of chlorinated solvent-contaminated groundwater using ZVI/organic carbon amendment in China: field pilot test and full-scale application.

PubMed

Yang, Jie; Meng, Liang; Guo, Lin

2018-02-01

Chlorinated solvents in groundwater pose threats to human health and the environment due to their carcinogenesis and bioaccumulation. These problems are often more severe in developing countries such as China. Thus, methods for chlorinated solvent-contaminated groundwater remediation are urgently needed. This study presents a technique of in situ remediation via the direct-push amendment injection that enhances the reductive dechlorination of chlorinated solvents in groundwater in the low-permeability aquifer. A field-based pilot test and a following real-world, full-scale application were conducted at an active manufacturing facility in Shanghai, China. The chlorinated solvents found at the clay till site included 1,1,1-trichloroethane (1,1,1-TCA), 1,1-dichloroethane (1,1-DCA), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), and chloroethane (CA). A commercially available amendment (EHC ® , Peroxychem, Philadelphia, PA) combining zero-valent iron and organic carbon was used to treat the above pollutants. Pilot test results showed that direct-push EHC injection efficiently facilitated the in situ reductive remediation of groundwater contaminated with chlorinated solvents. The mean removal rates of 1,1,1-TCA, 1,1-DCA, and 1,1-DCE at 270 days post-injection were 99.6, 99.3, and 73.3%, respectively, which were obviously higher than those of VC and CA (42.3 and 37.1%, respectively). Clear decreases in oxidation-reduction potential and dissolved oxygen concentration, and increases in Fe 2+ and total organic carbon concentration, were also observed during the monitoring period. These indicate that EHC promotes the anaerobic degradation of chlorinated hydrocarbons primarily via long-term biological reductive dechlorination, with instant chemical reductive dechlorination acting as a secondary pathway. The optimal effective time of EHC injection was 0-90 days, and its radius of influence was 1.5 m. In full-scale application, the maximum concentrations of 1,1,1-TCA and 1,1-DCA in the contaminate plume fell below the relevant Dutch Intervention Values at 180 days post-injection. Moreover, the dynamics of the target pollutant concentrations mirrored those of the pilot test. Thus, we have demonstrated that the direct-push injection of EHC successfully leads to the remediation of chlorinated solvent-contaminated groundwater in a real-world scenario. The parameters determined by this study (e.g., effectiveness, injection amount, injection depth, injection pressures, and radius of influence) are applicable to other low-permeability contaminated sites where in situ remediation by enhanced reductive dechlorination is required.

Towards multifunctional cellulosic fabric: UV photo-reduction and in-situ synthesis of silver nanoparticles into cellulose fabrics.

PubMed

Rehan, Mohamed; Barhoum, Ahmed; Van Assche, Guy; Dufresne, Alain; Gätjen, Linda; Wilken, Ralph

2017-05-01

Herein, the highly multifunctional cotton fabric surfaces were designed with excellent coloration, UV-protection function, and antimicrobial activity. These multifunctional functions were developed by in-situ synthesis of silver nanoparticles (Ag NPs) into the cotton fabric surface using a simple green one-pot "UV-reduction" method. Cotton fabrics were pretreated with non-anionic detergent, immersed into alcoholic silver nitrate solution (concentration ranging from 100 to 500ppm), squeezed to remove excess solution and then exposed to UV-irradiation (range 320-400nm) for 1h. The influence UV-irradiation on the thermal, chemical, optical and biological properties of the cotton fabric surface was discussed in details. The UV-irradiation promotes reducing of Ag + ions and the cotton fabrics act as seed medium for Ag NPs formation by "heterogeneous nucleation". Increasing Ag + concentration (from 100 to 500ppm) results in Ag NPs of particle size (distribution) of 50-100nm. Interestingly, the Ag NPs exhibited different localized surface Plasmon resonance properties causing a coloration of the cotton fabrics with different color shades ranging from bright to dark brown with excellent color fastness properties. The treated cotton fabrics also show high protecting functions against UV-transmission (reduction of 65%) and Escherichia coli growth (99%). The side-effects of the UV-reduction process are further investigated. Published by Elsevier B.V.

Preparation and thermal insulation performance of cast-in-situ phosphogypsum wall.

PubMed

Li, Yubo; Dai, Shaobin; Zhang, Yichao; Huang, Jun; Su, Ying; Ma, Baoguo

2018-01-01

The mass accumulation of phosphogypsum has caused serious environmental pollution, which has become a worldwide problem. Gypsum is a kind of green building material, which is lighter, has better heat and sound insulation performance, and is easier to recycle compared to cement. The application of cast-in-situ phosphogypsum wall could consume a large amount of pollutant, and improve the efficiency of building construction. The preparation and thermal insulation performance of cast-in-situ phosphogypsum wall were investigated. The property of phosphogypsum-fly ash-lime (PFL) triad cementing materials, the adaptability of retarders and superplasticizers, and the influences of vitrified microsphere as aggregates were explored. Thus, the optimum mix was proposed. Thermal insulation performance tests and ANSYS simulation of this material was carried out. Optimal structures based on heat channels and the method of calculation determining related parameters were proposed, which achieved a 12.3% reduction in the heat transfer coefficient of the wall. With good performance, phosphogypsum could be used in cast-in-situ walls. This paper provides the theoretical basis for the preparation and energy-saving application of phosphogypsum in the walls of buildings.

New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries.

PubMed

Shamie, Jack S; Liu, Caihong; Shaw, Leon L; Sprenkle, Vincent L

2017-02-08

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac) 2 , to vanadium acetylacetonate, V(acac) 3 , is introduced. V(acac) 3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac) 2 . In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H + ), the reduction can take place between 2.25 and 1.5 V versus Na/Na + via a one-electron-transfer reduction. This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na-Cs alloy as the anode. The in situ recovery of V(acac) 3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V 3+ /V 4+ and V 2+ /V 3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac) 3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ generation of highly dispersed metal nanoparticles on two-dimensional layered SiO2 by topotactic structure conversion and their superior catalytic activity

NASA Astrophysics Data System (ADS)

Chen, Zhe; Jia, Da-Shuang; Zhou, Yue; Hao, Jiang; Liang, Yu; Cui, Zhi-Min; Song, Wei-Guo

2018-03-01

Metal nanoparticles such as Ag, Cu and Fe are effective catalysts for many reactions, whereas a facile method to prepare metal nanoparticles with high uniformed dispersion is still desirable. Herein, the topotactic structure conversion of layered silicate, RUB-15, was utilized to support metal nanoparticles. Through simple ion-exchange and following calcination step, metal nanoparticles were generated in situ inside the interlayer space of layered silica, and the topotactic structure conversion process assured nano-sized and highly uniformed dispersion of metal nanoparticles. The obtained Ag/SiO2 composite showed superior catalytic activity for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB), with a rate constant as high as 0.0607 s-1 and 0.0778 s-1. The simple and universal synthesis method as well as high activity of the product composite endow the strategy good application prospect.

In-situ health monitoring of piezoelectric sensors using electromechanical impedance: A numerical perspective

NASA Astrophysics Data System (ADS)

Bilgunde, Prathamesh N.; Bond, Leonard J.

2018-04-01

Current work presents a numerical investigation to classify the in-situ health of the piezoelectric sensors deployed for structural health monitoring (SHM) of large civil, aircraft and automotive structures. The methodology proposed in this work attempts to model the in-homogeneities in the adhesive with which typically the sensor is bonded to the structure for SHM. It was found that weakening of the bond state causes reduction in the resonance frequency of the structure and eventually approaches the resonance characteristics of a piezoelectric material under traction-free boundary conditions. These changes in the resonance spectrum are further quantified using root mean square deviation-based damage index. Results demonstrate that the electromechanical impedance method can be used to monitor structural integrity of the sensor bonded to the host structure. This cost-effective method can potentially reduce misinterpretation of SHM data for critical infrastructures.

In Situ Industrial Bimetallic Catalyst Characterization using Scanning Transmission Electron Microscopy and X-ray Absorption Spectroscopy at One Atmosphere and Elevated Temperature.

PubMed

Prestat, Eric; Kulzick, Matthew A; Dietrich, Paul J; Smith, Mr Matthew; Tien, Mr Eu-Pin; Burke, M Grace; Haigh, Sarah J; Zaluzec, Nestor J

2017-08-18

We have developed a new experimental platform for in situ scanning transmission electron microscope (STEM) energy dispersive X-ray spectroscopy (EDS) which allows real time, nanoscale, elemental and structural changes to be studied at elevated temperature (up to 1000 °C) and pressure (up to 1 atm). Here we demonstrate the first application of this approach to understand complex structural changes occurring during reduction of a bimetallic catalyst, PdCu supported on TiO 2 , synthesized by wet impregnation. We reveal a heterogeneous evolution of nanoparticle size, distribution, and composition with large differences in reduction behavior for the two metals. We show that the data obtained is complementary to in situ STEM electron energy loss spectroscopy (EELS) and when combined with in situ X-ray absorption spectroscopy (XAS) allows correlation of bulk chemical state with nanoscale changes in elemental distribution during reduction, facilitating new understanding of the catalytic behavior for this important class of materials. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

In situ hydrogen consumption kinetics as an indicator of subsurface microbial activity

USGS Publications Warehouse

Harris, S.H.; Smith, R.L.; Suflita, J.M.

2007-01-01

There are few methods available for broadly assessing microbial community metabolism directly within a groundwater environment. In this study, hydrogen consumption rates were estimated from in situ injection/withdrawal tests conducted in two geochemically varying, contaminated aquifers as an approach towards developing such a method. The hydrogen consumption first-order rates varied from 0.002 nM h-1 for an uncontaminated, aerobic site to 2.5 nM h-1 for a contaminated site where sulfate reduction was a predominant process. The method could accommodate the over three orders of magnitude range in rates that existed between subsurface sites. In a denitrifying zone, the hydrogen consumption rate (0.02 nM h-1) was immediately abolished in the presence of air or an antibiotic mixture, suggesting that such measurements may also be sensitive to the effects of environmental perturbations on field microbial activities. Comparable laboratory determinations with sediment slurries exhibited hydrogen consumption kinetics that differed substantially from the field estimates. Because anaerobic degradation of organic matter relies on the rapid consumption of hydrogen and subsequent maintenance at low levels, such in situ measures of hydrogen turnover can serve as a key indicator of the functioning of microbial food webs and may be more reliable than laboratory determinations. ?? 2007 Federation of European Microbiological Societies.

Preparation and evaluation of injectable Rasagiline mesylate dual-controlled drug delivery system for the treatment of Parkinson's disease.

PubMed

Jiang, Ying; Zhang, Xuemei; Mu, Hongjie; Hua, Hongchen; Duan, Dongyu; Yan, Xiuju; Wang, Yiyun; Meng, Qingqing; Lu, Xiaoyan; Wang, Aiping; Liu, Wanhui; Li, Youxin; Sun, Kaoxiang

2018-11-01

A microsphere-gel in situ forming implant (MS-Gel ISFI) dual-controlled drug delivery system was applied to a high water-soluble small-molecule compound Rasagiline mesylate (RM) for effective treatment of Parkinson's disease. This injectable complex depot system combined an in situ phase transition gel with high drug-loading and encapsulation efficiency RM-MS prepared by a modified emulsion-phase separation method and optimized by Box-Behnken design. It was evaluated for in vitro drug release, in vivo pharmacokinetics, and in vivo pharmacodynamics. We found that the RM-MS-Gel ISFI system showed no initial burst release and had a long period of in vitro drug release (60 days). An in vivo pharmacokinetic study indicated a significant reduction (p < .01) in the initial high plasma drug concentration of the RM-MS-Gel ISFI system compared to that of the single RM-MS and RM-in situ gel systems after intramuscular injection to rats. A pharmacodynamic study demonstrated a significant reduction (p < .05) in 6-hydroxydopamine-induced contralateral rotation behavior and an effective improvement (p < .05) in dopamine levels in the striatum of the lesioned side after 28 days in animals treated with the RM-MS-Gel ISFI compared with that of animals treated with saline. MS-embedded in situ phase transition gel is superior for use as a biodegradable and injectable sustained drug delivery system with a low initial burst and long period of drug release for highly hydrophilic small molecule drugs.

Promising Emerging Mechanisms

EPA Science Inventory

Most applications of enhanced in situ bioremediation are based on biological reductive dechlorination. Anaerobic metabolism can also produce reactive minerals that allow for in situ biogeochemical transformation of chlorinated organic contaminants such as PCE, TCE, and cis-DCE. ...

Interactions between Biological and Abiotic Pathways in the Reduction of Chlorinated Solvents

EPA Science Inventory

While biologically mediated reductive dechlorination continues to be a significant focus of chlorinated solvent remediation, there has been an increased interest in abiotic reductive processes for the remediation of chlorinated solvents. In situ chemical reduction (ISCR) uses zer...

Laser irradiation-induced laminated graphene/MoS2 composites with synergistically improved tribological properties.

PubMed

Luo, Ting; Chen, Xinchun; Li, Peisheng; Wang, Ping; Li, Cuncheng; Cao, Bingqiang; Luo, Jianbin; Yang, Shikuan

2018-06-29

Engineering lubricant additives that have extraordinary friction reduction and anti-wear performance is critical to almost any modern mechanical machines. Here, we demonstrate the fabrication of laminated lubricant additives that can combine the advantages of zero-dimensional nanospheres and two-dimensional nanosheets. A simple in situ laser irradiation method is developed to prepare the laminated composite structure composed of ideally ultrasmooth MoS 2 sub-microspheres embedded within multiple layers of graphene. These ultrasmooth MoS 2 spheres within the laminated structure can change sliding friction into rolling friction under strong shear force created by moving contact surfaces to significantly reduce the friction. Meantime, the graphene layers can behave as 'protection pads' to efficiently avoid the formation of scars on the metal-to-metal contact surfaces. Overall, the laminated composites as lubricant additives synergistically improve the friction reduction and anti-wear properties. Additionally, due to the unique loosely packed laminated structure, the composites can stably disperse in the lubricant for more than 15 d and work under high temperatures without being oxidized. Such constructed laminated composites with outstanding tribological properties by an in situ laser irradiation method supply a new concept in designing lubricant additives that can combine the advantages of 0D and 2D structures.

Laser irradiation-induced laminated graphene/MoS2 composites with synergistically improved tribological properties

NASA Astrophysics Data System (ADS)

Luo, Ting; Chen, Xinchun; Li, Peisheng; Wang, Ping; Li, Cuncheng; Cao, Bingqiang; Luo, Jianbin; Yang, Shikuan

2018-06-01

Engineering lubricant additives that have extraordinary friction reduction and anti-wear performance is critical to almost any modern mechanical machines. Here, we demonstrate the fabrication of laminated lubricant additives that can combine the advantages of zero-dimensional nanospheres and two-dimensional nanosheets. A simple in situ laser irradiation method is developed to prepare the laminated composite structure composed of ideally ultrasmooth MoS2 sub-microspheres embedded within multiple layers of graphene. These ultrasmooth MoS2 spheres within the laminated structure can change sliding friction into rolling friction under strong shear force created by moving contact surfaces to significantly reduce the friction. Meantime, the graphene layers can behave as ‘protection pads’ to efficiently avoid the formation of scars on the metal-to-metal contact surfaces. Overall, the laminated composites as lubricant additives synergistically improve the friction reduction and anti-wear properties. Additionally, due to the unique loosely packed laminated structure, the composites can stably disperse in the lubricant for more than 15 d and work under high temperatures without being oxidized. Such constructed laminated composites with outstanding tribological properties by an in situ laser irradiation method supply a new concept in designing lubricant additives that can combine the advantages of 0D and 2D structures.

In-situ diagnostic tools for hydrogen transfer leak characterization in PEM fuel cell stacks part II: Operational applications

NASA Astrophysics Data System (ADS)

Niroumand, Amir M.; Homayouni, Hooman; DeVaal, Jake; Golnaraghi, Farid; Kjeang, Erik

2016-08-01

This paper describes a diagnostic tool for in-situ characterization of the rate and distribution of hydrogen transfer leaks in Polymer Electrolyte Membrane (PEM) fuel cell stacks. The method is based on reducing the air flow rate from a high to low value at a fixed current, while maintaining an anode overpressure. At high air flow rates, the reduction in air flow results in lower oxygen concentration in the cathode and therefore reduction in cell voltages. Once the air flow rate in each cell reaches a low value at which the cell oxygen-starves, the voltage of the corresponding cell drops to zero. However, oxygen starvation results from two processes: 1) the electrochemical oxygen reduction reaction which produces current; and 2) the chemical reaction between oxygen and the crossed over hydrogen. In this work, a diagnostic technique has been developed that accounts for the effect of the electrochemical reaction on cell voltage to identify the hydrogen leak rate and number of leaky cells in a fuel cell stack. This technique is suitable for leak characterization during fuel cell operation, as it only requires stack air flow and voltage measurements, which are readily available in an operational fuel cell system.

Light fluorous-tagged traceless one-pot synthesis of benzimidazoles facilitated by microwave irradiation.

PubMed

Tseng, Chih-Chung; Tasi, Cheng-Hsun; Sun, Chung-Ming

2012-06-01

A novel protocol for rapid assemble of benzimidazole framework has been demonstrated. This method incorporated with light fluorous-tag provides a convenient method for diversification of benzimidazoles and for easy purification via fluorous solid-phase extraction (F-SPE) in a parallel manner. The key transformation of this study involves in situ reduction of aromatic nitro compound, amide formation, cyclization and aromatization promoted by microwave irradiation in a one-pot fashion. The strategy is envisaged to be applied for the establishment of drug-like small molecule libraries for high throughput screening.

In situ synthesis of silver nanoparticles on the surface of PDMS with high antibacterial activity and biosafety toward an implantable medical device

NASA Astrophysics Data System (ADS)

Kim, Joong Hyun; Park, HyeungWoo; Seo, Soo Won

2017-11-01

We developed a straightforward method to fabricate antibacterial silicon films via the in situ synthesis of silver nanoparticles (AgNPs) on a polydimethylsiloxane (PDMS) film. To grow AgNPs attached on the film, AgNP seeds were synthesized through the reduction of silver ions electrostatically bound to hydroxyl groups formed on the surface of the film after treatment with air plasma. In the growth reaction, silver ions were reduced on the seeds of AgNPs by sodium citrate in a solution of AgNO3, which allowed for the formation of AgNPs with sizes of up to 500 nm, which The formed AgNPs on the films were characterized using UV-vis spectrophotometer, scattering electron microscope and induced coupled mass spectrometer. The amount of AgNPs was estimated to be less than 0.05% of the total film weight. Even though it was coated with a small amount of AgNPs, the PDMS film exhibited reduction of E. coli and S. aureus with values of log10 4.8 and log10 5.7, respectively. The biosafety of the AgNP-attached PDMS film was examined by contact of cells with the film or film eluent. Counting of viable cells revealed no significant cytotoxicity of the in situ-fabricated AgNPs on the PDMS film.

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

Core flooding tests to investigate the effects of IFT reduction and wettability alteration on oil recovery during MEOR process in an Iranian oil reservoir.

PubMed

Rabiei, Arash; Sharifinik, Milad; Niazi, Ali; Hashemi, Abdolnabi; Ayatollahi, Shahab

2013-07-01

Microbial enhanced oil recovery (MEOR) refers to the process of using bacterial activities for more oil recovery from oil reservoirs mainly by interfacial tension reduction and wettability alteration mechanisms. Investigating the impact of these two mechanisms on enhanced oil recovery during MEOR process is the main objective of this work. Different analytical methods such as oil spreading and surface activity measurements were utilized to screen the biosurfactant-producing bacteria isolated from the brine of a specific oil reservoir located in the southwest of Iran. The isolates identified by 16S rDNA and biochemical analysis as Enterobacter cloacae (Persian Type Culture Collection (PTCC) 1798) and Enterobacter hormaechei (PTCC 1799) produce 1.53 g/l of biosurfactant. The produced biosurfactant caused substantial surface tension reduction of the growth medium and interfacial tension reduction between oil and brine to 31 and 3.2 mN/m from the original value of 72 and 29 mN/m, respectively. A novel set of core flooding tests, including in situ and ex situ scenarios, was designed to explore the potential of the isolated consortium as an agent for MEOR process. Besides, the individual effects of wettability alteration and IFT reduction on oil recovery efficiency by this process were investigated. The results show that the wettability alteration of the reservoir rock toward neutrally wet condition in the course of the adsorption of bacteria cells and biofilm formation are the dominant mechanisms on the improvement of oil recovery efficiency.

Highly Stretchable and Conductive Silver Nanoparticle Embedded Graphene Flake Electrode Prepared by In situ Dual Reduction Reaction

PubMed Central

Yoon, Yeoheung; Samanta, Khokan; Lee, Hanleem; Lee, Keunsik; Tiwari, Anand P.; Lee, JiHun; Yang, Junghee; Lee, Hyoyoung

2015-01-01

The emergence of stretchable devices that combine with conductive properties offers new exciting opportunities for wearable applications. Here, a novel, convenient and inexpensive solution process was demonstrated to prepare in situ silver (Ag) or platinum (Pt) nanoparticles (NPs)-embedded rGO hybrid materials using formic acid duality in the presence of AgNO3 or H2PtCl6 at low temperature. The reduction duality of the formic acid can convert graphene oxide (GO) to rGO and simultaneously deposit the positively charged metal ion to metal NP on rGO while the formic acid itself is converted to a CO2 evolving gas that is eco-friendly. The AgNP-embedded rGO hybrid electrode on an elastomeric substrate exhibited superior stretchable properties including a maximum conductivity of 3012 S cm-1 (at 0 % strain) and 322.8 S cm-1 (at 35 % strain). Its fabrication process using a printing method is scalable. Surprisingly, the electrode can survive even in continuous stretching cycles. PMID:26383845

Reduced Graphene Oxide-Based Silver Nanoparticle-Containing Composite Hydrogel as Highly Efficient Dye Catalysts for Wastewater Treatment

PubMed Central

Jiao, Tifeng; Guo, Haiying; Zhang, Qingrui; Peng, Qiuming; Tang, Yongfu; Yan, Xuehai; Li, Bingbing

2015-01-01

New reduced graphene oxide-based silver nanoparticle-containing composite hydrogels were successfully prepared in situ through the simultaneous reduction of GO and noble metal precursors within the GO gel matrix. The as-formed hydrogels are composed of a network structure of cross-linked nanosheets. The reported method is based on the in situ co-reduction of GO and silver acetate within the hydrogel matrix to form RGO-based composite gel. The stabilization of silver nanoparticles was also achieved simultaneously within the gel composite system. The as-formed silver nanoparticles were found to be homogeneously and uniformly dispersed on the surface of the RGO nanosheets within the composite gel. More importantly, this RGO-based silver nanoparticle-containing composite hydrogel matrix acts as a potential catalyst for removing organic dye pollutants from an aqueous environment. Interestingly, the as-prepared catalytic composite matrix structure can be conveniently separated from an aqueous environment after the reaction, suggesting the potentially large-scale applications of the reduced graphene oxide-based nanoparticle-containing composite hydrogels for organic dye removal and wastewater treatment. PMID:26183266

Structure and function of subsurface microbial communities affecting radionuclide transport and bioimmobilization

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

Kostka, Joel E.; Prakash, Om; Green, Stefan J.

2012-05-01

Our objectives were to: 1) isolate and characterize novel anaerobic prokaryotes from subsurface environments exposed to high levels of mixed contaminants (U(VI), nitrate, sulfate), 2) elucidate the diversity and distribution of metabolically active metal- and nitrate-reducing prokaryotes in subsurface sediments, and 3) determine the biotic and abiotic mechanisms linking electron transport processes (nitrate, Fe(III), and sulfate reduction) to radionuclide reduction and immobilization. Mechanisms of electron transport and U(VI) transformation were examined under near in situ conditions in sediment microcosms and in field investigations. Field sampling was conducted at the Oak Ridge Field Research Center (ORFRC), in Oak Ridge, Tennessee. Themore » ORFRC subsurface is exposed to mixed contamination predominated by uranium and nitrate. In short, we effectively addressed all 3 stated objectives of the project. In particular, we isolated and characterized a large number of novel anaerobes with a high bioremediation potential that can be used as model organisms, and we are now able to quantify the function of subsurface sedimentary microbial communities in situ using state-of-the-art gene expression methods (molecular proxies).« less

Highly Stretchable and Conductive Silver Nanoparticle Embedded Graphene Flake Electrode Prepared by In situ Dual Reduction Reaction

NASA Astrophysics Data System (ADS)

Yoon, Yeoheung; Samanta, Khokan; Lee, Hanleem; Lee, Keunsik; Tiwari, Anand P.; Lee, Jihun; Yang, Junghee; Lee, Hyoyoung

2015-09-01

The emergence of stretchable devices that combine with conductive properties offers new exciting opportunities for wearable applications. Here, a novel, convenient and inexpensive solution process was demonstrated to prepare in situ silver (Ag) or platinum (Pt) nanoparticles (NPs)-embedded rGO hybrid materials using formic acid duality in the presence of AgNO3 or H2PtCl6 at low temperature. The reduction duality of the formic acid can convert graphene oxide (GO) to rGO and simultaneously deposit the positively charged metal ion to metal NP on rGO while the formic acid itself is converted to a CO2 evolving gas that is eco-friendly. The AgNP-embedded rGO hybrid electrode on an elastomeric substrate exhibited superior stretchable properties including a maximum conductivity of 3012 S cm-1 (at 0 % strain) and 322.8 S cm-1 (at 35 % strain). Its fabrication process using a printing method is scalable. Surprisingly, the electrode can survive even in continuous stretching cycles.

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

Vermeul, Vince R.; Szecsody, Jim E.; Truex, Michael J.

This treatability study was conducted by Pacific Northwest National Laboratory (PNNL), at the request of the U. S. Environmental Protection Agency (EPA) Region 2, to evaluate the feasibility of using in situ treatment technologies for chromate reduction and immobilization at the Puchack Well Field Superfund Site in Pennsauken Township, New Jersey. In addition to in situ reductive treatments, which included the evaluation of both abiotic and biotic reduction of Puchack aquifer sediments, natural attenuation mechanisms were evaluated (i.e., chromate adsorption and reduction). Chromate exhibited typical anionic adsorption behavior, with greater adsorption at lower pH, at lower chromate concentration, and atmore » lower concentrations of other competing anions. In particular, sulfate (at 50 mg/L) suppressed chromate adsorption by up to 50%. Chromate adsorption was not influenced by inorganic colloids.« less

In-situ Production of High Density Polyethylene and Other Useful Materials on Mars

NASA Technical Reports Server (NTRS)

Flynn, Michael

2005-01-01

This paper describes a revolutionary materials structure and power storage concept based on the in-situ production of abiotic carbon 4 compounds. One of the largest single mass penalties required to support the human exploration of Mars is the surface habitat. This proposal will use physical chemical technologies to produce high density polyethylene (HDPE) inflatable structures and construction materials from Mars atmospheric CO2. The formation of polyethylene from Mars CO2 is based on the use of the Sabatier and modified Fischer Tropsch reactions. The proposed system will fully integrate with existing in-situ propellant production concepts. The technology will also be capable of supplementing human caloric requirements, providing solid and liquid fuels for energy storage, and providing significant reduction in mission risk. The NASA Mars Reference Mission Definition Team estimated that a conventional Mars surface habitat structure would weigh 10 tonnes. It is estimated that this technology could reduce this mass by 80%. This reduction in mass will significantly contribute to the reduction in total mission cost need to make a Mars mission a reality. In addition the potential reduction of risk provided by the ability to produce C4 and potentially higher carbon based materials in-situ on Mars is significant. Food, fuel, and shelter are only three of many requirements that would be impacted by this research.

Contributions of Fe Minerals to Abiotic Dechlorination

EPA Science Inventory

Most applications of enhanced in situ bioremediation are based on biological reductive dechlorination. Anaerobic metabolism can also produce reactive minerals that allow for in situ biogeochemical transformation of chlorinated organic contaminants such as PCE, TCE, and cis-DCE. ...

Refractures of the paediatric forearm with the intramedullary nail in situ.

PubMed

van Egmond, Pim W; van der Sluijs, Hans A; van Royen, Barend J; Saouti, Rachid

2013-09-24

Forearm fractures in children are common. When conservative treatment fails, internal fixation with Elastic Stable Intramedullary Nailing (ESIN) become the first choice in the operative treatment of diaphyseal forearm shaft fractures. Refractures with the intramedullary nail in situ are known to occur but formal guidelines to guide management in such fractures are lacking. We present a well-documented case of a radius midshaft refracture in a 12-year-old boy with the intramedullary nail in situ, managed by closed reduction. Literature is reviewed for this type of complication, the treatment of 30 similar cases is discussed and a treatment strategy is defined. The refracture of the paediatric forearm fracture with the intramedullary nail in situ is a rare, but probably under recognised complication which is observed in approximately 2.3% of the study population. Closed reduction may be considered in these cases.

Tribological properties and lubrication mechanism of in situ graphene-nickel matrix composite impregnated with lubricating oil

NASA Astrophysics Data System (ADS)

Lei, Yu; Du, Jinfang; Pang, Xianjuan; Wang, Haizhong; Yang, Hua; Jiang, Jinlong

2018-05-01

A solid-liquid synergetic lubricating system has been designed to develop a novel self-lubricating nickel matrix composite. The graphene-nickel (G-Ni) matrix composite with porous structure was fabricated by in situ growing graphene in bulk nickel using a powder metallurgy method. The porous structures of the composite were used to store polyalphaolefin (PAO) oil for self-lubricating. It is found that the G-Ni matrix composite under oil lubrication condition exhibited superior tribological properties as compared to pure nickel and the composite under dry sliding condition. The prestored oil was released from pores to the sliding surface forming a lubricating oil film during friction process. This lubricating oil film can protect the worn surface from severe oxidation, and help the formation and transfer of a carbon-based solid tribofilm derived from graphene and lubricating oil. This solid (graphene)-liquid (oil) synergistic lubricating mechanism is responsible for the reduction of friction coefficient and improvement of wear resistance of the in situ fabricated G-Ni matrix composite.

Jeremy Dunklin | NREL

Science.gov Websites

;In Situ Reduction of Gold Nanoparticles on Liquid Exfoliated Tungsten Disulfide Nanosheets," ;Asymmetric reduction of gold nanoparticles into thermoplasmonic polydimethylsiloxane thin films," ACS

Universal Multifunctional Nanoplatform Based on Target-Induced in Situ Promoting Au Seeds Growth to Quench Fluorescence of Upconversion Nanoparticles.

PubMed

Wu, Qiongqiong; Chen, Hongyu; Fang, Aijin; Wu, Xinyang; Liu, Meiling; Li, Haitao; Zhang, Youyu; Yao, Shouzhuo

2017-12-22

Construction of a new multifunctional chemo/biosensing platform for small biomolecules and tumor markers is of great importance in analytical chemistry. Herein, a novel universal multifunctional nanoplatform for biomolecules and enzyme activity detection was proposed based on fluorescence resonance energy transfer (FRET) between upconversion nanoparticles (UCNPs) and target-inducing enlarged gold nanoparticles (AuNPs). The reductive molecule such as H 2 O 2 can act as the reductant to reduce HAuCl 4 , which will make the Au seeds grow. The enlarged AuNPs can effectively quench the fluorescence of UCNPs owing to the good spectral overlap between the absorption band of the AuNPs and the emission band of the UCNPs. Utilizing the FRET between the UCNPs and enlarged AuNPs, good linear relationship between the fluorescence of UCNPs and the concentration of H 2 O 2 can be found. Based on this strategy, H 2 O 2 related molecules such as l-lactate, glucose, and uric acid can also be quantified. On the basis of UCNPs and PVP/HAuCl 4 , a general strategy for other reductants such as ascorbic acid (AA), dopamine (DA), or enzyme activity can be established. Therefore, the universal multifunctional nanoplatform based on UCNPs and the target-inducing in situ enlarged Au NPs will show its potential as a simple method for the detection of some life related reductive molecules, enzyme substrates, as well as enzyme activity.

Reflective Silvered Polyimide Films Via In Situ Thermal Reduction Silver (I) Complexes

NASA Technical Reports Server (NTRS)

Southward, Robin E. (Inventor); Thompson, David W. (Inventor); St.Clair, Anne K. (Inventor); Stoakley, Diane M. (Inventor)

2000-01-01

Self-metallizing. flexible polyimide films with highly reflective surfaces are prepared by an in situ self-metallization procedure involving thermally initiated reduction of polymer-soluble silver(I) complexes. Polyamic acid solutions are doped with silver(I) acetate and solubilizing agents. Thermally curing the silver(I) doped resins leads to flexible. metallized films which have reflectivities as high as 100%. abrasion-resistant surfaces. thermal stability and, in some cases, electrical conductivity, rendering them useful for space applications.

A method for in situ absolute DD yield calibration of neutron time-of-flight detectors on OMEGA using CR-39-based proton detectors.

PubMed

Waugh, C J; Rosenberg, M J; Zylstra, A B; Frenje, J A; Séguin, F H; Petrasso, R D; Glebov, V Yu; Sangster, T C; Stoeckl, C

2015-05-01

Neutron time of flight (nTOF) detectors are used routinely to measure the absolute DD neutron yield at OMEGA. To check the DD yield calibration of these detectors, originally calibrated using indium activation systems, which in turn were cross-calibrated to NOVA nTOF detectors in the early 1990s, a direct in situ calibration method using CR-39 range filter proton detectors has been successfully developed. By measuring DD neutron and proton yields from a series of exploding pusher implosions at OMEGA, a yield calibration coefficient of 1.09 ± 0.02 (relative to the previous coefficient) was determined for the 3m nTOF detector. In addition, comparison of these and other shots indicates that significant reduction in charged particle flux anisotropies is achieved when bang time occurs significantly (on the order of 500 ps) after the trailing edge of the laser pulse. This is an important observation as the main source of the yield calibration error is due to particle anisotropies caused by field effects. The results indicate that the CR-39-nTOF in situ calibration method can serve as a valuable technique for calibrating and reducing the uncertainty in the DD absolute yield calibration of nTOF detector systems on OMEGA, the National Ignition Facility, and laser megajoule.

A method for in situ absolute DD yield calibration of neutron time-of-flight detectors on OMEGA using CR-39-based proton detectors

DOE PAGES

Waugh, C. J.; Rosenberg, M. J.; Zylstra, A. B.; ...

2015-05-27

Neutron time of flight (nTOF) detectors are used routinely to measure the absolute DD neutron yield at OMEGA. To check the DD yield calibration of these detectors, originally calibrated using indium activation systems, which in turn were cross-calibrated to NOVA nTOF detectors in the early 1990s, a direct in situ calibration method using CR-39 range filter proton detectors has been successfully developed. By measuring DD neutron and proton yields from a series of exploding pusher implosions at OMEGA, a yield calibration coefficient of 1.09 ± 0.02 (relative to the previous coefficient) was determined for the 3m nTOF detector. In addition,more » comparison of these and other shots indicates that significant reduction in charged particle flux anisotropies is achieved when bang time occurs significantly (on the order of 500 ps) after the trailing edge of the laser pulse. This is an important observation as the main source of the yield calibration error is due to particle anisotropies caused by field effects. The results indicate that the CR-39-nTOF in situ calibration method can serve as a valuable technique for calibrating and reducing the uncertainty in the DD absolute yield calibration of nTOF detector systems on OMEGA, the National Ignition Facility, and laser megajoule.« less

A method for in situ absolute DD yield calibration of neutron time-of-flight detectors on OMEGA using CR-39-based proton detectors

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

Waugh, C. J.; Rosenberg, M. J.; Zylstra, A. B.

Neutron time of flight (nTOF) detectors are used routinely to measure the absolute DD neutron yield at OMEGA. To check the DD yield calibration of these detectors, originally calibrated using indium activation systems, which in turn were cross-calibrated to NOVA nTOF detectors in the early 1990s, a direct in situ calibration method using CR-39 range filter proton detectors has been successfully developed. By measuring DD neutron and proton yields from a series of exploding pusher implosions at OMEGA, a yield calibration coefficient of 1.09 ± 0.02 (relative to the previous coefficient) was determined for the 3m nTOF detector. In addition,more » comparison of these and other shots indicates that significant reduction in charged particle flux anisotropies is achieved when bang time occurs significantly (on the order of 500 ps) after the trailing edge of the laser pulse. This is an important observation as the main source of the yield calibration error is due to particle anisotropies caused by field effects. The results indicate that the CR-39-nTOF in situ calibration method can serve as a valuable technique for calibrating and reducing the uncertainty in the DD absolute yield calibration of nTOF detector systems on OMEGA, the National Ignition Facility, and laser megajoule.« less

A method for in situ absolute DD yield calibration of neutron time-of-flight detectors on OMEGA using CR-39-based proton detectors

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

Waugh, C. J., E-mail: cjwaugh@mit.edu; Zylstra, A. B.; Frenje, J. A.

2015-05-15

Neutron time of flight (nTOF) detectors are used routinely to measure the absolute DD neutron yield at OMEGA. To check the DD yield calibration of these detectors, originally calibrated using indium activation systems, which in turn were cross-calibrated to NOVA nTOF detectors in the early 1990s, a direct in situ calibration method using CR-39 range filter proton detectors has been successfully developed. By measuring DD neutron and proton yields from a series of exploding pusher implosions at OMEGA, a yield calibration coefficient of 1.09 ± 0.02 (relative to the previous coefficient) was determined for the 3m nTOF detector. In addition,more » comparison of these and other shots indicates that significant reduction in charged particle flux anisotropies is achieved when bang time occurs significantly (on the order of 500 ps) after the trailing edge of the laser pulse. This is an important observation as the main source of the yield calibration error is due to particle anisotropies caused by field effects. The results indicate that the CR-39-nTOF in situ calibration method can serve as a valuable technique for calibrating and reducing the uncertainty in the DD absolute yield calibration of nTOF detector systems on OMEGA, the National Ignition Facility, and laser megajoule.« less

Effect of an in situ Hydrogen Plasma Pre-treatment on the Reduction of GaSb Native oxides Prior to Atomic Layer Deposition

DTIC Science & Technology

2013-04-12

absence of Sb-oxides, a reduction in elemental Sb, and an increase in the Ga2O3 content at the interface. The use of an in situ hydrogen...elemental Sb, and an increase in the Ga2O3 content at the interface. The use of an in situ hydrogen plasma pre-treatment eliminates the need for wet...the +1 state (Ga2O) and the +3 state ( Ga2O3 ), with peak positions found at 530.5 eV (Sb2O4), 20.1 eV (Ga2O), and 20.7 eV ( Ga2O3 ) [11,18]. The AFM image

Potential New Sensor for Use With Conventional Gas Carburizing

NASA Technical Reports Server (NTRS)

deGroot, W. A.

1997-01-01

Diagnostics developed for in-situ monitoring of rocket combustion environments have been adapted for use in heat treating furnaces. Simultaneous, in-situ monitoring of the carbon monoxide, carbon dioxide, methane, water, nitrogen and hydrogen concentrations in the endothermic gas of a heat treating furnace has been demonstrated under a Space Act Agreement between NASA Lewis, the Heat Treating Network, and Akron Steel Treating Company. Equipment installed at the Akron Steel Treating Company showed the feasibility of the method. Clear and well-defined spectra of carbon monoxide, nitrogen and hydrogen were obtained by means of an optical probe mounted on the endothermic gas line of a gas generator inside the plant, with the data reduction hardware located in the basement laboratory. Signals to and from the probe were transmitted via optical fibers.

Mercury emission to the atmosphere from municipal solid waste landfills: A brief review

NASA Astrophysics Data System (ADS)

Tao, Zhengkai; Dai, Shijin; Chai, Xiaoli

2017-12-01

Municipal solid waste (MSW) landfill is regarded as an important emission source of atmospheric mercury (Hg), which is associated with potential health and environmental risks, as outlined by the Minamata Convention on Hg. This review presents the current state of knowledge with regards to landfill Hg sources, Hg levels in MSW and cover soils, Hg emission to the atmosphere, available Hg biogeochemical transformations, research methods for Hg emission, and important areas for future research. In addition, strategies for controlling landfill Hg emissions are considered, including reducing the Hg load in landfill and in situ controls. These approaches mainly focus on Hg source reduction, Hg recycling programs, public education, and in situ technology such as timely soil cover, vegetation, and end-of-pipe technology for controlling Hg emission from landfill gas.

In Situ Elevated Temperature Testing of Fly Ash Based Geopolymer Composites.

PubMed

Vickers, Les; Pan, Zhu; Tao, Zhong; van Riessen, Arie

2016-06-03

In situ elevated temperature investigations using fly ash based geopolymers filled with alumina aggregate were undertaken. Compressive strength and short term creep tests were carried out to determine the onset temperature of viscous flow. Fire testing using the standard cellulose curve was performed. Applying a load to the specimen as the temperature increased reduced the temperature at which viscous flow occurred (compared to test methods with no applied stress). Compressive strength increased at the elevated temperature and is attributed to viscous flow and sintering forming a more compact microstructure. The addition of alumina aggregate and reduction of water content reduced the thermal conductivity. This led to the earlier onset and shorter dehydration plateau duration times. However, crack formation was reduced and is attributed to smaller thermal gradients across the fire test specimen.

Following the electroreduction of uranium dioxide to uranium in LiCl-KCl eutectic in situ using synchrotron radiation

NASA Astrophysics Data System (ADS)

Brown, L. D.; Abdulaziz, R.; Jervis, R.; Bharath, V. J.; Atwood, R. C.; Reinhard, C.; Connor, L. D.; Simons, S. J. R.; Inman, D.; Brett, D. J. L.; Shearing, P. R.

2015-09-01

The electrochemical reduction of uranium dioxide to metallic uranium has been investigated in lithium chloride-potassium chloride eutectic molten salt. Laboratory based electrochemical studies have been coupled with in situ energy dispersive X-ray diffraction, for the first time, to deduce the reduction pathway. No intermediate phases were identified using the X-ray diffraction before, during or after electroreduction to form α-uranium. This suggests that the electrochemical reduction occurs via a single, 4-electron-step, process. The rate of formation of α-uranium is seen to decrease during electrolysis and could be a result of a build-up of oxygen anions in the molten salt. Slow transport of O2- ions away from the UO2 working electrode could impede the electrochemical reduction.

IN-SITU CHEMICAL OXIDATION - DNAPL MASS REDUCTION TECHNOLOGY

EPA Science Inventory

In-situ chemical oxidation (ISCO) is a rapidly developing technology used at hazardous waste sites where oxidants and complimentary reagents are injected into the subsurface to transform organic contaminants into less toxic byproducts. This technology is being used at new sites ...

In situ growth of metal particles on 3D urchin-like WO3 nanostructures.

PubMed

Xi, Guangcheng; Ye, Jinhua; Ma, Qiang; Su, Ning; Bai, Hua; Wang, Chao

2012-04-18

Metal/semiconductor hybrid materials of various sizes and morphologies have many applications in areas such as catalysis and sensing. Various organic agents are necessary to stabilize metal nanoparticles during synthesis, which leads to a layer of organic compounds present at the interfaces between the metal particles and the semiconductor supports. Generally, high-temperature oxidative treatment is used to remove the organics, which can extensively change the size and morphology of the particles, in turn altering their activity. Here we report a facile method for direct growth of noble-metal particles on WO(3) through an in situ redox reaction between weakly reductive WO(2.72) and oxidative metal salts in aqueous solution. This synthetic strategy has the advantages that it takes place in one step and requires no foreign reducing agents, stabilizing agents, or pretreatment of the precursors, making it a practical method for the controlled synthesis of metal/semiconductor hybrid nanomaterials. This synthetic method may open up a new way to develop metal-nanoparticle-loaded semiconductor composites. © 2012 American Chemical Society

Electrochemical and in situ spectroscopic studies of materials of relevance to energy storage and electrocatalysis

NASA Astrophysics Data System (ADS)

Mo, Yibo

In situ X-ray absorption (XAS), surface enhanced Raman spectroscopy (SERS) and rotating ring disk electrode techniques have been employed for the characterization of materials of relevance to electrochemical energy storage and electrocatalysis. In particular, analysis of in situ Ir LIII-edge extended X-ray absorption fine structure (EXAFS) of IrO2 films electrodeposited on Au substrates yielded Ir-O bond lengths decreasing in the sequence 2.02, 1.97 and 1.93 A, for Ir3+, Ir4+ and Ir5+ sites, respectively. Although features consistent with the presence of crystalline IrO2 in the highly hydrated films were found from in situ SERS, the lack of intense shells in the FT of the EXAFS function beyond the nearest oxygen neighbors indicates that the films by and large do not display long range order. In similar studies, the Fourier transform of the k3-weighted Ru K-edge EXAFS of electrodeposited RuO2 films recorded in situ were characterized by two shells attributed to Ru-O and Ru-Ru interactions at 1.94(1) and 3.12(2) A, in agreement with results obtained ex situ for Ru4+ in hydrous RuO2, whereas films in the reduced state yielded a single Ru-O interaction shell at 2.02(1) A. Extensions of these in situ XAS to the study of electrocatalysts for the nitrite reduction made it possible to identify and characterize the electronic and structural properties of a nitrosyl iron porphyrin adduct adsorbed on an electrode surface via the analysis of Fe K-edge XAS data. The effects of Se and S ad-atoms on the electrocatalytic activity of Pt electrodes have been examined using RRDE techniques. In acid, within a rather narrow range of coverages, both S- and Se-modified Pt surfaces promote the 2-electron reduction of dioxygen to hydrogen peroxide at ca. 100% faradaic efficiency over a wide potential region. Also developed were methods for immobilizing unsupported dispersed high area Pt particles a glassy carbon (GC) disk of a rotating Pt(ring)/GC(disk) electrode assembly allowing electrochemical measurements to be performed under forced convection with only minimal losses of Pt from the surface.

A combined electrochemical-irradiation treatment of highly colored and polluted industrial wastewater

NASA Astrophysics Data System (ADS)

Barrera-Díaz, C.; Ureña-Nuñez, F.; Campos, E.; Palomar-Pardavé, M.; Romero-Romo, M.

2003-07-01

This study reports on the attainment of optimal conditions for two electrolytic methods to treat wastewater: namely, electrocoagulation and particle destabilization of a highly polluted industrial wastewater, and electrochemically induced oxidation induced by in situ generation of Fenton's reactive. Additionally, a combined method that consisted of electrochemical treatment plus γ-irradiation was carried out. A typical composition of the industrial effluent treated was COD 3400 mg/l, color 3750 Pt/Co units, and fecal coliforms 21000 MPN/ml. The best removal efficiency was obtained with electrochemical oxidation induced in situ , that resulted in the reduction of 78% for the COD, 86% color and 99.9% fecal coliforms removal. A treatment sequence was designed and carried out, such that after both electrochemical processes, a γ-irradiation technique was used to complete the procedure. The samples were irradiated with various doses in an ALC γ-cell unit provided with a Co-60 source. The removal efficiency obtained was 95% for the COD values, 90% color and 99.9% for fecal coliforms.

Detection of platinum dihydride bisphosphine complexes and studies of their reactivity through para-hydrogen-enhanced NMR methods.

PubMed

Godard, Cyril; López-Serrano, Joaquín; Gálvez-López, María-Dolores; Roselló-Merino, Marta; Duckett, Simon B; Khazal, Iman; Lledós, Agustí; Whitwood, Adrian C

2008-01-01

In-situ NMR studies on the reactions of Pt{CH2 = CHSi(Me)2}2O)(PCy3) with phosphines, HSiEt3 and--hydrogen or Pt(L)(L')(Me)(2) alone enable the detection of cis-Pt(L)(L')(H)2 [L = PCy3 and L' = PCy2H, PPh3 or PCy3] which then undergo hydride site interchange and H2 reductive elimination on the NMR timescale.

COST AND PERFORMANCE REPORT: IN SITU ANAEROBIC BIOREMEDIATION PINELLAS NORTHEAST SITE, LARGO, FLORIDA

EPA Science Inventory

The ITRD public/private partnership has conducted a pilot field demonstration of reductive anaerobic biological in-situ treatment technologies (RABITT) to evaluate its use as a standard remedial technology for chloroethene contamination. System design scenarios were evaluated wi...

Low-temperature thermal reduction of graphene oxide: In situ correlative structural, thermal desorption, and electrical transport measurements

NASA Astrophysics Data System (ADS)

Lipatov, Alexey; Guinel, Maxime J.-F.; Muratov, Dmitry S.; Vanyushin, Vladislav O.; Wilson, Peter M.; Kolmakov, Andrei; Sinitskii, Alexander

2018-01-01

Elucidation of the structural transformations in graphene oxide (GO) upon reduction remains an active and important area of research. We report the results of in situ heating experiments, during which electrical, mass spectrometry, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) measurements were carried out correlatively. The simultaneous electrical and temperature programmed desorption measurements allowed us to correlate the onset of the increase in the electrical conductivity of GO by five orders of magnitude at about 150 °C with the maxima of the rates of desorption of H2O, CO, and CO2. Interestingly, this large conductivity change happens at an intermediate level of the reduction of GO, which likely corresponds to the point when the graphitic domains become large enough to enable percolative electronic transport. We demonstrate that the gas desorption is intimately related to (i) the changes in the chemical structure of GO detected by XPS and Raman spectroscopy and (ii) the formation of nanoscopic holes in GO sheets revealed by TEM. These in situ observations provide a better understanding of the mechanism of the GO thermal reduction.

Prediction and characterization of application power use in a high-performance computing environment

DOE PAGES

Bugbee, Bruce; Phillips, Caleb; Egan, Hilary; ...

2017-02-27

Power use in data centers and high-performance computing (HPC) facilities has grown in tandem with increases in the size and number of these facilities. Substantial innovation is needed to enable meaningful reduction in energy footprints in leadership-class HPC systems. In this paper, we focus on characterizing and investigating application-level power usage. We demonstrate potential methods for predicting power usage based on a priori and in situ characteristics. Lastly, we highlight a potential use case of this method through a simulated power-aware scheduler using historical jobs from a real scientific HPC system.

In-situ Observation of Size and Irradiation Effects on Thermoelectric Properties of Bi-Sb-Te Nanowire in FIB Trimming

PubMed Central

Chien, Chia-Hua; Lee, Ping-Chung; Tsai, Wei-Han; Lin, Chien-Hung; Lee, Chih-Hao; Chen, Yang-Yuan

2016-01-01

In this report, the thermoelectric properties of a Bi0.8Sb1.2Te2.9 nanowire (NW) were in-situ studied as it was trimmed from 750 down to 490 and 285 nm in diameter by a focused ion beam. While electrical and thermal conductivities both indubitably decrease with the diameter reduction, the two physical properties clearly exhibit different diameter dependent behaviors. For 750 and 490 nm NWs, much lower thermal conductivities (0.72 and 0.69 W/m-K respectively) were observed as compared with the theoretical prediction of Callaway model. The consequence indicates that in addition to the size effect, extra phonon scattering of defects created by Ga ion irradiation was attributed to the reduction of thermal conductivities. As the NW was further trimmed down to 285 nm, both the electrical and thermal conductivities exhibited a dramatic reduction which was ascribed to the formation of amorphous structure due to Ga ion irradiation. The size dependence of Seebeck coefficient and figure of merit (ZT) show the maximum at 750 nm, then decrease linearly with size decrease. The study not only provides the thoroughly understanding of the size and defect effects on the thermoelectric properties but also proposes a possible method to manipulate the thermal conductivity of NWs via ion irradiation. PMID:27030206

Overview of the randomized trials of radiotherapy in ductal carcinoma in situ of the breast.

PubMed

Correa, C; McGale, P; Taylor, C; Wang, Y; Clarke, M; Davies, C; Peto, R; Bijker, N; Solin, L; Darby, S

2010-01-01

Individual patient data were available for all four of the randomized trials that began before 1995, and that compared adjuvant radiotherapy vs no radiotherapy following breast-conserving surgery for ductal carcinoma in situ (DCIS). A total of 3729 women were eligible for analysis. Radiotherapy reduced the absolute 10-year risk of any ipsilateral breast event (ie, either recurrent DCIS or invasive cancer) by 15.2% (SE 1.6%, 12.9% vs 28.1% 2 P <.00001), and it was effective regardless of the age at diagnosis, extent of breast-conserving surgery, use of tamoxifen, method of DCIS detection, margin status, focality, grade, comedonecrosis, architecture, or tumor size. The proportional reduction in ipsilateral breast events was greater in older than in younger women (2P < .0004 for difference between proportional reductions; 10-year absolute risks: 18.5% vs 29.1% at ages <50 years, 10.8% vs 27.8% at ages ≥ 50 years) but did not differ significantly according to any other available factor. Even for women with negative margins and small low-grade tumors, the absolute reduction in the 10-year risk of ipsilateral breast events was 18.0% (SE 5.5, 12.1% vs 30.1%, 2P = .002). After 10 years of follow-up, there was, however, no significant effect on breast cancer mortality, mortality from causes other than breast cancer, or all-cause mortality.

Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals.

PubMed

Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

2016-07-05

Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites.

Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals

PubMed Central

Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P.; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

2016-01-01

Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites. PMID:27378145

Growth of block copolymer stabilized metal nanoparticles probed simultaneously by in situ XAS and UV-Vis spectroscopy.

PubMed

Nayak, C; Bhattacharyya, D; Jha, S N; Sahoo, N K

2016-01-01

The growth of Au and Pt nanoparticles from their respective chloride precursors using block copolymer-based reducers has been studied by simultaneous in situ measurement of XAS and UV-Vis spectroscopy at the energy-dispersive EXAFS beamline (BL-08) at INDUS-2 SRS at RRCAT, Indore, India. While the XANES spectra of the precursor give real-time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed at the intermediate stages of growth. The growth kinetics of both types of nanoparticles are found to be almost similar and are found to follow three stages, though the first stage of nucleation takes place earlier in the case of Au than in the case of Pt nanoparticles due to the difference in the reduction potential of the respective precursors. The first two stages of the growth of Au and Pt nanoparticles as obtained by in situ XAS measurements could be corroborated by simultaneous in situ measurement of UV-Vis spectroscopy also.

Graphene/biofilm composites for enhancement of hexavalent chromium reduction and electricity production in a biocathode microbial fuel cell.

PubMed

Song, Tian-Shun; Jin, Yuejuan; Bao, Jingjing; Kang, Dongzhou; Xie, Jingjing

2016-11-05

In this study, a simple method of biocathode fabrication in a Cr(VI)-reducing microbial fuel cell (MFC) is demonstrated. A self-assembling graphene was decorated onto the biocathode microbially, constructing a graphene/biofilm, in situ. The maximum power density of the MFC with a graphene biocathode is 5.7 times that of the MFC with a graphite felt biocathode. Cr(VI) reduction was also enhanced, resulting in 100% removal of Cr(VI) within 48h, at 40mg/L Cr(VI), compared with only 58.3% removal of Cr(VI) in the MFC with a graphite felt biocathode. Cyclic voltammogram analyses showed that the graphene biocathode had faster electron transfer kinetics than the graphite felt version. Energy dispersive spectrometer (EDS) and X-ray photoelectron spectra (XPS) analysis revealed a possible adsorption-reduction mechanism for Cr(VI) reduction via the graphene biocathode. This study attempts to improve the efficiency of the biocathode in the Cr(VI)-reducing MFC, and provides a useful candidate method for the treatment of Cr(VI) contaminated wastewater, under neutral conditions. Copyright © 2016. Published by Elsevier B.V.

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

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

Zhang, Lulu; Su, Dong; Zhu, Shangqian

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

DOE PAGES

Zhang, Lulu; Su, Dong; Zhu, Shangqian; ...

2016-04-26

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

In situ reduction of antibacterial silver ions to metallic silver nanoparticles on bioactive glasses functionalized with polyphenols

NASA Astrophysics Data System (ADS)

Ferraris, S.; Miola, M.; Cochis, A.; Azzimonti, B.; Rimondini, L.; Prenesti, E.; Vernè, E.

2017-02-01

The realization of surfaces with antibacterial properties due to silver nanoparticles loaded through a green approach is a promising research challenge of the biomaterial field. In this research work, two bioactive glasses have been doubly surface functionalized with polyphenols (gallic acid or natural polyphenols extracted from red grape skins and green tea leaves) and silver nanoparticles deposited by in situ reduction from a silver nitrate aqueous solution. The presence of biomolecules - showing reducing ability to directly obtain in situ metallic silver - and silver nanoparticles was investigated by means of UV-vis spectroscopy, X-Ray Photoelectron Spectroscopy (XPS) and Field Emission Scanning Electron Microscopy (FESEM). The antibacterial activity of the modified surfaces was tested against a multidrug resistant Staphylococcus aureus bacterial strain.

Three-dimensional interconnected network of graphene-wrapped porous silicon spheres: in situ magnesiothermic-reduction synthesis and enhanced lithium-storage capabilities.

PubMed

Wu, Ping; Wang, Hui; Tang, Yawen; Zhou, Yiming; Lu, Tianhong

2014-03-12

A novel type of 3D porous Si-G micro/nanostructure (i.e., 3D interconnected network of graphene-wrapped porous silicon spheres, Si@G network) was constructed through layer-by-layer assembly and subsequent in situ magnesiothermic-reduction methodology. Compared with bare Si spheres, the as-synthesized Si@G network exhibits markedly enhanced anodic performance in terms of specific capacity, cycling stability, and rate capability, making it an ideal anode candidate for high-energy, long-life, and high-power lithium-ion batteries.

Further biogeochemical characterization of a trichloroethene-contaminated fractured dolomite aquifer: Electron source and microbial communities involved in reductive dechlorination

USGS Publications Warehouse

Hohnstock-Ashe, A. M.; Plummer, S.M.; Yager, R.M.; Baveye, P.; Madsen, E.L.

2001-01-01

A recent article presented geochemical and microbial evidence establishing metabolic adaptation to and in-situ reductive dechlorination of trichloroethene (TCE) in a fractured dolomite aquifer. This study was designed to further explore site conditions and microbial populations and to explain previously reported enhancement of reductive dechlorination by the addition of pulverized dolomite to laboratory microcosms. A survey of groundwater geochemical parameters (chlorinated ethenes, ethene, H2, CH4, DIC, DOC, and ??13C values for CH4, DIC, and DOC) indicated that in situ reductive dechlorination was ongoing and that an unidentified pool of organic carbon was contributing, likely via microbial respiration, to the large and relatively light onsite DIC pool. Petroleum hydrocarbons associated with the dolomite rock were analyzed by GC/MS and featured a characteristically low ??13C value. Straight chain hydrocarbons were extracted from the dolomite previously found to stimulate reductive dechlorination; these were particularly depleted in hexadecane (HD). Thus, we hypothesized that HD and related hydrocarbons might be anaerobically respired and serve both as the source of onsite DIC and support reductive dechlorination of TCE. Microcosms amended with pulverized dolomite demonstrated reductive dechlorination, whereas a combusted dolomite amendment did not. HD-amended microcosms were also inactive. Therefore, the stimulatory factor in the pulverized dolomite was heat labile, but that component was not HD. Amplified Ribosomal DNA Restriction Analysis (ARDRA) of the microbial populations in well waters indicated that a relatively low diversity, sulfur-transforming community outside the plume was shifted toward a high diversity community including Dehalococcoides ethenogenes-type microorganisms inside the zone of contamination. These observations illustrate biogeochemical intricacies of in situ reductive dechlorination reactions.

Synthesis and characterization of TiC nanopowders via sol-gel and subsequent carbothermal reduction process

NASA Astrophysics Data System (ADS)

Chen, Xu; Fan, Jinglian; Lu, Qiong

2018-06-01

TiC nanocrystalline powders were synthesized by in-situ carbothermic reduction of Ti-O-C precursor under vacuum atmosphere. And the Ti-O-C precursor was formed by sol-gel method from titanium butyrate (TBOT) and sucrose. To obtain stable sol, TBOT was directly added into mixed solution which contains water, sucrose, acetic acid (AcOH) and acetylacetone (ACAC). This procedure is more convenient and economical because it avoids the use of alcohol which is used as solvent in most reports of alkoxide hydrolysis sol-gel method. TG-DSC, XRD, FTIR and SEM/TEM were employed to analyze and characterize the product during the entire process. The phase composition and crystalline structure parameters of powders with different C/Ti molar ratio were investigated by Rietveld refinement method, and elemental quantitative analysis of the samples were performed. Furthermore, the optimal parameters of carbothermal reduction were obtained and the grain growth mechanism was demonstrated. The results show that TiC nanocrystalline powders (C/Ti molar ratio is 3.5 in the precursor) were synthesized at 1300 °C for 2 h, which have near standard lattice parameter, well crystallinity and fine average grain size ( 37.4 nm).

Assessment of In-Situ Reductive Dechlorination Using Compound-Specific Stable Isotopes, Functional-Gene Pcr, and Geochemical Data

PubMed Central

Carreón-Diazconti, Concepción; Santamaría, Johanna; Berkompas, Justin; Field, James A.; Brusseau, Mark L.

2010-01-01

Isotopic analysis and molecular-based bioassay methods were used in conjunction with geochemical data to assess intrinsic reductive dechlorination processes for a chlorinated-solvent contaminated site in Tucson, Arizona. Groundwater samples were obtained from monitoring wells within a contaminant plume comprising tetrachloroethene and its metabolites trichloroethene, cis-1,2-dichloroethene, vinyl chloride, and ethene, as well as compounds associated with free-phase diesel present at the site. Compound specific isotope (CSI) analysis was performed to characterize biotransformation processes influencing the transport and fate of the chlorinated contaminants. PCR analysis was used to assess the presence of indigenous reductive dechlorinators. The target regions employed were the 16s rRNA gene sequences of Dehalococcoides sp. and Desulfuromonas sp., and DNA sequences of genes pceA, tceA, bvcA, and vcrA, which encode reductive dehalogenases. The results of the analyses indicate that relevant microbial populations are present and that reductive dechlorination is presently occurring at the site. The results further show that potential degrader populations as well as biotransformation activity is non-uniformly distributed within the site. The results of laboratory microcosm studies conducted using groundwater collected from the field site confirmed the reductive dechlorination of tetrachloroethene to dichloroethene. This study illustrates the use of an integrated, multiple-method approach for assessing natural attenuation at a complex chlorinated-solvent contaminated site. PMID:19603638

Graphene Synthesis & Graphene/Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Liao, Ken-Hsuan

We successfully developed a novel, fast, hydrazine-free, high-yield method for producing single-layered graphene. Graphene sheets were formed from graphite oxide by reduction with de-ionized water at 130 ºC. Over 65% of the sheets are single graphene layers. A dehydration reaction of exfoliated graphene oxide was utilized to reduce oxygen and transform C-C bonds from sp3 to sp2. The reduction appears to occur in large uniform interconnected oxygen-free patches so that despite the presence of residual oxygen the sp2 carbon bonds formed on the sheets are sufficient to provide electronic properties comparable to reduced graphene sheets obtained using other methods. Cytotoxicity of aqueous graphene was investigated with Dr. Yu-Shen Lin by measuring mitochondrial activity in adherent human skin fibroblasts using two assays. The methyl-thiazolyl-diphenyl-tetrazolium bromide (MTT) assay, a typical nanotoxicity assay, fails to predict the toxicity of graphene oxide and graphene toxicity because of the spontaneous reduction of MTT by graphene and graphene oxide, resulting in a false positive signal. An appropriate alternate assessment, using the water soluble tetrazolium salt (WST-8) assay, reveals that the compacted graphene sheets are more damaging to mammalian fibroblasts than the less densely packed graphene oxide. Clearly, the toxicity of graphene and graphene oxide depends on the exposure environment (i.e. whether or not aggregation occurs) and mode of interaction with cells (i.e. suspension versus adherent cell types). Ultralow percolation concentration of 0.15 wt% graphene, as determined by surface resistance and modulus, was observed from in situ polymerized thermally reduced graphene (TRG)/ poly-urethane-acrylate (PUA) nanocomposite. A homogeneous dispersion of TRG in PUA was revealed by TEM images. The aspect ratio of dispersed TRG, calculated from percolation concentration and modulus, was found to be equivalent to the reported aspect ratio of single-layered free standing TRG. This indicates TRG is mono-layer-dispersed in the matrix polymer. How graphene/polymer nanocomposite glass transition temperatures ( Tg) vary was investigated in this study. We measured Tg in PMMA. We used isotactic PMMA (i-PMMA) and syndiotactic-rich atactic PMMA (a-PMMA) to make TRG/PMMA nanocomposites using solvent blending and in situ polymerization in order to investigate the stereo-regularity and processing effects on the Tg. A T g increase was found in i-PMMA and in situ PMMA but not in a-PMMA. The results can be explained by the thin film confinement effect of polymer. We attribute the Tg increase to both a higher interaction density and a stronger hydrogen bonding at the interfaces. We have studied the elastic modulus of graphene oxide with various oxygen content. We used in situ AFM nano-indentation to measure the influence of oxygen on the elastic modulus of graphene oxide with various carbon/oxygen (C/O) ratios. The results show that chemical reduction (lower oxygen contents) decreases the elastic modulus of graphene oxide. We speculate that chemical reduction of oxygen atoms of epoxy groups on graphene oxide surface removes the bridging effect between carbon atoms, which leads to more flexible sheets. (Abstract shortened by UMI.).

Feasibility studies of in-situ coal gasification in the Warrior coal field. Quarterly report

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

Douglas, G.W.; McKinley, M.D.

1979-03-01

Laboratory studies on a research combustor were used in an attempt to determine the length of oxidation and reduction zones. Unfortunately the buoyant effects of the heated gases caused the burn to proceed along the upper portion of the horizontal combustor. This made the interpretation of uncertain value. Methods of measuring the thermal conductivity and chemical reactivity of coke are discussed. A bibliography of the physical and chemical properties of coke is appended. (LTN)

Situ formation of apatite for sequestering radionuclides and heavy metals

DOEpatents

Moore, Robert C.

2003-07-15

Methods for in situ formation in soil of a permeable reactive barrier or zone comprising a phosphate precipitate, such as apatite or hydroxyapatite, which is capable of selectively trapping and removing radionuclides and heavy metal contaminants from the soil, while allowing water or other compounds to pass through. A preparation of a phosphate reagent and a chelated calcium reagent is mixed aboveground and injected into the soil. Subsequently, the chelated calcium reagent biodegrades and slowly releases free calcium. The free calcium reacts with the phosphate reagent to form a phosphate precipitate. Under the proper chemical conditions, apatite or hydroxyapatite can form. Radionuclide and heavy metal contaminants, including lead, strontium, lanthanides, and uranium are then selectively sequestered by sorbing them onto the phosphate precipitate. A reducing agent can be added for reduction and selective sequestration of technetium or selenium contaminants.

In situ/Operando studies of electrocatalysts using hard X-ray spectroscopy

DOE PAGES

Lassalle-Kaiser, Benedikt; Gul, Sheraz; Kern, Jan; ...

2017-05-02

This review focuses on the use of X-ray absorption and emission spectroscopy techniques using hard X-rays to study electrocatalysts under in situ/operando conditions. The importance and the versatility of methods in the study of electrodes in contact with the electrolytes are described, when they are being cycled through the catalytic potentials during the progress of the oxygen-evolution, oxygen reduction and hydrogen evolution reactions. The catalytic oxygen evolution reaction is illustrated with examples using three oxides, Co, Ni and Mn, and two sulfides, Mo and Co. These are used as examples for the hydrogen evolution reaction. A bimetallic, bifunctional oxygen evolvingmore » and oxygen reducing Ni/Mn oxide is also presented. The various advantages and constraints in the use of these techniques and the future outlook are discussed.« less

In Situ Elevated Temperature Testing of Fly Ash Based Geopolymer Composites

PubMed Central

Vickers, Les; Pan, Zhu; Tao, Zhong; van Riessen, Arie

2016-01-01

In situ elevated temperature investigations using fly ash based geopolymers filled with alumina aggregate were undertaken. Compressive strength and short term creep tests were carried out to determine the onset temperature of viscous flow. Fire testing using the standard cellulose curve was performed. Applying a load to the specimen as the temperature increased reduced the temperature at which viscous flow occurred (compared to test methods with no applied stress). Compressive strength increased at the elevated temperature and is attributed to viscous flow and sintering forming a more compact microstructure. The addition of alumina aggregate and reduction of water content reduced the thermal conductivity. This led to the earlier onset and shorter dehydration plateau duration times. However, crack formation was reduced and is attributed to smaller thermal gradients across the fire test specimen. PMID:28773568

Theoretical and experimental errors for in situ measurements of plant water potential.

PubMed

Shackel, K A

1984-07-01

Errors in psychrometrically determined values of leaf water potential caused by tissue resistance to water vapor exchange and by lack of thermal equilibrium were evaluated using commercial in situ psychrometers (Wescor Inc., Logan, UT) on leaves of Tradescantia virginiana (L.). Theoretical errors in the dewpoint method of operation for these sensors were demonstrated. After correction for these errors, in situ measurements of leaf water potential indicated substantial errors caused by tissue resistance to water vapor exchange (4 to 6% reduction in apparent water potential per second of cooling time used) resulting from humidity depletions in the psychrometer chamber during the Peltier condensation process. These errors were avoided by use of a modified procedure for dewpoint measurement. Large changes in apparent water potential were caused by leaf and psychrometer exposure to moderate levels of irradiance. These changes were correlated with relatively small shifts in psychrometer zero offsets (-0.6 to -1.0 megapascals per microvolt), indicating substantial errors caused by nonisothermal conditions between the leaf and the psychrometer. Explicit correction for these errors is not possible with the current psychrometer design.

Theoretical and Experimental Errors for In Situ Measurements of Plant Water Potential 1

PubMed Central

Shackel, Kenneth A.

1984-01-01

Errors in psychrometrically determined values of leaf water potential caused by tissue resistance to water vapor exchange and by lack of thermal equilibrium were evaluated using commercial in situ psychrometers (Wescor Inc., Logan, UT) on leaves of Tradescantia virginiana (L.). Theoretical errors in the dewpoint method of operation for these sensors were demonstrated. After correction for these errors, in situ measurements of leaf water potential indicated substantial errors caused by tissue resistance to water vapor exchange (4 to 6% reduction in apparent water potential per second of cooling time used) resulting from humidity depletions in the psychrometer chamber during the Peltier condensation process. These errors were avoided by use of a modified procedure for dewpoint measurement. Large changes in apparent water potential were caused by leaf and psychrometer exposure to moderate levels of irradiance. These changes were correlated with relatively small shifts in psychrometer zero offsets (−0.6 to −1.0 megapascals per microvolt), indicating substantial errors caused by nonisothermal conditions between the leaf and the psychrometer. Explicit correction for these errors is not possible with the current psychrometer design. PMID:16663701

Negligible degradation upon in situ voltage cycling of a PEMFC using an electrospun niobium-doped tin oxide supported Pt cathode.

PubMed

Savych, Iuliia; Subianto, Surya; Nabil, Yannick; Cavaliere, Sara; Jones, Deborah; Rozière, Jacques

2015-07-14

Novel platinum-catalysed, corrosion-resistant, loose-tube-structured electrocatalysts for proton exchange membrane fuel cells have been obtained using single-needle electrospinning associated with a microwave-assisted polyol method. Monodisperse platinum particles supported on Nb-SnO2 demonstrated higher electrochemical stability than conventional Pt/C electrodes during ex situ potential cycling and comparable activity in the oxygen reduction reaction. In situ fuel cell operation under accelerated stress test conditions of a membrane electrode assembly elaborated using a Pt/C anode and Pt/Nb-SnO2 cathode confirmed that the voltage loss is significantly lower for the novel cathode than for an MEA prepared using conventional Pt/C supported electrocatalysts. Furthermore, the Nb-SnO2 stabilised the supported platinum nanoparticles against dissolution, migration and reprecipitation in the membrane. Pt/Nb-SnO2 loose-tubes constitute a mitigation strategy for two known degradation mechanisms in PEMFC: corrosion of the carbon support at the cathode, and dissolution of Pt at high cell voltages.

Aluminothermic Reduction-Molten Salt Electrolysis Using Inert Anode for Oxygen and Al-Base Alloy Extraction from Lunar Soil Simulant

NASA Astrophysics Data System (ADS)

Xie, Kaiyu; Shi, Zhongning; Xu, Junli; Hu, Xianwei; Gao, Bingliang; Wang, Zhaowen

2017-10-01

Aluminothermic reduction-electrolysis using an inert anode process is proposed to extract oxygen and metals from Minnesota Lunar Simulant-1 (MLS-1). Effective aluminothermic reduction between dissolved MLS-1 and dissolved metal aluminum was achieved in cryolite salt media. The product phases obtained by aluminothermic reduction at 980°C for 4 h were Al, Si, and Al5FeSi, while the chemical components were 79.71 mass% aluminum, 12.03 mass% silicon, 5.91 mass% iron, and 2.35 mass% titanium. The cryolite salt containing Al2O3 was subsequently electrolyzed with Fe0.58-Ni0.42 inert anode at 960°C for 4 h. Oxygen was evolved at the anode with an anodic current efficiency of 78.28%. The results demonstrate that this two-step process is remarkably feasible for the extraterrestrial extraction of oxygen and metals. This process will help expand the existing in situ resource utilization methods.

In Situ and In Vitro Effects of Two Bleaching Treatments on Human Enamel Hardness.

PubMed

Henn-Donassollo, Sandrina; Fabris, Cristiane; Gagiolla, Morgana; Kerber, Ícaro; Caetano, Vinícius; Carboni, Vitor; Salas, Mabel Miluska Suca; Donassollo, Tiago Aurélio; Demarco, Flávio Fernando

2016-01-01

The aim of this study was to evaluate in vitro and in situ the effects of two bleaching treatments on human enamel surface microhardness. Sixty enamel slabs from recently extracted thirty molars were used. The specimens were polished with sandpapers under water-cooling. The enamel samples were randomly divided in four groups, treated with 10% hydrogen peroxide (HP) or Whitening Strips (WS) containing 10% hydrogen peroxide and using two conditions: in vitro or in situ model. For in situ condition, six volunteers wore an intra-oral appliance containing enamel slabs, while for in vitro condition the specimens were kept in deionized water after the bleaching protocols. The bleaching treatments were applied one-hour daily for 14 days. Similar amounts of bleaching agents were used in both conditions. Before and after bleaching treatments, microhardness was measured. Statistical analysis (ANOVA and Tukey test) showed that in the in situ condition there was no statistically significant microhardness reduction in the bleached enamel (p>0.05). Significant decrease in hardness was observed for enamel slabs bleached with both treatments in the in vitro condition (p<0.05). Regarding the bleaching agents, in situ results showed no difference between HP and WS, while in vitro WS produced the lowest hardness value. It could be concluded that there was no deleterious effect on enamel produced by any of the bleaching protocols used in the in situ model. The reduction of hardness was only observed in vitro.

Trimetallic Hybrid Nanoflower-Decorated MoS2 Nanosheet Sensor for Direct in Situ Monitoring of H2O2 Secreted from Live Cancer Cells.

PubMed

Dou, Baoting; Yang, Jianmei; Yuan, Ruo; Xiang, Yun

2018-05-01

In situ monitoring of hydrogen peroxide (H 2 O 2 ) secreted from live cells plays a critical role in elucidating many cellular signaling pathways, and it is a significant challenge to selectively detect these low levels of endogenous H 2 O 2 . To address this challenge, we report the establishment of a trimetallic hybrid nanoflower-decorated MoS 2 nanosheet-modified sensor for in situ monitoring of H 2 O 2 secreted from live MCF-7 cancer cells. The Au-Pd-Pt nanoflower-dispersed MoS 2 nanosheets are synthesized by a simple wet-chemistry method, and the resulting nanosheet composites exhibit significantly enhanced catalytic activity toward electrochemical reduction of H 2 O 2 , due to the synergistic effect of the highly dispersed trimetallic hybrid nanoflowers and the MoS 2 nanosheets, thereby resulting in ultrasensitive detection of H 2 O 2 with a subnanomolar level detection limit in vitro. Also the immobilization of the laminin glycoproteins on the surface of the nanocomposites increases its biocompatibility for cell adhesion and growth, which enables in situ electrochemical monitoring of H 2 O 2 directly secreted from live cells for potential application of such sensor in cellular biology, clinical diagnosis, and pathophysiology.

Stereochemistry of Furfural Reduction by a Saccharomyces cerevisiae Aldehyde Reductase That Contributes to In Situ Furfural Detoxification

USDA-ARS?s Scientific Manuscript database

Ari1p from Saccharomyces cerevisiae, recently identified as an intermediate subclass short-chain dehydrogenase/reductase, contributes in situ to the detoxification of furfural. Furfural inhibits efficient ethanol production by the yeast, particularly when the carbon source is acid-treated lignocell...

IN-SITU REMEDIATION OF CHROMIUM-CONTAMINATED SOILS AND SEDIMENTS

EPA Science Inventory

The objectives of this study were to characterize the extent of total chromium and Cr(VI)contamination in the underlying soils and sediments of a chrome-plating shop at the USCG Support Center near Elizabeth City, NC and to evaluate the use of liquid reductants for in situ treatm...

Evaluation Of In Situ Steam-Injection Processes For Reduction Of Petroleum Compounds Within An Abandoned Canal

EPA Science Inventory

A conceptual approach of a novel application of in-situ thermal processes that would either use a steam injection process or a steam/surfactant injection process was considered to remediate petroleum contaminated sediment residing in an abandoned canal. Laboratory tests were c...

Combined abiotic and biotic in-situ reduction of hexavalent chromium in groundwater using nZVI and whey: A remedial pilot test.

PubMed

Němeček, Jan; Pokorný, Petr; Lacinová, Lenka; Černík, Miroslav; Masopustová, Zuzana; Lhotský, Ondřej; Filipová, Alena; Cajthaml, Tomáš

2015-12-30

The paper describes a pilot remediation test combining two Cr(VI) geofixation methods - chemical reduction by nanoscale zero-valent iron (nZVI) and subsequent biotic reduction supported by whey. Combination of the methods exploited the advantages of both - a rapid decrease in Cr(VI) concentrations by nZVI, which prevented further spreading of the contamination and facilitated subsequent use of the cheaper biological method. Successive application of whey as an organic substrate to promote biotic reduction of Cr(VI) after application of nZVI resulted in a further and long-term decrease in the Cr(VI) contents in the groundwater. The effect of biotic reduction was observed even in a monitoring well located at a distance of 22 m from the substrate injection wells after 10 months. The results indicated a reciprocal effect of both the phases - nZVI oxidized to Fe(III) during the abiotic phase was microbially reduced back to Fe(II) and acted as a reducing agent for Cr(VI) even when the microbial density was already low due to the consumed substrate. Community analysis with pyrosequencing of the 16S rRNA genes further confirmed partial recycling of nZVI in the form of Fe(II), where the results showed that the Cr(VI) reducing process was mediated mainly by iron-reducing and sulfate-reducing bacteria. Copyright © 2015 Elsevier B.V. All rights reserved.

Implementation of laser induced fluorescence in a pulse radiolysis experiment--a new way to analyze resazurin-like reduction mechanisms.

PubMed

Balcerzyk, A; Baldacchino, G

2014-04-07

Resazurin (RNO) reduction by hydrated electrons produces a fluorescent molecule: resorufin (RN). To take advantage of RN fluorescence, a novel setup is designed by implementing fluorescence detection induced by laser in a pulse radiolysis experiment. Time resolved fluorescence spectra were recorded with a fast gated intensified CCD camera during the reduction of RNO from μs to ms. Two 532 nm laser types have been used to describe the short μs range by a 5 ns Q-switch laser and the μs-ms range by a CW DPSS laser. By fitting the simulated model to the experimental data a second order rate constant of 10(9) M(-1) s(-1) was re-evaluated. This method should be considered in the near future in many in situ and real time measurements for evaluating radical production.

Carbothermic reduction and prereduced charge for producing aluminum-silicon alloys

DOEpatents

Stevenson, David T.; Troup, Robert L.

1985-01-01

Disclosed is a method for the carbothermic reduction of aluminum oxide to form an aluminum alloy including producing silicon carbide by heating a first mix of carbon and silicon oxide in a combustion reactor to an elevated temperature sufficient to produce silicon carbide at an accelerated rate, the heating being provided by an in situ combustion with oxygen gas, and then admixing the silicon carbide with carbon and aluminum oxide to form a second mix and heating the second mix in a second reactor to an elevated metal-forming temperature sufficient to produce aluminum-silicon alloy. The prereduction step includes holding aluminum oxide substantially absent from the combustion reactor. The metal-forming step includes feeding silicon oxide in a preferred ratio with silicon carbide.

ZnO and cobalt phthalocyanine hybridized graphene: efficient photocatalysts for degradation of rhodamine B

PubMed Central

Neelgund, Gururaj M.; Oki, Aderemi; Luo, Zhiping

2014-01-01

A novel method has been developed to synthesize graphene-ZnO composite as a highly efficient catalyst by reduction of graphite oxide and in-situ deposition of ZnO nanoparticles by chemical reduction reaction. The graphene-ZnO catalyst is capable of complete degradation of rhodamine B under exposure to natural sunlight. Further, the catalytic efficiency of graphene-ZnO catalyst was enhanced by sensitizing with cobalt phthalocyanine. The formation of graphene-ZnO pcatalyst and its further sensitization with cobalt phthalocyanine was characterized using UV-vis, ATR-IR and Raman spectroscopy, powder XRD and thermogravimetric analysis. The morphology of both graphene-ZnO and graphene-ZnO-CoPC catalysts was analyzed using scanning and transmission electron microscopes. PMID:24972296

Efficient reduction of CO2 to CO with high current density using in situ or ex situ prepared Bi-based materials.

PubMed

Medina-Ramos, Jonnathan; DiMeglio, John L; Rosenthal, Joel

2014-06-11

The development of inexpensive electrocatalysts that can promote the reduction of CO2 to CO with high selectivity, efficiency, and large current densities is an important step on the path to renewable production of liquid carbon-based fuels. While precious metals such as gold and silver have historically been the most active cathode materials for CO2 reduction, the price of these materials precludes their use on the scale required for fuel production. Bismuth, by comparison, is an affordable and environmentally benign metal that shows promise for CO2 conversion applications. In this work, we show that a bismuth-carbon monoxide evolving catalyst (Bi-CMEC) can be formed under either aqueous or nonaqueous conditions using versatile electrodeposition methods. In situ formation of this thin-film catalyst on an inexpensive carbon electrode using an organic soluble Bi(3+) precursor streamlines preparation of this material and generates a robust catalyst for CO2 reduction. In the presence of appropriate imidazolium based ionic liquid promoters, the Bi-CMEC platform can selectively catalyze conversion of CO2 to CO without the need for a costly supporting electrolyte. This inexpensive system can catalyze evolution of CO with current densities as high as jCO = 25-30 mA/cm(2) and attendant energy efficiencies of ΦCO ≈ 80% for the cathodic half reaction. These metrics highlight the efficiency of Bi-CMEC, since only noble metals have been previously shown to promote this fuel forming half reaction with such high energy efficiency. Moreover, the rate of CO production by Bi-CMEC ranges from approximately 0.1-0.5 mmol·cm(-2)·h(-1) at an applied overpotential of η ≈ 250 mV for a cathode with surface area equal to 1.0 cm(2). This CO evolution activity is much higher than that afforded by other non-noble metal cathode materials and distinguishes Bi-CMEC as a superior and inexpensive platform for electrochemical conversion of CO2 to fuel.

In-situ X-ray diffraction activation study on an Fe/TiO2 pre-catalyst.

PubMed

Rayner, Matthew K; Billing, David G; Coville, Neil J

2014-06-01

This study focuses on the use of in situ powder X-ray diffraction (PXRD) and quantitative phase analysis using the Rietveld method to monitor the structural properties of a titania-supported iron (10% Fe/TiO2) pre-catalyst during calcination (oxidation) and activation (reduction) in the temperature range 25-900°C. The TiO2 oxidation study revealed an increase in anatase particle size before the anatase to rutile phase transformation, lending credibility to the bridging mechanism proposed by Kim et al. [(2007), Mater. Sci. Forum, 534-536, 65-68]. Pre-catalyst oxidation experiments allowed for the determination of a suitable calcination temperature (450°C) of the pre-catalyst in terms of maximum hematite concentration and appropriate particle size. These experiments also confirmed that the anatase to rutile phase transformation occurred at higher temperatures after Fe addition and that anatase was the sole donor of Ti(4+) ions, which are known to migrate into hematite (Gennari et al., 1998), during the formation of pseudobrookite (Fe2TiO5) at temperatures above 690°C. Using the results from the oxidation experiments, two pre-catalyst samples were calcined at different temperatures; one to represent the preferred case and one to represent a case where the pre-catalyst had been excessively heated. Samples of the excessively heated catalysts were exposed to different reducing gas atmospheres (5, 10 and 100% H2/N2) and heated in the in situ PXRD reactor, so that diffraction data could be collected during the activation process. The results show that reduction with gases containing low concentrations of H2 (5 and 10%) led to the formation of ilmenite (FeTiO3) and we were able to show that both anatase and rutile are consumed in the reaction. Higher concentrations of H2 led to the formation of magnetite (Fe3O4) and metallic iron (Fe(0)). We also noted a decrease in the anatase to rutile transformation temperature under reducing atmospheres when compared with the pre-catalyst heat-treatment experiment. A reduced calcination temperature prior to reduction allowed more facile Fe reduction.

The treatment of idiopathic scoliosis in adolescents: rotation or in situ bending?

PubMed

Gennari, J M; Tallet, J M; Hornung, H; Bergoin, M

1997-12-01

Rotation alone is not fully efficient in order to correct all types of scoliotic curvatures. We report a series of 30 cases instrumented with the EUROS spine system and analyse reductions obtained with in situ rotation or bending alone or with combined maneuvres. The average age of surgery is 17 years for this series composed of 24 female and 6 male patients. The average follow-up is 2.3 years. The curve patterns are displayed with 6 major thoracic, 5 genuine double major, 4 double major thoracic predominant, 6 double major lumbar predominant and 9 double thoracic curves. Combination of both reduction techniques is advisable and is to be made according to the type of curvature and its reducibility in situ bending is made easier with this system without lockers and by reduced diameter of the rod.

Reduction of Cr(VI) to Cr(III) by wetland plants: Potential for in situ heavy metal detoxification

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

Lytle, C.M.; Qian, J.H.; Hansen, D.

1998-10-15

Reduction of heavy metals in situ by plants may be a useful detoxification mechanism for phytoremediation. Using X-ray spectroscopy, the authors show that Eichhornia crassipes (water hyacinth), supplied with Cr(VI) in nutrient culture, accumulated nontoxic Cr(III) in root and shoot tissues. The reduction of Cr(VI) to Cr(III) appeared to occur in the fine lateral roots. The Cr(III) was subsequently translocated to leaf tissues. Extended X-ray absorption fine structure of Cr in leaf and petiole differed when compared to Cr in roots. In roots, Cr(III) was hydrated by water, but in petiole and more so in leaf, a portion of themore » Cr(III) may be bound to oxalate ligands. This suggests that E. crassipes detoxified Cr(VI) upon root uptake and transported a portion of the detoxified Cr to leaf tissues. Cr-rich crystalline structures were observed on the leaf surface. The chemical species of Cr in other plants, collected from wetlands that contained Cr(VI)-contaminated wastewater, was also found to be Cr(III). The authors propose that this plant-based reduction of Cr(VI) by E. crassipes has the potential to be used for the in situ detoxification of Cr(VI)-contaminated wastestreams.« less

Applications of laser-induced breakdown spectroscopy in the aluminum electrolysis industry

NASA Astrophysics Data System (ADS)

Sun, Lanxiang; Yu, Haibin; Cong, Zhibo; Lu, Hui; Cao, Bin; Zeng, Peng; Dong, Wei; Li, Yang

2018-04-01

The industrial aluminum reduction cell is an electrochemistry reactor that operates under high temperatures and corrosive conditions. Monitoring the molten aluminum and electrolyte components is very important for controlling the chemical reaction process. Due to the lack of fast methods to monitor the components, controlling aluminum reduction cells is difficult. In this work, laser-induced breakdown spectroscopy (LIBS) was applied to aluminum electrolysis. A new method for calculating the molecular ratio, which is an important control parameter that represents the acidity of the electrolyte, was proposed. Experiments were first performed on solid electrolyte samples to test the performance of the proposed method. Using this method, the average relative standard deviation (RSD) of the molecular ratio measurement was 0.39%, and the average root mean square error (RMSE) was 0.0236. These results prove that LIBS can accurately measure the molecular ratio. Then, in situ measurements of the molten aluminum and electrolyte were performed in industrial aluminum induction cells using the developed LIBS equipment. The spectra of the molten electrolyte were successfully obtained and were consistent with the spectra of the solid electrolyte.

High-Throughput Fabrication Method for Producing a Silver-Nanoparticles-Doped Nanoclay Polymer Composite with Novel Synergistic Antibacterial Effects at the Material Interface.

PubMed

Cai, Shaobo; Pourdeyhimi, Behnam; Loboa, Elizabeth G

2017-06-28

In this study, we report a high-throughput fabrication method at industrial pilot scale to produce a silver-nanoparticles-doped nanoclay-polylactic acid composite with a novel synergistic antibacterial effect. The obtained nanocomposite has a significantly lower affinity for bacterial adhesion, allowing the loading amount of silver nanoparticles to be tremendously reduced while maintaining satisfactory antibacterial efficacy at the material interface. This is a great advantage for many antibacterial applications in which cost is a consideration. Furthermore, unlike previously reported methods that require additional chemical reduction processes to produce the silver-nanoparticles-doped nanoclay, an in situ preparation method was developed in which silver nanoparticles were created simultaneously during the composite fabrication process by thermal reduction. This is the first report to show that altered material surface submicron structures created with the loading of nanoclay enables the creation of a nanocomposite with significantly lower affinity for bacterial adhesion. This study provides a promising scalable approach to produce antibacterial polymeric products with minimal changes to industry standard equipment, fabrication processes, or raw material input cost.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

PubMed

Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

2017-06-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

GREEN AND SUSTAINABLE REMEDIATION BEST MANAGEMENT PRACTICES

DTIC Science & Technology

2016-09-07

adoption. The technologies covered include air sparging, biosparging, soil vapor extraction (SVE), enhanced reductive dechlorination (ERD), in situ...RPM Remedial Project Manager SCR selective catalytic reduction SEE steam enhanced extraction SVE soil vapor extraction TCE trichloroethene...further promote their adoption. The technologies covered include air sparging, biosparging, soil vapor extraction (SVE), enhanced reductive

Phosphorus Amendment Efficacy for In Situ Remediation of ...

EPA Pesticide Factsheets

A validated method is needed to measure reductions of in vitro bioaccessible (IVBA) Pb in urban soil remediated with amendments. This study evaluated the effect of in vitro extraction solution pH and glycine buffer on bioaccesible Pb in P-treated soils. Two Pb-contaminated soils (790-1300 mg Pb kg-1), one from a garden and one from a city lot in Cleveland, OH, were incubated in a bench scale experiment for 1 yr. Six phosphate amendments, including bone meal, fish bone, poultry litter, monoammonium phosphate, diammonium phosphate, and triple superphosphate, were added to containers at two application rates. Lead IVBA was assessed using USEPA Method 1340 and three modified versions of this method. Modifications included using solutions with pH 1.5 and 2.5 as well as using solutions with and without 0.4 mol L-1 glycine. Soil amendments were effective in reducing IVBA Pb in these soils as measured by pH 1.5 with glycine buffer. The greatest reductions in IVBA Pb, from 5 to 26%, were found using pH 2.5 extractions. Lead mineral results showed several soil amendments promoted Pb phosphate formation, an indicator of remediation success. A significant negative linear relationship between reduction in IVBA Pb and Pb-phosphate formation was found only for pH 2.5 without glycine extraction solution. A modified USEPA Method 1340 without glycine and using pH 2.5 has the potential to predict P soil treatment efficacy and reductions in bioavailable Pb. Developing mana

Multifunctional nanocomposites of Fe3O4-graphene-Au for repeated use in simultaneous adsorption, in situ SERS detection and catalytic reduction of 4-nitrophenol in water

NASA Astrophysics Data System (ADS)

Chen, Fenghua; Wang, Yongwei; Chen, Qingtao; Han, Lifeng; Chen, Zhijun; Fang, Shaoming

2014-12-01

This work is directed towards the synthesis of a ternary nanocomposite of Fe3O4-graphene-Au, i.e. Fe3O4 nanoparticles (˜300 nm in size) and Au nanoparticles (˜50 nm in size) loaded on the carbon basal planes of reduced graphene oxide, aimed for repeated use in simultaneous adsorption, in situ SERS detection and catalytic reduction of 4-nitrophenol (4-NP) in water, and also for recovering the useful reduction product of 4-aminophenol (4-AP). The results indicate that the amount of 4-NP and 4-AP absorbed to the prepared Fe3O4-graphene-Au nanocomposite can reach 170 mg g-1 and 447 mg g-1, respectively. The reduction reaction of 4-NP to 4-AP by NaBH4 with the Fe3O4-graphene-Au nanocomposite as a catalyst follows first-order kinetics with a rate constant (k) of about 0.4964 min-1, remarkably superior to the 0.1199 min-1 for the reduction reaction with the bare Au nanoparticles under the same conditions. In addition, in situ SERS can also be carried out to detect 4-NP and to monitor the reduction reaction with Fe3O4-graphene-Au as the substrate. Recycling of the composite can be achieved by simply applying an external magnetic field and the results demonstrate that it can be reused at least eight times with almost unaffected catalytic efficiency.

Novel, in-situ Raman and fluorescence measurement techniques: Imaging using optical waveguides

NASA Astrophysics Data System (ADS)

Carter, Jerry Chance

The following dissertation describes the development of methods for performing standoff and in- situ Raman and fluorescence spectroscopy for chemical imaging and non-imaging analytical applications. The use of Raman spectroscopy for the in- situ identification of crack cocaine and cocaine.HCl using a fiberoptic Raman probe and a portable Raman spectrograph has been demonstrated. We show that the Raman spectra of both forms of cocaine are easily distinguishable from common cutting agents and impurities such as benzocaine and lidocaine. We have also demonstrated the use of Raman spectroscopy for in-situ identification of drugs separated by thin layer chromatography. We have investigated the use of small, transportable, Raman systems for standoff Raman spectroscopy (e.g. <20 m). For this work, acousto-optical (AOTF) and liquid crystal tunable filters (LCTF) are being used both with, and in place of dispersive spectrographs and fixed filtering devices. In addition, we improved the flexibility of the system by the use of a modified holographic fiber-optic probe for light and image collection. A comparison of tunable filter technologies for standoff Raman imaging is discussed along with the merits of image transfer devices using small diameter image guides. A standoff Raman imaging system has been developed that utilizes a unique polymer collection mirror. The techniques used to produce these mirrors make it easy to design low f/# polymer mirrors. The performance of a low f/# polymer mirror system for standoff Raman chemical imaging has been demonstrated and evaluated. We have also demonstrated remote Raman hyperspectral imaging using a dimension-reduction, 2-dimensional (2-D) to 1-dimensional (1-D), fiber optic array. In these studies, a modified holographic fiber-optic probe was combined with the dimension-reduction fiber array for remote Raman imaging. The utility of this setup for standoff Raman imaging is demonstrated by monitoring the polymerization of dibromostyrene. To further demonstrate the utility of in- situ spectral imaging, we have shown that small diameter (350 μm) image guides can be used for in-situ measurements of analyte transport in thin membranes. This has been applied to the measurement of H2O diffusion in Nafion™ membranes using the luminescent compound, [Ru(phen)2dppz] 2+, which is a H2O indicator.

Redox-active ionic-liquid-assisted one-step general method for preparing gold nanoparticle thin films: applications in refractive index sensing and catalysis.

PubMed

Dinda, Enakshi; Rashid, Md Harunar; Biswas, Mrinmoy; Mandal, Tarun K

2010-11-16

We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.

Combination of TOPEX/POSEIDON Data with a Hydrographic Inversion for Determination of the Oceanic General Circulation and its Relation to Geoid Accuracy

NASA Technical Reports Server (NTRS)

Ganachaud, Alexandre; Wunsch, Carl; Kim, Myung-Chan; Tapley, Byron

1997-01-01

A global estimate of the absolute oceanic general circulation from a geostrophic inversion of in situ hydrographic data is tested against and then combined with an estimate obtained from TOPEX/POSEIDON altimetric data and a geoid model computed using the JGM-3 gravity-field solution. Within the quantitative uncertainties of both the hydrographic inversion and the geoid estimate, the two estimates derived by very different methods are consistent. When the in situ inversion is combined with the altimetry/geoid scheme using a recursive inverse procedure, a new solution, fully consistent with both hydrography and altimetry, is found. There is, however, little reduction in the uncertainties of the calculated ocean circulation and its mass and heat fluxes because the best available geoid estimate remains noisy relative to the purely oceanographic inferences. The conclusion drawn from this is that the comparatively large errors present in the existing geoid models now limit the ability of satellite altimeter data to improve directly the general ocean circulation models derived from in situ measurements. Because improvements in the geoid could be realized through a dedicated spaceborne gravity recovery mission, the impact of hypothetical much better, future geoid estimates on the circulation uncertainty is also quantified, showing significant hypothetical reductions in the uncertainties of oceanic transport calculations. Full ocean general circulation models could better exploit both existing oceanographic data and future gravity-mission data, but their present use is severely limited by the inability to quantify their error budgets.

Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode.

PubMed

Yang, Haifeng; Liu, Yanli; Liu, Zhimin; Yang, Yu; Jiang, Jianhui; Zhang, Zongrang; Shen, Guoli; Yu, Ruqin

2005-02-24

The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.

Fatigue Damage Assessment Leveraging Nondestructive Evaluation Data

NASA Astrophysics Data System (ADS)

Mazur, K.; Wisner, B.; Kontsos, A.

2018-05-01

Fatigue in materials depends on several microstructural parameters. The length and time scales involved in such processes have been investigated by characterization methods that target microstructural effects or that rely on specimen-level observations. Combinations of in situ and ex situ techniques are also used to correlate microstructural changes to bulk properties. We present herein an effort to directly link local changes with specimen-level fatigue damage assessment. To achieve this goal, grain-scale observations in an aluminum alloy are linked with deformation measurements made by digital image correlation and with acoustic emission monitoring obtained from inside the scanning electron microscope. Damage assessment is attempted using a data-processing framework that involves noise removal, data reduction, and classification. The results demonstrate that nondestructive evaluation combined with small-scale testing can provide a means for fatigue damage assessment applicable to a broad range of materials and testing conditions.

Two BASIC computer programs for the determination of in situ stresses using the CSIRO hollow inclusion stress cell and the USBM borehole deformation gage

USGS Publications Warehouse

Smith, W.K.

1982-01-01

The mathematical method of determining in-situ stresses by overcoring, using either the U.S. Bureau of Mines Borehole Deformation Gage or the Commonwealth Scientific and Industrial Research Organisation Hollow Inclusion Stress Cell, is summarized, and data reduction programs for each type of instrument, written in BASIC, are presented. The BASIC programs offer several advantages over previously available FORTRAN programs. They can be executed on a desk-top microcomputer at or near the field site, allowing the investigator to assess the quality of the data and make decisions on the need for additional testing while the crew is still in the field. Also, data input is much simpler than with currently available FORTRAN programs; either English or SI units can be used; and standard deviations of the principal stresses are computed as well as those of the geographic components.

In Situ Determination of Sulfide Turnover Rates in a Meromictic Alpine Lake

PubMed Central

Lüthy, Lucas; Fritz, Markus; Bachofen, Reinhard

2000-01-01

A push-pull method, previously used in groundwater analyses, was successfully adapted for measuring sulfide turnover rates in situ at different depths in the meromictic Lake Cadagno. In the layer of phototrophic bacteria at about 12 m in depth net sulfide consumption was observed during the day, indicating active bacterial photosynthesis. During the night the sulfide turnover rates were positive, indicating a net sulfide production from the reduction of more-oxidized sulfur compounds. Because of lack of light, no photosynthesis takes place in the monimolimnion; thus, only sulfide formation is observed both during the day and the night. Sulfide turnover rates in the oxic mixolimnion were always positive as sulfide is spontaneously oxidized by oxygen and as the rates of sulfide oxidation depend on the oxygen concentrations present. Sulfide oxidation by chemolithotrophic bacteria may occur at the oxicline, but this cannot be distinguished from spontaneous chemical oxidation. PMID:10653740

Pneumatic Regolith Transfer Systems for In-Situ Resource Utilization

NASA Technical Reports Server (NTRS)

Mueller, Robert P.; Townsend, Ivan I., III; Mantovani, James G.

2010-01-01

One aspect of In-Situ Resource Utilization (lSRU) in a lunar environment is to extract oxygen and other elements from the minerals that make up the lunar regolith. Typical ISRU oxygen production processes include but are not limited to hydrogen reduction, carbothermal and molten oxide electrolysis. All of these processes require the transfer of regolith from a supply hopper into a reactor for chemical reaction processing, and the subsequent extraction of the reacted regolith from the reactor. This paper will discuss recent activities in the NASA ISRU project involved with developing pneumatic conveying methods to achieve lunar regolith simulant transfer under I-g and 1/6-g gravitational environments. Examples will be given of hardware that has been developed and tested by NASA on reduced gravity flights. Lessons learned and details of pneumatic regolith transfer systems will be examined as well as the relative performance in a 1/6th G environment

Strong Inverse Correlation Between MicroRNA-125b and Human Papillomavirus DNA in Productive Infection

PubMed Central

Nuovo, Gerard J.; Wu, Xin; Volinia, Stefano; Yan, Fengting; di Leva, Gianpiero; Chin, Nena; Nicol, Alcina F.; Jiang, Jinmai; Otterson, Gregory; Schmittgen, Thomas D.; Croce, Carlo

2014-01-01

Infection by the human papillomavirus (HPV) is a cause of cervical intraepithelial neoplasia (CIN) and cancer. microRNA (miRNA) in situ analysis of the transformation zone epithelia, the site of initial cervical HPV infection, showed that miRNAs let-7c, — 99a, 26a, and 125b were the most abundantly expressed. In situ testing of CIN 1 showed a dramatic reduction in miR-125b expression in the koilocytes, the cytologic marker of productive HPV infection. A marked reduction in miR-125b was likewise observed in the HPV-infected cells of the condyloma acuminatum, verruca vulgaris, and epidermodysplasia verruciformis. Reverse transcriptase in situ polymerase chain reaction (PCR) showed that the pre-miRNA 125b was present in the koilocyte, suggesting direct inactivation of the mature miRNA. HEK cells transfected with only the antimiR-125b showed perinuclear halos equivalent to HPV-infected koilocytes. NIH 3T3 cells transfected with the HPV 16 full-length genome and mimetic miR-125b showed a marked reduction in viral DNA and protein synthesis by quantitative PCR and in situ-based analyses, respectively (P=0.002). Alternatively, cotransfection with anti-miR-125b and HPV 16 markedly increased HPV DNA (P=0.002). Sequence analyses showed strong homology between L2 of different HPV genotypes and miR-125b. Transfection with HPV 16 L2 resulted in a marked reduction in miR-125b levels in the NIH 3T3 cells. HPV L2-induced inactivation of miR-125b is associated with the classic cytologic changes of the koilocyte, and the exogenous application of mimetic miR-125b markedly inhibits HPV DNA synthesis. PMID:20736742

Strong inverse correlation between microRNA-125b and human papillomavirus DNA in productive infection.

PubMed

Nuovo, Gerard J; Wu, Xin; Volinia, Stefano; Yan, Fengting; di Leva, Gianpiero; Chin, Nena; Nicol, Alcina F; Jiang, Jinmai; Otterson, Gregory; Schmittgen, Thomas D; Croce, Carlo

2010-09-01

Infection by the human papillomavirus (HPV) is a cause of cervical intraepithelial neoplasia (CIN) and cancer. microRNA (miRNA) in situ analysis of the transformation zone epithelia, the site of initial cervical HPV infection, showed that miRNAs let-7c, -99a, 26a, and 125b were the most abundantly expressed. In situ testing of CIN 1 showed a dramatic reduction in miR-125b expression in the koilocytes, the cytologic marker of productive HPV infection. A marked reduction in miR-125b was likewise observed in the HPV-infected cells of the condyloma acuminatum, verruca vulgaris, and epidermodysplasia verruciformis. Reverse transcriptase in situ polymerase chain reaction (PCR) showed that the pre-miRNA 125b was present in the koilocyte, suggesting direct inactivation of the mature miRNA. HEK cells transfected with only the antimiR-125b showed perinuclear halos equivalent to HPV-infected koilocytes. NIH 3T3 cells transfected with the HPV 16 full-length genome and mimetic miR-125b showed a marked reduction in viral DNA and protein synthesis by quantitative PCR and in situ-based analyses, respectively (P=0.002). Alternatively, cotransfection with anti-miR-125b and HPV 16 markedly increased HPV DNA (P=0.002). Sequence analyses showed strong homology between L2 of different HPV genotypes and miR-125b. Transfection with HPV 16 L2 resulted in a marked reduction in miR-125b levels in the NIH 3T3 cells. HPV L2-induced inactivation of miR-125b is associated with the classic cytologic changes of the koilocyte, and the exogenous application of mimetic miR-125b markedly inhibits HPV DNA synthesis.

In situ SAXS study on size changes of platinum nanoparticles with temperature

NASA Astrophysics Data System (ADS)

Wang, W.; Chen, X.; Cai, Q.; Mo, G.; Jiang, L. S.; Zhang, K.; Chen, Z. J.; Wu, Z. H.; Pan, W.

2008-09-01

Poly(vinylpyrrolidone) (PVP)-coated platinum (Pt) nanoparticles were prepared in methanol-water reduction method. In situ small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) techniques were used to probe the size change of particles and crystallites with temperature. Tangent-by-tangent (TBT) method of SAXS data analysis was improved and used to get the particle size distribution (PSD) from SAXS intensity. Scherrer’s equation was used to derive the crystallite size from XRD pattern. Combining SAXS and XRD results, a step-like characteristic of the Pt nanoparticle growth has been found. Three stages (diffusion, aggregation, and agglomeration) can be used to describe the growth of the Pt nanoparticles and nanocrystallites. Aggregation was found to be the main growth mode of the Pt nanoparticles during heating. The maximum growth rates of Pt nanoparticles and Pt nanocrystallites, as well as the maximum aggregation degree of Pt nanocrystallites were found, respectively, at 250 °C, 350 °C and 300 °C. These results are helpful to understanding the growth mode of nanoparticles, as well as controlling the nanoparticle size.

Method for enhanced longevity of in situ microbial filter used for bioremediation

DOEpatents

Carman, M. Leslie; Taylor, Robert T.

1999-01-01

An improved method for in situ microbial filter bioremediation having increasingly operational longevity of an in situ microbial filter emplaced into an aquifer. A method for generating a microbial filter of sufficient catalytic density and thickness, which has increased replenishment interval, improved bacteria attachment and detachment characteristics and the endogenous stability under in situ conditions. A system for in situ field water remediation.

Dislocation Density Reduction in Cadmium Telluride and Mercury Cadmium Telluride Grown on Silicon Using Thermal Cycle Annealing

NASA Astrophysics Data System (ADS)

Farrell, Stuart Bennett

Mercury Cadmium Telluride (HgCdTe) is a material of great importance for infrared focal plane array applications. In order to produce large format detector arrays this material needs to be grown on a large area substrate, with silicon being the most mature substrate, it is the optimal choice for large format arrays. To help mitigate the effect of the lattice mismatch between the two materials, cadmium telluride (CdTe) is used as a buffer layer. The CdTe itself has nearly the same lattice mismatch (19.3%) to silicon, but due to the technological advantages it offers and compatibility with HgCdTe, it is the best buffer layer choice. The lattice mismatch between HgCdTe/CdTe and the silicon substrate leads to the formation of dislocations at densities in the mid 106 to low 107 cm-2 range in the epilayers. Such a high dislocation density greatly effects detector device performance quantities such as operability and sensitivity. Hence, the dislocation density should be brought down by at least an order of magnitude by adopting novel in situ and ex situ material processing techniques. In this work, in situ and ex situ thermal cycle annealing (TCA) methods have been used to decrease dislocation density in CdTe and HgCdTe. During the molecular beam epitaxial (MBE) growth of the CdTe buffer layer, the growth was interrupted and the layer was subjected to an annealing cycle within the growth chamber under tellurium overpressure. During the annealing cycle the temperature is raised to beyond the growth temperature (290 → 550 °C) and then allowed to cool before resuming growth again. This process was repeated several times during the growth. After growth, a portion of the material was subjected to a dislocation decoration etch in order to count the etch pit density (EPD) which has a direct correspondence with the dislocation density in the crystal. The crystalline quality was also characterized by x-ray diffraction rocking curves and photoluminescence. The in situ TCA resulted in almost a two order of magnitude reduction in the dislocation density, and factor of two reduction in the full width at half maximum of the x-ray rocking curves. Photoluminescence also suggested a decrease in the number of dislocations present in the material. This decrease is attributed to the movement of the dislocations during the annealing cycles and their subsequent interaction and annihilation. To decrease the dislocation density in HgCdTe layers grown on CdTe/Si composite substrates, ex situ TCA has been performed in a sealed quartz ampoule under a mercury overpressure in a conventional clam-shell furnace. The reduction in the dislocation density has been studied as a function of growth/annealing parameters such as the initial (as grown) dislocation density, buffer layer quality, Hg overpressure, annealing temperature, annealing duration, and the number of annealing cycles. It was found that the primary parameters that affect dislocation density reduction are the annealing temperature and the number of annealing cycles. Some secondary affects were observed by varying the duration spent at the maximum annealing temperature. Parameters such as the initial dislocation density and buffer layer quality did not play a significant role in dislocation reduction. Though no correlation between Hg overpressure and dislocation density was found, it did play a vital role in maintaining the quality of the surface. By using the ex situ TCA, a dislocation density of 1 x 106 cm-2 could be reliably and consistently achieved in HgCdTe layers that had a starting density ranging from 0.5 -- 3 x 107 cm-2. Examination of the annealing parameters revealed an exponential decay in the dislocation density as a function of increasing number of annealing cycles. In addition, a similar exponential decay was observed between the dislocation density and the annealing temperature. The decrease in the dislocation density is once again attributed to moving dislocations that interact and annihilate. This behavior was modeled using a second order reaction equation. It was found that the results of the model closely agreed with the experimental values for a wide range of annealing temperatures and number of annealing cycles.

Aerobic method for the synthesis of nearly size-monodisperse bismuth nanoparticles from a redox non-innocent precursor

NASA Astrophysics Data System (ADS)

Winter, H.; Christopher-Allison, E.; Brown, A. L.; Goforth, A. M.

2018-04-01

Herein, we report an aerobic synthesis method to produce bismuth nanoparticles (Bi NPs) with average diameters in the range 40-80 nm using commercially available bismuth triiodide (BiI3) as the starting material; the method uses only readily available chemicals and conventional laboratory equipment. Furthermore, size data from replicates of the synthesis under standard reaction conditions indicate that this method is highly reproducible in achieving Bi NP populations with low standard deviations in the mean diameters. We also investigated the mechanism of the reaction, which we determined results from the reduction of a soluble alkylammonium iodobismuthate precursor species formed in situ. Under appropriate concentration conditions of iodobismuthate anion, we demonstrate that burst nucleation of Bi NPs results from reduction of Bi3+ by the coordinated, redox non-innocent iodide ligands when a threshold temperature is exceeded. Finally, we demonstrate phase transfer and silica coating of the Bi NPs, which results in stable aqueous colloids with retention of size, morphology, and colloidal stability. The resultant, high atomic number, hydrophilic Bi NPs prepared using this synthesis method have potential for application in emerging x-ray contrast and x-ray therapeutic applications.

Embedded Si/Graphene Composite Fabricated by Magnesium-Thermal Reduction as Anode Material for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhu, Jiangliu; Ren, Yurong; Yang, Bo; Chen, Wenkai; Ding, Jianning

2017-12-01

Embedded Si/graphene composite was fabricated by a novel method, which was in situ generated SiO2 particles on graphene sheets followed by magnesium-thermal reduction. The tetraethyl orthosilicate (TEOS) and flake graphite was used as original materials. On the one hand, the unique structure of as-obtained composite accommodated the large volume change to some extent. Simultaneously, it enhanced electronic conductivity during Li-ion insertion/extraction. The MR-Si/G composite is used as the anode material for lithium ion batteries, which shows high reversible capacity and ascendant cycling stability reach to 950 mAh·g-1 at a current density of 50 mA·g-1 after 60 cycles. These may be conducive to the further advancement of Si-based composite anode design.

Carbothermic reduction and prereduced charge for producing aluminum-silicon alloys

DOEpatents

Stevenson, D.T.; Troup, R.L.

1985-01-01

Disclosed is a method for the carbothermic reduction of aluminum oxide to form an aluminum alloy including producing silicon carbide by heating a first mix of carbon and silicon oxide in a combustion reactor to an elevated temperature sufficient to produce silicon carbide at an accelerated rate, the heating being provided by an in situ combustion with oxygen gas, and then admixing the silicon carbide with carbon and aluminum oxide to form a second mix and heating the second mix in a second reactor to an elevated metal-forming temperature sufficient to produce aluminum-silicon alloy. The prereduction step includes holding aluminum oxide substantially absent from the combustion reactor. The metal-forming step includes feeding silicon oxide in a preferred ratio with silicon carbide. 1 fig.

Silver particle monolayers — Formation, stability, applications.

PubMed

Oćwieja, Magdalena; Adamczyk, Zbigniew; Morga, Maria; Kubiak, Katarzyna

2015-08-01

The formation of silver particle monolayers at solid substrates in self-assembly processes is thoroughly reviewed. Initially, various silver nanoparticle synthesis routes are discussed with the emphasis focused on the chemical reduction in aqueous media. Subsequently, the main experimental methods aimed at bulk suspension characterization are critically reviewed by pointing out their advantages and limitations. Also, various methods enabling the in situ studies of particle deposition and release kinetics, especially the streaming potential method are discussed. In the next section, experimental data are invoked illustrating the most important features of particle monolayer formation, in particular, the role of bulk suspension concentration, particle size, ionic strength, temperature and pH. Afterward, the stability of monolayers and particle release kinetics are extensively discussed. The results obtained by the ex situ AFM/SEM imaging of particles are compared with the in situ streaming potential measurements. An equivalency of both methods is demonstrated, especially in respect to the binding energy determination. It is shown that these experimental results can be adequately interpreted in terms of the hybrid theoretical approach that combines the bulk transport step with the surface blocking effects derived from the random sequential adsorption model. It is also concluded that the particle release kinetics is governed by the discrete electrostatic interactions among ion pairs on particle and substrate surfaces. The classical theories based on the mean-field (averaged) zeta potential concept proved inadequate. Using the ion pair concept the minor dependence of the binding energy on particle size, ionic strength, pH and temperature is properly explained. The final sections of this review are devoted to the application of silver nanoparticles and their monolayers in medicine, analytical chemistry and catalysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Reduction of Bacterial Pathogenic Risk during Ex-situ Stabilization of Previously Buried Foot-and-Mouth Disease Carcasses in a Pilot-scale Bio-augmented Aerobic Composting

NASA Astrophysics Data System (ADS)

Kim, S.; Park, J.; Park, J. K.; Park, S.; Jeon, H.; Kwon, H.

2017-12-01

Foot and mouth disease outbreaks globally occur. Although livestock suspected to be infected or actually infected by animal infectious diseases is typically treated with various methods including burial, burning, incineration, rendering, and composting, burial into soil is currently the major treatment method in Korea. However, buried carcasses are often found to remain undecomposed or incompletely decomposed even after the legal burial period (3 years). To reuse the land used for the burial purposes, Korea government is considering a novel approach to conduct in-situ burial treatment and then to move remaining carcasses from the burial sites to other sites designated for further ex-situ stabilization treatment (burial-composting sequential treatment). In this work, the feasibility of the novel approach was evaluated at a pilot scale facility. For the ex-situ stabilization, we tested the validity of use of a bio-augmented aerobic composting with carcass-degrading microorganisms, with emphasis on examining if the novel aerobic composting has reducing effects on potential pathogenic bacteria. As results, the decreased chemical oxygen demand (COD, 160,000 mg/kg to 40,000 mg/kg) and inorganic nitrogen species (total nitrogen, 5,000 mg/kg to 2,000 mg/kg) indicated effective bio-stabilization of carcasses. During the stabilization, bacterial community structure and dynamics determined by bacterial 16S rRNA sequencing were significantly changed. The prediction of potential pathogenic bacteria showed that bacterial pathogenic risk was significantly reduced up to a normal soil level during the ex-situ stabilization. The conclusion was confirmed by the following functional analysis of dominant bacteria using PICRUST. The findings support the microbiological safety of the ex-site use of the novel burial-composting sequential treatment. Acknowledgement : This study is supported by Korea Ministry of Environmental as "The GAIA Project"

NOx Emission Reduction and its Effects on Ozone during the 2008 Olympic Games

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

Yang, Qing; Wang, Yuhang; Zhao, Chun

2011-07-15

We applied a daily-assimilated inversion method to estimate NOx (NO+NO2) emissions for June-September 2007 and 2008 on the basis of the Aura Ozone Monitoring Instrument (OMI) observations of nitrogen dioxide (NO2) and model simulations using the Regional chEmistry and trAnsport Model (REAM). Over urban Beijing, rural Beijing, and the Huabei Plain, OMI column NO2 reductions are approximately 45%, 33%, and 14%, respectively, while the corresponding anthropogenic NOx emission reductions are only 28%, 24%, and 6%, during the full emission control period (July 20 – Sep 20, 2008). The emission reduction began in early July and was in full force bymore » July 20, corresponding to the scheduled implementation of emission controls over Beijing. The emissions did not appear to recover after the emission control period. Meteorological change from summer 2007 to 2008 is the main factor contributing to the column NO2 decreases not accounted for by the emission reduction. Model simulations suggest that the effect of emission reduction on ozone concentrations over Beijing is relatively minor using a standard VOC emission inventory in China. With an adjustment of the model emissions to reflect in situ observations of VOCs in Beijing, the model simulation suggests a larger effect of the emission reduction.« less

A novel gravity-driven nanofibrous membrane for point-of-use water disinfection: polydopamine-induced in situ silver incorporation.

PubMed

Wang, Jianqiang; Wu, Yichao; Yang, Zhe; Guo, Hao; Cao, Bin; Tang, Chuyang Y

2017-05-24

We report a facile method for preparing silver-loaded membranes for point-of-use disinfection and disaster relief applications. A bio-inspired material, polydopamine, was coated onto a highly porous nanofibrous polyacrylonitrile substrate. We then take advantage of the redox properties of polydopamine to form silver nanoparticles in situ. These nanoparticles were uniformly distributed on the surface of nanofibers with no apparent agglomeration at a silver loading up to 4.36 wt.% (cPAN-Ag1.5). The silver-incorporated membrane cPAN-Ag1.5 achieved a high pure water flux of 130 Lm -2 h -1 at 10-cm water head, demonstrating the feasibility of energy-efficient gravity-driven filtration and eliminating the need for electrical power. The strong anti-bacterial activity and high physical rejection of the membrane led to an excellent disinfection power, with no viable bacterial cells detected in its permeate water. The membrane exhibited >7 log reduction for E. coli and >6 log reduction for B. subtilis. The strategy reported here provides an efficient and green route to synthesize point-of-use membranes. Combining their excellent permeability and disinfection effectiveness, these membranes offer an ideal solution to water supply in disaster-affected areas.

Elucidation of structure and nature of the PdO-Pd transformation using in situ PDF and XAS techniques.

PubMed

Keating, Jonathan; Sankar, Gopinathan; Hyde, Timothy I; Kohara, Shinji; Ohara, Koji

2013-06-14

The PdO-Pd phase transformation in a 4 wt% Pd/Al2O3 catalyst has been investigated using in situ X-ray absorption spectroscopy (XAS) and in situ X-ray total scattering (also known as high-energy X-ray diffraction) techniques. Both the partial and total pair distribution functions (PDF) from these respective techniques have been analysed in depth. New information from PDF analysis of total scattering data has been garnered using the differential PDF (d-PDF) approach where only correlations orginating from PdO and metallic Pd are extracted. This method circumvents problems encountered in characerising the catalytically active components due to the diffuse scattering from the disordered γ-Al2O3 support phase. Quantitative analysis of the palladium components within the catalyst allowed for the phase composition to be established at various temperatures. Above 850 °C it was found that PdO had converted to metallic Pd, however, the extent of reduction was of the order ca. 70% Pd metal and 30% PdO. Complementary in situ XANES and EXAFS were performed, with heating to high temperature and subsequent cooling in air, and the results of the analyses support the observations, that residual PdO is detected at elevated temperatures. Hysteresis in the transformation upon cooling is confirmed from XAS studies where reoxidation occurs below 680 °C.

Assessment of the availability of As and Pb in soils after in situ stabilization.

PubMed

Zhang, Wanying; Yang, Jie; Li, Zhongyuan; Zhou, Dongmei; Dang, Fei

2017-10-01

The in situ stabilization has been widely used to remediate metal-contaminated soil. However, the long-term retaining performance of heavy metals and the associated risk after in situ stabilization remains unclear and has evoked amounting concerns. Here, Pb- or As-contaminated soil was stabilized by a commercial amendment. The availability of Pb and As after in situ stabilization were estimated by ten different in vitro chemical extractions and DGT technique. After amendment application, a significant decline in extractable Pb or As was observed in treatments of Milli-Q water, 0.01 M CaCl 2 , 0.1 M NaNO 3 , 0.05 M (NH 4 ) 2 SO 4 , and 0.43 M HOAc. Potential available metal(loid)s determined by DGT also showed remarkable reduction. Meanwhile, the results of in vivo uptake assays demonstrated that Pb concentrations in shoots of ryegrass Lolium perenne L. declined to 12% of the control samples, comparable to the extraction ratio of 0.1 M NaNO 3 (15.8%) and 0.05 M (NH 4 ) 2 SO 4 (17.3%). For As-contaminated soil, 0.43 M HOAC provided a better estimation of relative phytoavailability (64.6 vs. 65.4% in ryegrass) compared to other extraction methods. We propose that 0.1 M NaNO 3 or 0.05 M (NH 4 ) 2 SO 4 for Pb and 0.43 M HOAc for As may serve as surrogate measures to estimate the lability of metal(loid)s after soil remediation of the tested contaminated soils. Further studies over a wider range of soil types and amendments are necessary to validate extraction methods.

Nanostructural Engineering of Nanoporous Anodic Alumina for Biosensing Applications

PubMed Central

Ferré-Borrull, Josep; Pallarès, Josep; Macías, Gerard; Marsal, Lluis F.

2014-01-01

Modifying the diameter of the pores in nanoporous anodic alumina opens new possibilities in the application of this material. In this work, we review the different nanoengineering methods by classifying them into two kinds: in situ and ex situ. Ex situ methods imply the interruption of the anodization process and the addition of intermediate steps, while in situ methods aim at realizing the in-depth pore modulation by continuous changes in the anodization conditions. Ex situ methods permit a greater versatility in the pore geometry, while in situ methods are simpler and adequate for repeated cycles. As an example of ex situ methods, we analyze the effect of changing drastically one of the anodization parameters (anodization voltage, electrolyte composition or concentration). We also introduce in situ methods to obtain distributed Bragg reflectors or rugate filters in nanoporous anodic alumina with cyclic anodization voltage or current. This nanopore engineering permits us to propose new applications in the field of biosensing: using the unique reflectance or photoluminescence properties of the material to obtain photonic barcodes, applying a gold-coated double-layer nanoporous alumina to design a self-referencing protein sensor or giving a proof-of-concept of the refractive index sensing capabilities of nanoporous rugate filters. PMID:28788127

IN SITU CR(VI) TREATMENT USING A FERROUS IRON-BASED REDUCTANT

EPA Science Inventory

Laboratory and field studies were conducted to evaluate the performance of a ferrous sulfate/ sodium hydrosulfite (dithionite) reductant blend in treating a hexavalent chromium (Cr(VI)) source area and Cr(VI) dissolved phase plume at a former industrial site in Charleston, South ...

Development of a solenoid pumped in situ zinc analyzer for environmental monitoring

USGS Publications Warehouse

Chapin, T.P.; Wanty, R.B.

2005-01-01

A battery powered submersible chemical analyzer, the Zn-DigiScan (Zn Digital Submersible Chemical Analyzer), has been developed for near real-time, in situ monitoring of zinc in aquatic systems. Microprocessor controlled solenoid pumps propel sample and carrier through an anion exchange column to separate zinc from interferences, add colorimetric reagents, and propel the reaction complex through a simple photometric detector. The Zn-DigiScan is capable of self-calibration with periodic injections of standards and blanks. The detection limit with this approach was 30 ??g L-1. Precision was 5-10% relative standard deviation (R.S.D.) below 100 ??g L-1, improving to 1% R.S.D. at 1000 ??g L-1. The linear range extended from 30 to 3000 ??g L-1. In situ field results were in agreement with samples analyzed by inductively coupled plasma mass spectrometry (ICPMS). This pump technology is quite versatile and colorimetric methods with complex online manipulations such as column reduction, preconcentration, and dilution can be performed with the DigiScan. However, long-term field deployments in shallow high altitude streams were hampered by air bubble formation in the photometric detector. ?? 2005 Elsevier B.V. All rights reserved.

Synthesis of Pt-Ni-Fe/CNT/CP nanocomposite as an electrocatalytic electrode for PEM fuel cell cathode

NASA Astrophysics Data System (ADS)

Litkohi, Hajar Rajaei; Bahari, Ali; Ojani, Reza

2017-08-01

In order to use carbon nanotube (CNT)-supported catalyst as fuel cell electrodes, Pt-Ni-Fe/CNT/carbon paper (CP) electrode was prepared using an ethylene glycol reduction method. CNTs were directly synthesized on Ni-impregnated carbon paper, plain carbon cloth, and Teflonized carbon cloth using chemical vapor deposition. FESEM and TEM images and thermogravimetric analysis indicated that in situ CNT on carbon paper (ICNT/CP) possesses more appropriate structural quality and stronger adhesion to the substrate than other substrates. The contact angle analysis demonstrated that the degree of ICNT/CP surface hydrophobicity encountered a 24% increase in comparison to CP and promoted to superhydrophobicity from hydrophobicity. The polarization curves and electrochemical impedance spectroscopy results of the loaded Pt-Ni-Fe on in situ and ex situ CNT/CP illustrated that the power density increased and charge transfer resistance reduced compared to commercial Pt/C loaded on CP. The results can be attributed to the outstanding properties of CNTs and high catalytic activity of triple catalysts causing alloying of Pt with Ni and Fe, which makes them a proper candidate to be used as cathode electrodes in proton exchange membrane fuel cells.

High-temperature Raman spectroscopy of solid oxide fuel cell materials and processes.

PubMed

Pomfret, Michael B; Owrutsky, Jeffrey C; Walker, Robert A

2006-09-07

Chemical and material processes occurring in high temperature environments are difficult to quantify due to a lack of experimental methods that can probe directly the species present. In this letter, Raman spectroscopy is shown to be capable of identifying in-situ and noninvasively changes in material properties as well as the formation and disappearance of molecular species on surfaces at temperatures of 715 degrees C. The material, yttria-stabilized zirconia or YSZ, and the molecular species, Ni/NiO and nanocrystalline graphite, factor prominently in the chemistry of solid oxide fuel cells (SOFCs). Experiments demonstrate the ability of Raman spectroscopy to follow reversible oxidation/reduction kinetics of Ni/NiO as well as the rate of carbon disappearance when graphite, formed in-situ, is exposed to a weakly oxidizing atmosphere. In addition, the Raman active phonon mode of YSZ shows a temperature dependent shift that correlates closely with the expansion of the lattice parameter, thus providing a convenient internal diagnostic for identifying thermal gradients in high temperature systems. These findings provide direct insight into processes likely to occur in operational SOFCs and motivate the use of in-situ Raman spectroscopy to follow chemical processes in these high-temperature, electrochemically active environments.

Diallyl disulphide as natural organosulphur friction modifier via the in-situ tribo-chemical formation of tungsten disulphide

NASA Astrophysics Data System (ADS)

Rodríguez Ripoll, Manel; Totolin, Vladimir; Gabler, Christoph; Bernardi, Johannes; Minami, Ichiro

2018-01-01

The present work shows a novel method for generating in-situ low friction tribofilms containing tungsten disulphide in lubricated contacts using diallyl disulphide as sulphur precursor. The approach relies on the tribo-chemical interaction between the diallyl disulphide and a surface containing embedded sub-micrometer tungsten carbide particles. The results show that upon sliding contact between diallyl disulphide and the tungsten-containing surface, the coefficient of friction drops to values below 0.05 after an induction period. The reason for the reduction in friction is due to tribo-chemical reactions that leads to the in-situ formation of a complex tribofilm that contains iron and tungsten components. X-ray photoelectron spectroscopy analyses indicate the presence of tungsten disulphide at the contact interface, thus justifying the low coefficient of friction achieved during the sliding experiments. It was proven that the low friction tribofilms can only be formed by the coexistence of tungsten and sulphur species, thus highlighting the synergy between diallyl disulphide and the tungsten-containing surface. The concept of functionalizing surfaces to react with specific additives opens up a wide range of possibilities, which allows tuning on-site surfaces to target additive interactions.

A novel APPI-MS setup for in situ degradation product studies of atmospherically relevant compounds: capillary atmospheric pressure photo ionization (cAPPI).

PubMed

Kersten, Hendrik; Derpmann, Valerie; Barnes, Ian; Brockmann, Klaus J; O'Brien, Rob; Benter, Thorsten

2011-11-01

We report on the development of a novel atmospheric pressure photoionization setup and its applicability for in situ degradation product studies of atmospherically relevant compounds. A custom miniature spark discharge lamp was embedded into an ion transfer capillary, which separates the atmospheric pressure from the low pressure region in the first differential pumping stage of a conventional atmospheric pressure ionization mass spectrometer. The lamp operates with a continuous argon flow and produces intense light emissions in the VUV. The custom lamp is operated windowless and efficiently illuminates the sample flow through the transfer capillary on an area smaller than 1 mm(2). Limits of detection in the lower ppbV range, a temporal resolution of milliseconds in the positive as well as the quasi simultaneously operating negative ion mode, and a significant reduction of ion transformation processes render this system applicable to real time studies of rapidly changing chemical systems. The method termed capillary atmospheric pressure photo ionization (cAPPI) is characterized with respect to the lamp emission properties as a function of the operating conditions, temporal response, and its applicability for in situ degradation product studies of atmospherically relevant compounds, respectively.

Enhanced Reduction of Few-Layer Graphene Oxide via Supercritical Water Gasification of Glycerol

PubMed Central

Arcelus-Arrillaga, Pedro; Millan, Marcos; Suelves, Isabel

2017-01-01

A sustainable and effective method for de-oxygenation of few-layer graphene oxide (FLGO) by glycerol gasification in supercritical water (SCW) is described. In this manner, reduction of FLGO and valorization of glycerol, in turn catalyzed by FLGO, are achieved simultaneously. The addition of glycerol enhanced FLGO oxygen removal by up to 59% due to the in situ hydrogen generation as compared to the use of SCW only. Physicochemical characterization of the reduced FLGO (rFLGO) showed a high restoration of the sp2-conjugated carbon network. FLGO sheets with a starting C/O ratio of 2.5 are reduced by SCW gasification of glycerol to rFLGO with a C/O ratio of 28.2, above those reported for hydrazine-based methods. Additionally, simultaneous glycerol gasification resulted in the concurrent production of H2, CO, CH4 and valuable hydrocarbons such as alkylated and non-alkylated long chain hydrocarbon (C12–C31), polycyclic aromatic hydrocarbons (PAH), and phthalate, phenol, cresol and furan based compounds. PMID:29240720

Method for enhanced longevity of in situ microbial filter used for bioremediation

DOEpatents

Carman, M.L.; Taylor, R.T.

1999-03-30

An improved method is disclosed for in situ microbial filter bioremediation having increasingly operational longevity of an in situ microbial filter emplaced into an aquifer. A method is presented for generating a microbial filter of sufficient catalytic density and thickness, which has increased replenishment interval, improved bacteria attachment and detachment characteristics and the endogenous stability under in situ conditions. A system is also disclosed for in situ field water remediation. 31 figs.

Parallel In Situ Screening of Remediation Strategies for Improved Decision Making, Remedial Design, and Cost Savings

DTIC Science & Technology

2012-11-01

vitamin B12. Additionally, a reductant reacts directly with hexavalent chromium to reduce it to the trivalent state. SRS®-M provides a readily...experiments ......................................................................... 27 Figure 8. Hexavalent chromium detected in ISMA effluent post in situ...ground surface cis-DCE cis-dichloroethene CERCLA Comprehensive Environmental Response, Compensation, and Liability Act Cr(VI) hexavalent chromium

Management of groundwater in-situ bioremediation system using reactive transport modelling under parametric uncertainty: field scale application

NASA Astrophysics Data System (ADS)

Verardo, E.; Atteia, O.; Rouvreau, L.

2015-12-01

In-situ bioremediation is a commonly used remediation technology to clean up the subsurface of petroleum-contaminated sites. Forecasting remedial performance (in terms of flux and mass reduction) is a challenge due to uncertainties associated with source properties and the uncertainties associated with contribution and efficiency of concentration reducing mechanisms. In this study, predictive uncertainty analysis of bio-remediation system efficiency is carried out with the null-space Monte Carlo (NSMC) method which combines the calibration solution-space parameters with the ensemble of null-space parameters, creating sets of calibration-constrained parameters for input to follow-on remedial efficiency. The first step in the NSMC methodology for uncertainty analysis is model calibration. The model calibration was conducted by matching simulated BTEX concentration to a total of 48 observations from historical data before implementation of treatment. Two different bio-remediation designs were then implemented in the calibrated model. The first consists in pumping/injection wells and the second in permeable barrier coupled with infiltration across slotted piping. The NSMC method was used to calculate 1000 calibration-constrained parameter sets for the two different models. Several variants of the method were implemented to investigate their effect on the efficiency of the NSMC method. The first variant implementation of the NSMC is based on a single calibrated model. In the second variant, models were calibrated from different initial parameter sets. NSMC calibration-constrained parameter sets were sampled from these different calibrated models. We demonstrate that in context of nonlinear model, second variant avoids to underestimate parameter uncertainty which may lead to a poor quantification of predictive uncertainty. Application of the proposed approach to manage bioremediation of groundwater in a real site shows that it is effective to provide support in management of the in-situ bioremediation systems. Moreover, this study demonstrates that the NSMC method provides a computationally efficient and practical methodology of utilizing model predictive uncertainty methods in environmental management.

Phosphorus Amendment Efficacy for In Situ Remediation of Soil Lead Depends on the Bioaccessible Method.

PubMed

Obrycki, John F; Basta, Nicholas T; Scheckel, Kirk; Stevens, Brooke N; Minca, Kristen K

2016-01-01

A validated method is needed to measure reductions of in vitro bioaccessible (IVBA) Pb in urban soil remediated with amendments. This study evaluated the effect of in vitro extraction solution pH and glycine buffer on bioaccessible Pb in P-treated soils. Two Pb-contaminated soils (790-1300 mg Pb kg), one from a garden and one from a city lot in Cleveland, OH, were incubated in a bench scale experiment for 1 yr. Six phosphate amendments, including bone meal, fish bone, poultry litter, monoammonium phosphate, diammonium phosphate, and triple superphosphate, were added to containers at two application rates. Lead IVBA was assessed using USEPA Method 1340 and three modified versions of this method. Modifications included using solutions with pH 1.5 and 2.5 as well as using solutions with and without 0.4 mol L glycine. Soil amendments were ineffective in reducing IVBA Pb in these soils as measured by pH 1.5 with glycine buffer. The greatest reductions in IVBA Pb, from 5 to 26%, were found using pH 2.5 extractions. Lead mineral results showed several soil amendments promoted Pb phosphate formation, an indicator of remediation success. A significant negative linear relationship between reduction in IVBA Pb and Pb-phosphate formation was found only for pH 2.5 without glycine extraction solution. A modified USEPA Method 1340 without glycine and using pH 2.5 has the potential to predict P soil treatment efficacy and reductions in bioavailable Pb. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

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

Principal Investigator: Baolin Deng, University of Missouri, Columbia, MO; Co-Principal Investigator: Silvia Sabine Jurisson, University of Missouri, Columbia, MO; Co-Principal Investigator: Edward C. Thornton, Pacific Northwest National Laboratory Richland, WA

2008-05-12

There are many soil contamination sites at the Department of Energy (DOE) installations that contain radionuclides and toxic metals such as uranium (U), technetium (Tc), and chromium (Cr). Since these contaminants are the main 'risk drivers' at the Hanford site (WA) and some of them also pose significant risk at other DOE facilities (e.g., Oak Ridge Reservation - TN; Rocky Flats - CO), development of technologies for cost effective site remediation is needed. Current assessment indicates that complete removal of these contaminants for ex-situ disposal is infeasible, thus in-situ stabilization through reduction to insoluble species is considered one of themore » most important approaches for site remediation. In Situ Gaseous Reduction (ISGR) is a technology developed by Pacific Northwest National Laboratory (PNNL) for vadose zone soil remediation. The ISGR approach uses hydrogen sulfide (H{sub 2}S) for reductive immobilization of contaminants that show substantially lower mobility in their reduced forms (e.g., Tc, U, and Cr). The technology can be applied in two ways: (i) to immobilize or stabilize pre-existing contaminants in the vadose zone soils by direct H{sub 2}S treatment, or (ii) to create a permeable reactive barrier (PRB) that prevents the migration of contaminants. Direct treatment involves reduction of the contaminants by H{sub 2}S to less mobile species. Formation of a PRB is accomplished through reduction of ferric iron species in the vadose zone soils by H{sub 2}S to iron sulfides (e.g., FeS), which provides a means for capturing the contaminants entering the treated zone. Potential future releases may occur during tank closure activities. Thus, the placement of a permeable reactive barrier by ISGR treatment can be part of the leak mitigation program. Deployment of these ISGR approaches, however, requires a better understanding of the immobilization kinetics and mechanisms, and a better assessment of the long-term effectiveness of treatment. The primary objective of this project was to understand the complex interactions among the contaminants (i.e., Cr, Tc, and U), H{sub 2}S, and various soil constituents. The reaction with iron sulfide is also the focus of the research, which could be formed from iron oxide reduction by hydrogen sulfide. Factors controlling the reductive immobilization of these contaminants were identified and quantified. The results and fundamental knowledge obtained from this project shall help better evaluate the potential of in situ gaseous treatment to immobilize toxic and radioactive metals examined.« less

Laboratory method used for bioremediation

DOEpatents

Carman, M. Leslie; Taylor, Robert T.

2000-01-01

An improved method for in situ microbial filter bioremediation having increasingly operational longevity of an in situ microbial filter emplaced into an aquifer. A method for generating a microbial filter of sufficient catalytic density and thickness, which has increased replenishment interval, improved bacteria attachment and detachment characteristics and the endogenous stability under in situ conditions. A system for in situ field water remediation.

Volatile fatty acids as substrates for iron and sulfate reduction in Arctic marine sediments, Svalbard

NASA Astrophysics Data System (ADS)

Finke, N.; Vandieken, V.; Jorgensen, B. B.

2006-12-01

Anaerobic degradation of complex organic material in aquatic systems is a multi-step process. The metabolic products of fermentative bacteria serve as electron donors for the terminal oxidizing bacteria. In marine sediments, iron reduction and sulfate reduction are generally the most important terminal oxidation processes in the upper anoxic zone [1]. Microorganisms that reduce iron and sulfate may use a broad range of electron donors, yet the list of potential substrates provides little information about the substrates used in situ by these organisms. Investigations on the electron donors for sulfate reducers in marine sediments have shown that volatile fatty acids (VFA), and in particular acetate, together with hydrogen are the major substrates (e.g. [2-4]). Similar investigations for iron reduction or simultaneous iron and sulfate reduction are lacking for marine sediments. Furthermore, most of these studies were made in temperate sediments and little is known about the substrates for sulfate reducers in permanently cold sediments, which account for >90% of the ocean floor [5]. We investigated the relative contributions of iron reduction and sulfate reduction to the terminal oxidation of organic carbon and the importance of acetate, lactate, propionate, and isobutyrate as electron donors for iron and sulfate reduction in permanently cold, Arctic sediments from Svalbard. In the surface layer (0-2 cm) sulfate reduction accounted for 2/3 of the organic carbon oxidation (determined as DIC production), the remaining 1/3 were attributed to iron reduction. In the 5-9 cm layer sulfate reduction was the sole important terminal oxidation step. The contribution of acetate to terminal oxidation was determined by radiotracer incubation as well as from the accumulation after the inhibition of sulfate reduction by selenate. The rates determined with the two methods varied by less than 20%. Acetate turnover, determined with the tracer incubations, accounted for 10 and 40% of the sulfate reduction in the 0-2 cm and 5-9 cm layer, respectively. Together acetate, lactate, propionate and isobutyrate accounted for 21 and 52% of the sulfate reduction, in the 0-2 cm and 5-9 cm layer, respectively. Assigning all acetate and lactate turnover in the selenate inhibited samples, these two VFA account for less than 10 and 2%, respectively, of the iron reduction in the 0-2 cm layer. Thus, 67 and 48% of the terminal oxidation in the 0-2cm and 5-9 cm layer must be driven by electron donors other than the investigated VFA. The sulfate reduction rates as well as the VFA turnover rates were at the lower end of reported rates from similar studies, mostly measured in temperate sites (e.g. [2-4, 6, 7]). Comparing a series of studies with different in situ temperatures shows, parameters other than in situ temperature seem to be more important in determining the sulfate reduction and VFA turnover rates. [1] Thamdrup, B. (2000) Bacterial manganese and iron reduction in aquatic sediments, 41-84 pp. Kluwer Academic / Plenum Publ., New York. [2] Parkes, R.J., Gibson, G.R., Mueller-Harvey, I., Buckingham, W.J. and Herbert, R.A. (1989) J. Gen. Microbiol. 135, 175-187. [3] Christensen, D. (1984) Limnol. Oceanogr. 29, 189-192. [4] Shaw, D.G. and McIntosh, D.J. (1990) Estuarine Coastal & Shelf Science 31, 775-788. [5] Levitus, S. and Boyer, T. (1994) World Ocean Atlas, pp. US Department of Commerce, Washington, DC. [6] Kristensen, E., King, G.M., Holmer, M., Banta, G.T., Jensen, M.H., Hansen, K. and Bussarawit, N. (1994) Mar. Ecol.-Prog. Ser. 109, 245-255. [7] Wellsbury, P. and Parkes, R.J. (1995) FEMS Microbiol. Ecol. 17, 85-94.

In-situ evidence for uranium immobilization and remobilization

USGS Publications Warehouse

Senko, John M.; Istok, Jonathan D.; Suflita, Joseph M.; Krumholz, Lee R.

2002-01-01

The in-situ microbial reduction and immobilization of uranium was assessed as a means of preventing the migration of this element in the terrestrial subsurface. Uranium immobilization (putatively identified as reduction) and microbial respiratory activities were evaluated in the presence of exogenous electron donors and acceptors with field push−pull tests using wells installed in an anoxic aquifer contaminated with landfill leachate. Uranium(VI) amended at 1.5 μM was reduced to less than 1 nM in groundwater in less than 8 d during all field experiments. Amendments of 0.5 mM sulfate or 5 mM nitrate slowed U(VI) immobilization and allowed for the recovery of 10% and 54% of the injected element, respectively, as compared to 4% in the unamended treatment. Laboratory incubations confirmed the field tests and showed that the majority of the U(VI) immobilized was due to microbial reduction. In these tests, nitrate treatment (7.5 mM) inhibited U(VI) reduction, and nitrite was transiently produced. Further push−pull tests were performed in which either 1 or 5 mM nitrate was added with 1.0 μM U(VI) to sediments that already contained immobilized uranium. After an initial loss of the amendments, the concentration of soluble U(VI) increased and eventually exceeded the injected concentration, indicating that previously immobilized uranium was remobilized as nitrate was reduced. Laboratory experiments using heat-inactivated sediment slurries suggested that the intermediates of dissimilatory nitrate reduction (denitrification or dissimilatory nitrate reduction to ammonia), nitrite, nitrous oxide, and nitric oxide were all capable of oxidizing and mobilizing U(IV). These findings indicate that in-situ subsurface U(VI) immobilization can be expected to take place under anaerobic conditions, but the permanence of the approach can be impaired by disimilatory nitrate reduction intermediates that can mobilize previously reduced uranium.

Facile preparation of surfactant-free Au NPs/RGO/Ni foam for degradation of 4-nitrophenol and detection of hydrogen peroxide.

PubMed

Liu, Y Y; Guo, X L; Zhao, L; Zhu, L; Chen, Z T; Chen, J; Zhang, Y; Sun, L T; Zhao, Y H

2018-06-08

The application of Au nanoparticles (Au NPs) often requires surface modification with chemical surfactants, which dramatically reduce the surface activity and increase the chemical contamination and cost of Au NPs. In this research, we have developed a novel Au NPs/reduced graphene oxide/Ni foam hybrid (Au NPs/RGO/NiF) by in situ reduction through ascorbic acid and replacement reaction. This method is green, facile and efficient. The Au NPs are free of chemical surfactants and are homogeneously distributed on the surface of the RGO/NiF. The as-prepared Au NPs/RGO/NiF hybrid is uniform, stable and exhibits not only a high reduction efficiency for the reduction of 4-nitrophenol with a catalytic kinetic constant of up to 0.46 min -1 (0.15 cm 3 catalysis) but also a sensitive and selective detection of H 2 O 2 with a detection limit of ∼1.60 μM.

Facile preparation of surfactant-free Au NPs/RGO/Ni foam for degradation of 4-nitrophenol and detection of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Liu, Y. Y.; Guo, X. L.; Zhao, L.; Zhu, L.; Chen, Z. T.; Chen, J.; Zhang, Y.; Sun, L. T.; Zhao, Y. H.

2018-06-01

The application of Au nanoparticles (Au NPs) often requires surface modification with chemical surfactants, which dramatically reduce the surface activity and increase the chemical contamination and cost of Au NPs. In this research, we have developed a novel Au NPs/reduced graphene oxide/Ni foam hybrid (Au NPs/RGO/NiF) by in situ reduction through ascorbic acid and replacement reaction. This method is green, facile and efficient. The Au NPs are free of chemical surfactants and are homogeneously distributed on the surface of the RGO/NiF. The as-prepared Au NPs/RGO/NiF hybrid is uniform, stable and exhibits not only a high reduction efficiency for the reduction of 4-nitrophenol with a catalytic kinetic constant of up to 0.46 min‑1 (0.15 cm3 catalysis) but also a sensitive and selective detection of H2O2 with a detection limit of ∼1.60 μM.

Development of Multi-functional Properties on Cotton Fabric by In Situ Application of TiO2 and ZnO Nanoparticles

NASA Astrophysics Data System (ADS)

Butola, B. S.; Garg, Aayush; Garg, Aman; Chauhan, Indu

2018-06-01

Cotton fabrics functionalized with different combinations of TiO2 and ZnO were evaluated for multifunctional properties including UV protection, antimicrobial and self-cleaning. The ZnO nanoparticles synthesized using sol gel method were applied on cotton fabric by pad-dry-cure method and TiO2 was deposited in situ. The deposition of both TiO2 and ZnO was examined and confirmed by SEM and EDX analysis. Application of both metal oxides resulted in good improvement in UV protection of treated fabrics. The fabrics which were finished with combination of both Zinc and Titanium oxides, showed UPF rating of 50+ as compared to UPF rating of untreated cotton, which was only 5. The same fabrics also showed higher self-cleaning extent as compared to untreated cotton fabric. It was found that the sequence of application of ZnO and TiO2 affected the antimicrobial activity of the finished fabric and also the durability. When application of TiO2 was followed by ZnO, the combination resulted in development of excellent antimicrobial property against Escherichia coli ( 99% colony reduction) which was retained after 10 wash cycles. However, when application of ZnO nanoparticles was followed by application of TiO2, the improvement in antimicrobial activity was found to be moderate ( 48% colony reduction) and had poor wash durability. Hence, the specific sequence of application of these metals oxides can be utilized for obtaining good durability of the multifunctional properties on cotton fabric.

Silver/poly(vinyl alcohol) nanocomposite film prepared using water in oil microemulsion for antibacterial applications.

PubMed

Fatema, Ummul K; Rahman, M Muhibur; Islam, M Rakibul; Mollah, M Yousuf A; Susan, Md Abu Bin Hasan

2018-03-15

Water in oil microemulsion (w/o) is a simple preparative route for nanoparticles where water droplets (dispersed in continuous oil medium and stabilized by surfactants and cosurfactants) act as nanoreactors to carry out chemical reactions. If polymeric matrix is incorporated inside the core of the microemulsions, it should prevent the agglomeration of nanoparticles after separation from microemulsions. Thus polymer nanocomposite films prepared from w/o microemulsions are expected to give narrow and homogeneous size distribution of nanoparticles throughout the polymer host. Silver/poly(vinyl alcohol) (Ag/PVA) nanocomposite film was successfully prepared, for the first time, using Triton X-100 (TX-100)/1-butanol/cyclohexane/water microemulsion. Reduction of the metal salt was carried out in the core of w/o microemulsion droplets containing PVA polymeric matrix. After separation from the microemulsion, Ag/PVA nanocomposite film was then prepared by solution casting method. The antibacterial activity of the nanocomposites was tested against Gram-negative, Escherichia coli and Gram-positive, Staphylococcus aureus by agar diffusion method. Ag nanoparticles with an average diameter of 105 nm could be synthesized using PVA, whereas in the absence of PVA the nanoparticles agglomerated. The distribution of Ag nanoparticles on PVA surface of the nanocomposite film prepared using microemulsion was uniform, whereas the film prepared through in situ generation of Ag nanoparticles by chemical reduction process on PVA host showed non-uniform, coagulated, bunches of Ag nanoparticles. The film synthesized using microemulsion exhibited enhanced antibacterial efficacy compared to that prepared through in situ synthesis under the same test condition. Copyright © 2017 Elsevier Inc. All rights reserved.

Development of Multi-functional Properties on Cotton Fabric by In Situ Application of TiO2 and ZnO Nanoparticles

NASA Astrophysics Data System (ADS)

Butola, B. S.; Garg, Aayush; Garg, Aman; Chauhan, Indu

2018-05-01

Cotton fabrics functionalized with different combinations of TiO2 and ZnO were evaluated for multifunctional properties including UV protection, antimicrobial and self-cleaning. The ZnO nanoparticles synthesized using sol gel method were applied on cotton fabric by pad-dry-cure method and TiO2 was deposited in situ. The deposition of both TiO2 and ZnO was examined and confirmed by SEM and EDX analysis. Application of both metal oxides resulted in good improvement in UV protection of treated fabrics. The fabrics which were finished with combination of both Zinc and Titanium oxides, showed UPF rating of 50+ as compared to UPF rating of untreated cotton, which was only 5. The same fabrics also showed higher self-cleaning extent as compared to untreated cotton fabric. It was found that the sequence of application of ZnO and TiO2 affected the antimicrobial activity of the finished fabric and also the durability. When application of TiO2 was followed by ZnO, the combination resulted in development of excellent antimicrobial property against Escherichia coli ( 99% colony reduction) which was retained after 10 wash cycles. However, when application of ZnO nanoparticles was followed by application of TiO2, the improvement in antimicrobial activity was found to be moderate ( 48% colony reduction) and had poor wash durability. Hence, the specific sequence of application of these metals oxides can be utilized for obtaining good durability of the multifunctional properties on cotton fabric.

A ternary Cu2O-Cu-CuO nanocomposite: a catalyst with intriguing activity.

PubMed

Sasmal, Anup Kumar; Dutta, Soumen; Pal, Tarasankar

2016-02-21

In this work, the syntheses of Cu2O as well as Cu(0) nanoparticle catalysts are presented. Copper acetate monohydrate produced two distinctly different catalyst particles with varying concentrations of hydrazine hydrate at room temperature without using any surfactant or support. Then both of them were employed separately for 4-nitrophenol reduction in aqueous solution in the presence of sodium borohydride at room temperature. To our surprise, it was noticed that the catalytic activity of Cu2O was much higher than that of the metal Cu(0) nanoparticles. We have confirmed the reason for the exceptionally high catalytic activity of cuprous oxide nanoparticles over other noble metal nanoparticles for 4-nitrophenol reduction. A plausible mechanism has been reported. The unusual activity of Cu2O nanoparticles in the reduction reaction has been observed because of the in situ generated ternary nanocomposite, Cu2O-Cu-CuO, which rapidly relays electrons and acts as a better catalyst. In this ternary composite, highly active in situ generated Cu(0) is proved to be responsible for the hydride transfer reaction. The mechanism of 4-nitrophenol reduction has been established from supporting TEM studies. To further support our proposition, we have prepared a compositionally similar Cu2O-Cu-CuO nanocomposite using Cu2O and sodium borohydride which however displayed lower rate of reduction than that of the in situ produced ternary nanocomposite. The evolution of isolated Cu(0) nanoparticles for 4-nitrophenol reduction from Cu2O under surfactant-free condition has also been taken into consideration. The synthetic procedures of cuprous oxide as well as its catalytic activity in the reduction of 4-nitrophenol are very convenient, fast, cost-effective, and easily operable in aqueous medium and were followed spectrophotometrically. Additionally, the Cu2O-catalyzed 4-nitrophenol reduction methodology was extended further to the reduction of electronically diverse nitroarenes. This concise catalytic process in aqueous medium at room temperature revealed an unprecedented catalytic performance which would draw attention across the whole research community.

Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces

NASA Astrophysics Data System (ADS)

Li, Peiqiang; Wang, Huying; Xu, Jinfeng; Jing, Hua; Zhang, Jun; Han, Haixiang; Lu, Fusui

2013-11-01

In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels.In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels. Electronic supplementary information (ESI) available: Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces. See DOI: 10.1039/c3nr03352j

Use of Sodium Dithionite as Part of a More Efficient Groundwater Restoration Method Following In-situ Recovery of Uranium at the Smith-Ranch Highland Site in Wyoming

NASA Astrophysics Data System (ADS)

Harris, R.; Reimus, P. W.; Ware, D.; Williams, K.; Chu, D.; Perkins, G.; Migdissov, A. A.; Bonwell, C.

2017-12-01

Uranium is primarily mined for nuclear power production using an aqueous extraction technique called in-situ recovery (ISR). ISR can pollute groundwater with residual uranium and other heavy metals. Reverse osmosis and groundwater sweep are currently used to restore groundwater after ISR mining, but are not permanent solutions. Sodium dithionite is being tested as part of a method to more permanently restore groundwater after ISR mining at the Smith-Ranch Highland site in Wyoming. Sodium dithionite is a chemical reductant that can reduce sediments that were oxidized during ISR. The reduced sediments can reduce soluble uranium (VI) in the groundwater to insoluble uranium (IV). Laboratory studies that use sodium dithionite to treat sediments and waters from the site may help predict how it will behave during a field deployment. An aqueous batch experiment showed that sodium dithionite reduced uranium in post-mined untreated groundwater from 38 ppm to less than 1 ppm after 1 day. A sediment reduction batch experiment showed that sodium dithionite-treated sediments were capable of reducing uranium in post-mined untreated groundwater from 38 ppm to 2 ppm after 7 days. One column experiment is showing post-mined sodium dithionite-treated sediments are capable of reducing uranium in post-mined groundwater for over 30 pore volumes past the initial injection. While these results are promising for field deployments of sodium dithionite, another column experiment with sodium dithionite-treated sediments containing uranium rich organic matter is showing net production of uranium instead of uranium uptake. Sodium dithionite appears to liberate uranium from the organic matter. Another sediment reduction experiment is being conducted to further investigate this hypothesis. These experiments are helping guide plans for field deployments of sodium dithionite at uranium ISR mining sites.

A graphene-based electrochemical competitive immunosensor for the sensitive detection of okadaic acid in shellfish

NASA Astrophysics Data System (ADS)

Eissa, Shimaa; Zourob, Mohammed

2012-11-01

A novel graphene-based voltammetric immunosensor for sensitive detection of okadaic acid (OA) was developed. A simple and efficient electrografting method was utilized to functionalize graphene-modified screen-printed carbon electrodes (GSPE) by the electrochemical reduction of in situ generated 4-carboxyphenyl diazonium salt in acidic aqueous solution. Next, the okadaic acid antibody was covalently immobilized on the carboxyphenyl modified graphene electrodes via carbodiimide chemistry. Square wave voltammetry (SWV) was used to investigate the stepwise assembly of the immunosensor. A competitive assay between OA and a fixed concentration of okadaic acid-ovalbumin conjugate (OA-OVA) for the immobilized antibodies was employed for the detection of okadaic acid. The decrease of the [Fe(CN)6]3-/4- reduction peak current in the square wave voltammetry for various concentrations of okadaic acid was used for establishing the calibration curve. A linear relationship between the SWV peak current difference and OA concentration was obtained up to ~5000 ng L-1. The developed immunosensor allowed a detection limit of 19 ng L-1 of OA in PBS buffer. The matrix effect studied with spiked shellfish tissue extracts showed a good percentage of recovery and the method was also validated with certified reference mussel samples.A novel graphene-based voltammetric immunosensor for sensitive detection of okadaic acid (OA) was developed. A simple and efficient electrografting method was utilized to functionalize graphene-modified screen-printed carbon electrodes (GSPE) by the electrochemical reduction of in situ generated 4-carboxyphenyl diazonium salt in acidic aqueous solution. Next, the okadaic acid antibody was covalently immobilized on the carboxyphenyl modified graphene electrodes via carbodiimide chemistry. Square wave voltammetry (SWV) was used to investigate the stepwise assembly of the immunosensor. A competitive assay between OA and a fixed concentration of okadaic acid-ovalbumin conjugate (OA-OVA) for the immobilized antibodies was employed for the detection of okadaic acid. The decrease of the [Fe(CN)6]3-/4- reduction peak current in the square wave voltammetry for various concentrations of okadaic acid was used for establishing the calibration curve. A linear relationship between the SWV peak current difference and OA concentration was obtained up to ~5000 ng L-1. The developed immunosensor allowed a detection limit of 19 ng L-1 of OA in PBS buffer. The matrix effect studied with spiked shellfish tissue extracts showed a good percentage of recovery and the method was also validated with certified reference mussel samples. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32146g

Particle size effect of redox reactions for Co species supported on silica

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

Chotiwan, Siwaruk; Tomiga, Hiroki; Katagiri, Masaki

Conversions of chemical states during redox reactions of two silica-supported Co catalysts, which were prepared by the impregnation method, were evaluated by using an in situ XAFS technique. The addition of citric acid into the precursor solution led to the formation on silica of more homogeneous and smaller Co particles, with an average diameter of 4 nm. The supported Co{sub 3}O{sub 4} species were reduced to metallic Co via the divalent CoO species during a temperature-programmed reduction process. The reduced Co species were quantitatively oxidized with a temperature-programmed oxidation process. The higher observed reduction temperature of the smaller CoO particlesmore » and the lower observed oxidation temperature of the smaller metallic Co particles were induced by the higher dispersion of the Co oxide species, which apparently led to a stronger interaction with supporting silica. The redox temperature between CoO and Co{sub 3}O{sub 4} was found to be independent of the particle size. - Graphical abstract: Chemical state conversions of SiO{sub 2}-supported Co species and the particle size effect have been analyzed by means of in situ XAFS technique. The small CoO particles have endurance against the reduction and exist in a wide temperature range. Display Omitted - Highlights: • The conversions of the chemical state of supported Co species during redox reaction are evaluated. • In operando XAFS technique were applied to measure redox properties of small Co particles. • A small particle size affects to the redox temperatures of cobalt catalysts.« less

In situ microbial filter used for bioremediation

DOEpatents

Carman, M. Leslie; Taylor, Robert T.

2000-01-01

An improved method for in situ microbial filter bioremediation having increasingly operational longevity of an in situ microbial filter emplaced into an aquifer. A method for generating a microbial filter of sufficient catalytic density and thickness, which has increased replenishment interval, improved bacteria attachment and detachment characteristics and the endogenous stability under in situ conditions. A system for in situ field water remediation.

Molecular Analysis of the In Situ Growth Rates of Subsurface Geobacter Species

PubMed Central

Giloteaux, Ludovic; Barlett, Melissa; Chavan, Milind A.; Smith, Jessica A.; Williams, Kenneth H.; Wilkins, Michael; Long, Philip; Lovley, Derek R.

2013-01-01

Molecular tools that can provide an estimate of the in situ growth rate of Geobacter species could improve understanding of dissimilatory metal reduction in a diversity of environments. Whole-genome microarray analyses of a subsurface isolate of Geobacter uraniireducens, grown under a variety of conditions, identified a number of genes that are differentially expressed at different specific growth rates. Expression of two genes encoding ribosomal proteins, rpsC and rplL, was further evaluated with quantitative reverse transcription-PCR (qRT-PCR) in cells with doubling times ranging from 6.56 h to 89.28 h. Transcript abundance of rpsC correlated best (r2 = 0.90) with specific growth rates. Therefore, expression patterns of rpsC were used to estimate specific growth rates of Geobacter species during an in situ uranium bioremediation field experiment in which acetate was added to the groundwater to promote dissimilatory metal reduction. Initially, increased availability of acetate in the groundwater resulted in higher expression of Geobacter rpsC, and the increase in the number of Geobacter cells estimated with fluorescent in situ hybridization compared well with specific growth rates estimated from levels of in situ rpsC expression. However, in later phases, cell number increases were substantially lower than predicted from rpsC transcript abundance. This change coincided with a bloom of protozoa and increased attachment of Geobacter species to solid phases. These results suggest that monitoring rpsC expression may better reflect the actual rate that Geobacter species are metabolizing and growing during in situ uranium bioremediation than changes in cell abundance. PMID:23275510

EFFECTS OF THREE CONCENTRATIONS OF MIXED FATTY ACIDS ON DECHLORINATION OF TETRACHLOROETHENE IN AQUIFER MICRO- COSMS

EPA Science Inventory

Chloroethenes are among the most common organic contaminants of ground water. The biotransformation of these compounds by reductive dechlorination is a promising technology for in situ treatment. The effects of three concentrations of a fatty acids mixture on the reductive dehalo...

Reductive amination of tertiary anilines and aldehydes.

PubMed

Lv, Yunhe; Zheng, Yiying; Li, Yan; Xiong, Tao; Zhang, Jingping; Liu, Qun; Zhang, Qian

2013-10-09

An unprecedented oxidant-mediated reductive amination of tertiary anilines and aldehydes without external reducing agents was developed via the nucleophilic attack of the oxygen atom of the carbonyl group to in situ generated iminium ions, in which tertiary anilines were used as both nitrogen source and reducing agent for the first time.

Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy

DOE PAGES

Eilert, André; Roberts, F. Sloan; Friebel, Daniel; ...

2016-04-04

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Approaching bathymetry estimation from high resolution multispectral satellite images using a neuro-fuzzy technique

NASA Astrophysics Data System (ADS)

Corucci, Linda; Masini, Andrea; Cococcioni, Marco

2011-01-01

This paper addresses bathymetry estimation from high resolution multispectral satellite images by proposing an accurate supervised method, based on a neuro-fuzzy approach. The method is applied to two Quickbird images of the same area, acquired in different years and meteorological conditions, and is validated using truth data. Performance is studied in different realistic situations of in situ data availability. The method allows to achieve a mean standard deviation of 36.7 cm for estimated water depths in the range [-18, -1] m. When only data collected along a closed path are used as a training set, a mean STD of 45 cm is obtained. The effect of both meteorological conditions and training set size reduction on the overall performance is also investigated.

A fresnoite-structure-related mixed valent titanium(III/IV) chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl: A flux crystal growth route to Ti(III) containing oxides

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

Abeysinghe, Dileka; Smith, Mark D.; Loye, Hans-Conrad zur, E-mail: zurloye@mailbox.sc.edu

Single crystals of mixed valent barium titanium(III/IV) chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09}, were grown in a high temperature molten chloride flux involving an in situ reduction step. The fresnoite structure related Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09} crystallizes in the tetragonal space group P4/mbm with lattice parameters of a=8.6717(2) Å, c=18.6492(5) Å. The title compound exhibits a 3D structure consisting of 2D layers of fused Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} groups and 2D layers of fused Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} groups that are linked via barium atoms. The in situmore » reduction of Ti(IV) to Ti(III) is achieved via the addition of metallic Mg to the flux to function as the reducing agent. The temperature dependence of the magnetic susceptibility shows simple paramagnetism above 100 K. There is a discontinuity in the susceptibility data below 100 K, which might be due to a structural change that takes place resulting in charge ordering. - Graphical abstract: The fresnoite structure related novel reduced barium titanium chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09}, were synthesized via flux method. An in situ reduction of Ti(IV) to Ti(III) achieved using Mg metal. The 3D structure consists 2D layers of fused Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} and 2D layers of fused Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} connected via barium atoms. Compound shows simple paramagnetism above 100 K. - Highlights: • The fresnoite related Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09} were grown via molten flux method. • The in situ reduction of Ti(IV) to Ti(III) is achieved using metallic Mg. • 2D layers of Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} and Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} connect via Ba atoms. • The magnetic susceptibility shows simple paramagnetism above 100 K.« less

CHROTRAN 1.0: A mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

NASA Astrophysics Data System (ADS)

Hansen, Scott K.; Pandey, Sachin; Karra, Satish; Vesselinov, Velimir V.

2017-12-01

Groundwater contamination by heavy metals is a critical environmental problem for which in situ remediation is frequently the only viable treatment option. For such interventions, a multi-dimensional reactive transport model of relevant biogeochemical processes is invaluable. To this end, we developed a model, chrotran, for in situ treatment, which includes full dynamics for five species: a heavy metal to be remediated, an electron donor, biomass, a nontoxic conservative bio-inhibitor, and a biocide. Direct abiotic reduction by donor-metal interaction as well as donor-driven biomass growth and bio-reduction are modeled, along with crucial processes such as donor sorption, bio-fouling, and biomass death. Our software implementation handles heterogeneous flow fields, as well as arbitrarily many chemical species and amendment injection points, and features full coupling between flow and reactive transport. We describe installation and usage and present two example simulations demonstrating its unique capabilities. One simulation suggests an unorthodox approach to remediation of Cr(VI) contamination.

CHROTRAN: a mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

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

Hansen, Scott; Pandey, Sachin; Karra, Satish

Groundwater contamination by heavy metals is a critical environmental problem for which in situ remediation is frequently the only viable treatment option. For such interventions, a three-dimensional reactive transport model of relevant biogeochemical processes is invaluable. To this end, we developed a model, CHROTRAN, for in situ treatment, which includes full dynamics for five species: a heavy metal to be remediated, an electron donor, biomass, a nontoxic conservative bio-inhibitor, and a biocide. Direct abiotic reduction by donor-metal interaction as well as donor-driven biomass growth and bio-reduction are modeled, along with crucial processes such as donor sorption, bio-fouling and biomass death.more » Our software implementation handles heterogeneous flow fields, arbitrarily many chemical species and amendment injection points, and features full coupling between flow and reactive transport. We describe installation and usage and present two example simulations demonstrating its unique capabilities. One simulation suggests an unorthodox approach to remediation of Cr(VI) contamination.« less

Preparing for in situ processing on upcoming leading-edge supercomputers

DOE PAGES

Kress, James; Churchill, Randy Michael; Klasky, Scott; ...

2016-10-01

High performance computing applications are producing increasingly large amounts of data and placing enormous stress on current capabilities for traditional post-hoc visualization techniques. Because of the growing compute and I/O imbalance, data reductions, including in situ visualization, are required. These reduced data are used for analysis and visualization in a variety of different ways. Many of he visualization and analysis requirements are known a priori, but when they are not, scientists are dependent on the reduced data to accurately represent the simulation in post hoc analysis. The contributions of this paper is a description of the directions we are pursuingmore » to assist a large scale fusion simulation code succeed on the next generation of supercomputers. Finally, these directions include the role of in situ processing for performing data reductions, as well as the tradeoffs between data size and data integrity within the context of complex operations in a typical scientific workflow.« less

CHROTRAN: a mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

DOE PAGES

Hansen, Scott; Pandey, Sachin; Karra, Satish; ...

2017-04-25

Groundwater contamination by heavy metals is a critical environmental problem for which in situ remediation is frequently the only viable treatment option. For such interventions, a three-dimensional reactive transport model of relevant biogeochemical processes is invaluable. To this end, we developed a model, CHROTRAN, for in situ treatment, which includes full dynamics for five species: a heavy metal to be remediated, an electron donor, biomass, a nontoxic conservative bio-inhibitor, and a biocide. Direct abiotic reduction by donor-metal interaction as well as donor-driven biomass growth and bio-reduction are modeled, along with crucial processes such as donor sorption, bio-fouling and biomass death.more » Our software implementation handles heterogeneous flow fields, arbitrarily many chemical species and amendment injection points, and features full coupling between flow and reactive transport. We describe installation and usage and present two example simulations demonstrating its unique capabilities. One simulation suggests an unorthodox approach to remediation of Cr(VI) contamination.« less

From Nanowires to Biofilms: An Exploration of Novel Mechanisms of Uranium Transformation Mediated by Geobacter Bacteria

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

REGUERA, GEMMA

2014-01-16

One promising strategy for the in situ bioremediation of radioactive groundwater contaminants that has been identified by the SBR Program is to stimulate the activity of dissimilatory metal-reducing microorganisms to reductively precipitate uranium and other soluble toxic metals. The reduction of U(VI) and other soluble contaminants by Geobacteraceae is directly dependent on the reduction of Fe(III) oxides, their natural electron acceptor, a process that requires the expression of Geobacter’s conductive pili (pilus nanowires). Expression of conductive pili by Geobacter cells leads to biofilm development on surfaces and to the formation of suspended biogranules, which may be physiological closer to biofilmsmore » than to planktonic cells. Biofilm development is often assumed in the subsurface, particularly at the matrix-well screen interface, but evidence of biofilms in the bulk aquifer matrix is scarce. Our preliminary results suggest, however, that biofilms develop in the subsurface and contribute to uranium transformations via sorption and reductive mechanisms. In this project we elucidated the mechanism(s) for uranium immobilization mediated by Geobacter biofilms and identified molecular markers to investigate if biofilm development is happening in the contaminated subsurface. The results provided novel insights needed in order to understand the metabolic potential and physiology of microorganisms with a known role in contaminant transformation in situ, thus having a significant positive impact in the SBR Program and providing novel concept to monitor, model, and predict biological behavior during in situ treatments.« less

Laboratory Investigations of Enhanced Sulfate Reduction as a Groundwater Arsenic Remediation Strategy

PubMed Central

KEIMOWITZ, A. R.; MAILLOUX, B. J.; COLE, P.; STUTE, M.; SIMPSON, H. J.; CHILLRUD, S. N.

2011-01-01

Landfills have the potential to mobilize arsenic via induction of reducing conditions in groundwater and subsequent desorption from or dissolution of arsenic-bearing iron phases. Laboratory incubation experiments were conducted with materials from a landfill where such processes are occurring. These experiments explored the potential for induced sulfate reduction to immobilize dissolved arsenic in situ. The native microbial community at this site reduced sulfate in the presence of added acetate. Acetate respiration and sulfate reduction were observed concurrent with dissolved iron concentrations initially increasing from 0.6 μM (0.03 mg L−1) to a maximum of 111 μM (6.1 mg L−1) and subsequently decreasing to 0.74 μM (0.04 mg L−1). Dissolved arsenic concentrations initially covaried with iron but subsequently increased again as sulfide accumulated, consistent with the formation of soluble thioarsenite complexes. Dissolved arsenic concentrations subsequently decreased again from a maximum of 2 μM (148 μg L−1) to 0.3 μM (22 μg L−1), consistent with formation of sulfide mineral phases or increased arsenic sorption at higher pH values. Disequilibrium processes may also explain this second arsenic peak. The maximum iron and arsenic concentrations observed in the lab represent conditions most equivalent to the in situ conditions. These findings indicate that enhanced sulfate reduction merits further study as a potential in situ groundwater arsenic remediation strategy at landfills and other sites with elevated arsenic in reducing groundwater. PMID:17969686

Embedded Si/Graphene Composite Fabricated by Magnesium-Thermal Reduction as Anode Material for Lithium-Ion Batteries.

PubMed

Zhu, Jiangliu; Ren, Yurong; Yang, Bo; Chen, Wenkai; Ding, Jianning

2017-12-16

Embedded Si/graphene composite was fabricated by a novel method, which was in situ generated SiO 2 particles on graphene sheets followed by magnesium-thermal reduction. The tetraethyl orthosilicate (TEOS) and flake graphite was used as original materials. On the one hand, the unique structure of as-obtained composite accommodated the large volume change to some extent. Simultaneously, it enhanced electronic conductivity during Li-ion insertion/extraction. The MR-Si/G composite is used as the anode material for lithium ion batteries, which shows high reversible capacity and ascendant cycling stability reach to 950 mAh·g -1 at a current density of 50 mA·g -1 after 60 cycles. These may be conducive to the further advancement of Si-based composite anode design.

Development of Permeable Reactive Barriers (PRB) Using Edible Oils

DTIC Science & Technology

2008-06-01

developed for the in-situ treatment of hazardous constituents including chlorinated solvents, perchlorate (ClO4-), chromate (CrO4-2) and oxidized... beef tallow, melted corn oil margarine, coconut oil and molasses supported the complete reductive dehalogenation of PCE to ethene in microcosms using...anaerobic bioremediation processes are being developed for the in-situ treatment of hazardous constituents including chlorinated solvents, perchlorate

Field-Scale Evaluation of Monitored Natural Attenuation for Dissolved Chlorinated Solvent Plumes

DTIC Science & Technology

2009-04-01

biological in-situ treatment, an air sparging pilot study, and a phytoremediation study. The innovative technology studies were conducted within the source... phytoremediation (June to September 1997), reductive anaerobic biological in-situ treatment technology (RABITT; 1998), and groundwater recirculation wells...u g / L ) Measured Concentrations in 1381MWS09 Air Sparge Pilot Test (1996/1997) Phytoremediation Pilot Test (1997) RABITT Pilot Test (1998

System for enhanced longevity of in situ microbial filter used for bioremediation

DOEpatents

Carman, M. Leslie; Taylor, Robert T.

2000-01-01

An improved method for in situ microbial filter bioremediation having increasingly operational longevity of an in situ microbial filter emplaced into an aquifer. A method for generating a microbial filter of sufficient catalytic density and thickness, which has increased replenishment interval, improved bacteria attachment and detachment characteristics and the endogenous stability under in situ conditions. A system for in situ field water remediation.

Psychological treatment for panic disorder with agoraphobia: a randomized controlled trial to examine the role of therapist-guided exposure in situ in CBT.

PubMed

Gloster, Andrew T; Wittchen, Hans-Ulrich; Einsle, Franziska; Lang, Thomas; Helbig-Lang, Sylvia; Fydrich, Thomas; Fehm, Lydia; Hamm, Alfons O; Richter, Jan; Alpers, Georg W; Alpers, George W; Gerlach, Alexander L; Ströhle, Andreas; Kircher, Tilo; Deckert, Jürgen; Zwanzger, Peter; Höfler, Michael; Arolt, Volker

2011-06-01

Cognitive-behavioral therapy (CBT) is a first-line treatment for panic disorder with agoraphobia (PD/AG). Nevertheless, an understanding of its mechanisms and particularly the role of therapist-guided exposure is lacking. This study was aimed to evaluate whether therapist-guided exposure in situ is associated with more pervasive and long-lasting effects than therapist-prescribed exposure in situ. A multicenter randomized controlled trial, in which 369 PD/AG patients were treated and followed up for 6 months. Patients were randomized to 2 manual-based variants of CBT (T+/T-) or a wait-list control group (WL; n = 68) and were treated twice weekly for 12 sessions. CBT variants were identical in content, structure, and length, except for implementation of exposure in situ: In the T+ variant (n = 163), therapists planned and supervised exposure in situ exercises outside the therapy room; in the T- group (n = 138), therapists planned and discussed patients' in situ exposure exercises but did not accompany them. Primary outcome measures were (a) Hamilton Anxiety Scale, (b) Clinical Global Impression, (c) number of panic attacks, and (d) agoraphobic avoidance (Mobility Inventory). For T+ and T- compared with WL, all outcome measures improved significantly with large effect sizes from baseline to post (range = -0.5 to -2.5) and from post to follow-up (range = -0.02 to -1.0). T+ improved more than T- on the Clinical Global Impression and Mobility Inventory at post and follow-up and had greater reduction in panic attacks during the follow-up period. Reduction in agoraphobic avoidance accelerated after exposure was introduced. A dose-response relation was found for Time × Frequency of Exposure and reduction in agoraphobic avoidance. Therapist-guided exposure is more effective for agoraphobic avoidance, overall functioning, and panic attacks in the follow-up period than is CBT without therapist-guided exposure. Therapist-guided exposure promotes additional therapeutic improvement--possibly mediated by increased physical engagement in feared situations--beyond the effects of a CBT treatment in which exposure is simply instructed. (PsycINFO Database Record (c) 2011 APA, all rights reserved).

Photocatalytic reduction of CO2 with H2O to CH4 on Cu(I) supported TiO2 nanosheets with defective {001} facets.

PubMed

Zhu, Shuying; Liang, Shijing; Tong, Yuecong; An, Xiaohan; Long, Jinlin; Fu, Xianzhi; Wang, Xuxu

2015-04-21

Highly dispersed Cu2O clusters loaded on TiO2 nanosheets with dominant exposed {001} facets are prepared by a hydrothermal treatment followed by photodeposition. The physicochemical properties of the as-prepared samples are characterized carefully. The deposition position and chemical state of the Cu2O clusters are characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, EPR spectroscopy, and in situ CO-adsorbed FTIR spectroscopy, respectively. The results show that in situ Cu deposition leads to in situ formation of abundant oxygen vacancies (Vo) on the surface of the TiO2 nanosheets. Interestingly, the co-existence of Vo and Cu2O clusters could promote the photoactivity of CO2 reduction efficiently. The surface Vo play a significant role in the reduction of CO2. Meanwhile, the deposited Cu(I) species serve also as active sites for the formation of CH4, and then protect CH4 from degradation by generated oxidation species. For the photoreduction of CO2 to CH4, it is found that the content level of Cu2O has a significant influence on the activity. Cu-TiO2-1.0 shows the highest photocatalytic activity, which is over 30 times higher than that of the parent TiO2. This great enhancement of photocatalytic activity may be contributed by high CO2 adsorption capacity, high electron mobility, and high concentration of Vo. However, the effect of the surface area of the samples on the activity is negligible. All of this evidence is obtained by CO2-sorption, electrochemistry, in situ FTIR spectroscopy, in situ ERP techniques, etc. The reaction intermediates are detected by in situ FTIR spectroscopy. Finally, a probable mechanism is proposed based on the experimental results. It is hoped that our work could render one of the most effective strategies to achieve advanced properties over photofunctional materials for solar energy conversion of CO2.

Speciation and reactivity of uranium products formed during in situ bioremediation in a shallow alluvial aquifer.

PubMed

Alessi, Daniel S; Lezama-Pacheco, Juan S; Janot, Noémie; Suvorova, Elena I; Cerrato, José M; Giammar, Daniel E; Davis, James A; Fox, Patricia M; Williams, Kenneth H; Long, Philip E; Handley, Kim M; Bernier-Latmani, Rizlan; Bargar, John R

2014-11-04

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans.

Speciation and Reactivity of Uranium Products Formed during in Situ Bioremediation in a Shallow Alluvial Aquifer

PubMed Central

2015-01-01

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans. PMID:25265543

Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth.

PubMed

Sutter, Eli A; Sutter, Peter W

2014-12-03

In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important, as they provide direct insight into processes in liquids, such as solution growth of nanoparticles, among others. In liquid cell TEM/STEM redox reaction experiments, the hydrated electrons e(-)aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e(-)aq generated by the electron beam during in situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e(-)aq]. By comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e(-)aq] but also the rate of reduction of a metal-ion complex to zerovalent metal atoms in solution.

Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth

DOE PAGES

Sutter, Eli A.; Sutter, Peter W.

2014-11-19

In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important as they provide direct insight into processes in liquids, such as solution growth of nanoparticles among others. In liquid cell TEM/STEM redox reaction experiments the hydrated electrons e⁻ aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e⁻ aq generated by the electron beam during in-situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the ratemore » of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e⁻ aq]. In addition, by comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e⁻ aq] but also the rate of reduction of a metal-ion complex to zero-valent metal atoms in solution.« less

Chemical and Microbial Characterization of North Slope Viscous Oils to Assess Viscosity Reduction and Enhanced Recovery

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

Shirish Patil; Abhijit Dandekar; Mary Beth Leigh

2008-12-31

A large proportion of Alaska North Slope (ANS) oil exists in the form of viscous deposits, which cannot be produced entirely using conventional methods. Microbially enhanced oil recovery (MEOR) is a promising approach for improving oil recovery for viscous deposits. MEOR can be achieved using either ex situ approaches such as flooding with microbial biosurfactants or injection of exogenous surfactant-producing microbes into the reservoir, or by in situ approaches such as biostimulation of indigenous surfactant-producing microbes in the oil. Experimental work was performed to analyze the potential application of MEOR to the ANS oil fields through both ex situ andmore » in situ approaches. A microbial formulation containing a known biosurfactant-producing strain of Bacillus licheniformis was developed in order to simulate MEOR. Coreflooding experiments were performed to simulate MEOR and quantify the incremental oil recovery. Properties like viscosity, density, and chemical composition of oil were monitored to propose a mechanism for oil recovery. The microbial formulation significantly increased incremental oil recovery, and molecular biological analyses indicated that the strain survived during the shut-in period. The indigenous microflora of ANS heavy oils was investigated to characterize the microbial communities and test for surfactant producers that are potentially useful for biostimulation. Bacteria that reduce the surface tension of aqueous media were isolated from one of the five ANS oils (Milne Point) and from rock oiled by the Exxon Valdez oil spill (EVOS), and may prove valuable for ex situ MEOR strategies. The total bacterial community composition of the six different oils was evaluated using molecular genetic tools, which revealed that each oil tested possessed a unique fingerprint indicating a diverse bacterial community and varied assemblages. Collectively we have demonstrated that there is potential for in situ and ex situ MEOR of ANS oils. Future work should focus on lab and field-scale testing of ex situ MEOR using Bacillus licheniformis as well as the biosurfactant-producing strains we have newly isolated from the Milne Point reservoir and the EVOS environment.« less

Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

NASA Astrophysics Data System (ADS)

Liu, Ying; Zhang, Kun; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

2016-04-01

The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol-gel method, and subsequently with surface modifying with amino in the purpose to form SiO2-NH2 shell. Thus, metal particles were easily adsorbed into the SiO2-NH2 shell and in-situ reduced by NaBH4 solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu2(OH)3Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water.

In situ determination of the effects of lead and copper on cyanobacterial populations in microcosms.

PubMed

Burnat, Mireia; Diestra, Elia; Esteve, Isabel; Solé, Antonio

2009-07-10

Biomass has been studied as biomarker to evaluate the effect of heavy metals on microbial communities. Nevertheless, the most important methodological problem when working with natural and artificial microbial mats is the difficulty to evaluate changes produced on microorganism populations that are found in thicknesses of just a few mm depth. Here, we applied for first time a recently published new method based on confocal laser scanning microscopy and image-program analysis to determine in situ the effect of Pb and Cu stress in cyanobacterial populations. The results showed that both in the microcosm polluted by Cu and by Pb, a drastic reduction in total biomass for cyanobacterial and Microcoleus sp. (the dominant filamentous cyanobacterium in microbial mats) was detected within a week. According to the data presented in this report, this biomass inspection has a main advantage: besides total biomass, diversity, individual biomass of each population and their position can be analysed at microscale level. CLSM-IA could be a good method for analyzing changes in microbial biomass as a response to the addition of heavy metals and also to other kind of pollutants.

In situ spectroscopic characterization of Ni 1-xZn x/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

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

Spanjers, Charles S.; Sim, Richard S.; Sturgis, Nicholas P.

2015-10-30

The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. N₀̣̣₈₅ Zn₀̣̣₁₅O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni 1-xZn x, at ~400 °C with x increasingmore » with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β₁-NiZn formation at ~550 °C. In comparison to a Ni/SiO₂ catalyst, Ni/ZnO necessitates a higher temperature for the reduction of Ni II to Ni⁰, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO₂. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H–D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO₂.These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.« less

Experimental investigation on thermochemical sulfate reduction in the presence of 1-pentanethiol at 200 and 250 °C: Implications for in situ TSR processes occurring in some MVT deposits

USGS Publications Warehouse

Yuan, Shunda; Ellis, Geoffrey S.; Chou, I-Ming; Burruss, Robert

2017-01-01

Organic sulfur compounds are ubiquitous in natural oil and gas fields and moderate-low temperature sulfide ore deposits. Previous studies have shown that organic sulfur compounds are important in enhancing the rates of thermochemical sulfate reduction (TSR) reactions, but the details of these reaction mechanisms remain unclear. In order to assess the extent of sulfate reduction in the presence of labile sulfur species at temperature conditions near to those where TSR occurs in nature, we conducted a series of experiments using the fused silica capillary capsule (FCSS) method. The tested systems containing labile sulfur species are MgSO4 + 1-pentanethiol (C5H11SH) + 1-octene (C8H16), MgSO4 + 1-octene (C8H16), MgSO4 + 1-pentanethiol (C5H11SH), 1-pentanethiol (C5H11SH)+H2O, and MgSO4 + 1-pentanethiol (C5H11SH) + ZnBr2 systems. Our results show that: (1) intermediate oxidized carbon species (ethanol and acetic acid) are formed during TSR simulation experiments when 1-pentanethiol is present; (2) in the presence of ZnBr2, 1-pentanethiol can be oxidized by sulfate to CO2 at 200 °C, which is within the temperature range observed in natural TSR; and (3) the precipitation of sulfide minerals may significantly promote the rate of TSR, indicating that the rates of in situ TSR reactions in ore deposits could be much faster than previously thought. This may be important for understanding the possibility of in situ TSR as a mechanism for the precipitation of metal sulfides in some ore deposits. These findings provide important experimental evidence for understanding the role of organic sulfur compounds in TSR reactions and the pathway of TSR reactions initiated by organic sulfur compounds under natural conditions.

Volumetric muscle loss injury repair using in situ fibrin gel cast seeded with muscle-derived stem cells (MDSCs)

PubMed Central

Matthias, Nadine; Hunt, Samuel D.; Wu, Jianbo; Lo, Jonathan; Smith Callahan, Laura A.; Li, Yong; Huard, Johnny; Darabi, Radbod

2018-01-01

Volumetric muscle defect, caused by trauma or combat injuries, is a major health concern leading to severe morbidity. It is characterized by partial or full thickness loss of muscle and its bio-scaffold, resulting in extensive fibrosis and scar formation. Therefore, the ideal therapeutic option is to use stem cells combined with bio-scaffolds to restore muscle. For this purpose, muscle-derived stem cells (MDSCs) are a great candidate due to their unique multi-lineage differentiation potential. In this study, we evaluated the regeneration potential of MDSCs for muscle loss repair using a novel in situ fibrin gel casting. Muscle defect was created by a partial thickness wedge resection in the tibialis anterior (TA)muscles of NSG mice which created an average of 25% mass loss. If untreated, this defect leads to severe muscle fibrosis. Next, MDSCs were delivered using a novel in situ fibrin gel casting method. Our results demonstrated MDSCs are able to engraft and form new myofibers in the defect when casted along with fibrin gel. LacZ labeled MDSCs were able to differentiate efficiently into new myofibers and significantly increase muscle mass. This was also accompanied by significant reduction of fibrotic tissue in the engrafted muscles. Furthermore, transplanted cells also contributed to new vessel formation and satellite cell seeding. These results confirmed the therapeutic potential of MDSCs and feasibility of direct in situ casting of fibrin/MDSC mixture to repair muscle mass defects. PMID:29331939

Antibacterial activity of silver nanoparticles synthesized In-situ by solution spraying onto cellulose.

PubMed

Yan, Jinhua; Abdelgawad, Abdelrahman M; El-Naggar, Mehrez E; Rojas, Orlando J

2016-08-20

Spray technique was used for the adsorption of in-situ silver nanoparticles (AgNPs) onto and inside the surface of nano- and micro- fibrillar cellulose (NFC and MFC) as well as filter paper. The abundance of hydroxyl and carboxyl groups located in NFC and MFC are used to stabilize Ag ions (Ag(+)) which were then in-situ reduced to (AgNPs) by chemical or UV reduction. The surface characteristic features, elemental analysis, particle size as well as size distribution of the obtained MFC, NFC and filter paper loaded with AgNPs were characterized via field emission scanning electron microscopy connected to energy dispersive X-ray spectroscopy (FESEM- EDX) and transmission electron microscopy (TEM). The associated chemical changes after growth of AgNPs onto the cellulose substrates were assessed by fourier transform infra-red (FT-IR) while the thermal stability of such systems were investigated by thermogravimetrical analyses (TGA). The antibacterial properties of AgNPs loaded NFC, MFC and filter paper as well was investigated against Escherichia Coli. The resulted data indicate that the particle size was found to be 11 and 26nm for AgNPs nucleated on NFC and MFC-based papers respectively. The antibacterial activity of AgNPs loaded MFC exhibited higher antibacterial activity than that of AgNPs loaded NFC. Overall, the present research demonstrates facile and fast method for in-situ antibacterial AgNPs loading on cellulose substrates. Copyright © 2016 Elsevier Ltd. All rights reserved.

In situ laser-induced breakdown spectroscopy measurements of chemical compositions in stainless steels during tungsten inert gas welding

NASA Astrophysics Data System (ADS)

Taparli, Ugur Alp; Jacobsen, Lars; Griesche, Axel; Michalik, Katarzyna; Mory, David; Kannengiesser, Thomas

2018-01-01

A laser-induced breakdown spectroscopy (LIBS) system was combined with a bead-on-plate Tungsten Inert Gas (TIG) welding process for the in situ measurement of chemical compositions in austenitic stainless steels during welding. Monitoring the weld pool's chemical composition allows governing the weld pool solidification behavior, and thus enables the reduction of susceptibility to weld defects. Conventional inspection methods for weld seams (e.g. ultrasonic inspection) cannot be performed during the welding process. The analysis system also allows in situ study of the correlation between the occurrence of weld defects and changes in the chemical composition in the weld pool or in the two-phase region where solid and liquid phase coexist. First experiments showed that both the shielding Ar gas and the welding arc plasma have a significant effect on the selected Cr II, Ni II and Mn II characteristic emissions, namely an artificial increase of intensity values via unspecific emission in the spectra. In situ investigations showed that this artificial intensity increase reached a maximum in presence of weld plume. Moreover, an explicit decay has been observed with the termination of the welding plume due to infrared radiation during sample cooling. Furthermore, LIBS can be used after welding to map element distribution. For austenitic stainless steels, Mn accumulations on both sides of the weld could be detected between the heat affected zone (HAZ) and the base material.

In situ XANES and EXAFS Analysis of Redox Active Fe Center Ionic Liquids

DOE PAGES

Apblett, Christopher A.; Stewart, David M.; Fryer, Robert T.; ...

2015-10-23

We apply in situ X-Ray Absorption Near Edge Spectroscopy (XANES) and Extended X-Ray Absorption Fine Structure (EXAFS) techniques to a metal center ionic liquid undergoing oxidation and reduction in a three electrode spectroscopic cell. Furthermore, the determination of the extent of reduction under negative bias on the working electrode and the extent of oxidation are determined after pulse voltammetry to quiescence. While the ionic liquid undergoes full oxidation, it undergoes only partial reduction, likely due to transport issues on the timescale of the experiment. Nearest neighbor Fe-O distances in the fully oxidized state match well to expected values for similarlymore » coordinated solids, but reduction does not result in an extension of the Fe-O bond length, as would be expected from comparisons to the solid phase. Instead, little change in bond length is observed. Finally, we suggest that this may be due to a more complex interaction between the monodentate ligands of the metal center anion and the surrounding charge cloud, rather than straightforward electrostatics between the metal center and the nearest neighbor grouping.« less

Synthesis of an efficient heteroatom-doped carbon electro-catalyst for oxygen reduction reaction by pyrolysis of protein-rich pulse flour cooked with SiO2 nanoparticles.

PubMed

Gokhale, Rohan; Unni, Sreekuttan M; Puthusseri, Dhanya; Kurungot, Sreekumar; Ogale, Satishchandra

2014-03-07

Development of a highly durable, fuel-tolerant, metal-free electro-catalyst for oxygen reduction reaction (ORR) is essential for robust and cost-effective Anion Exchange Membrane Fuel Cells (AEMFCs). Herein, we report the development of a nitrogen-doped (N-doped) hierarchically porous carbon-based efficient ORR electrocatalyst from protein-rich pulses. The process involves 3D silica nanoparticle templating of the pulse flour(s) followed by their double pyrolysis. The detailed experiments are performed on gram flour (derived from chickpeas) without any in situ/ex situ addition of dopants. The N-doped porous carbon thus generated shows remarkable electrocatalytic activity towards ORR in the alkaline medium. The oxygen reduction on this material follows the desired 4-electron transfer mechanism involving the direct reduction pathway. Additionally, the synthesized carbon catalyst also exhibits good electrochemical stability and fuel tolerance. The results are also obtained and compared with the case of soybean flour having higher nitrogen content to highlight the significance of different parameters in the ORR catalyst performance.

In-situ sequential laser transfer and laser reduction of graphene oxide films

NASA Astrophysics Data System (ADS)

Papazoglou, S.; Petridis, C.; Kymakis, E.; Kennou, S.; Raptis, Y. S.; Chatzandroulis, S.; Zergioti, I.

2018-04-01

Achieving high quality transfer of graphene on selected substrates is a priority in device fabrication, especially where drop-on-demand applications are involved. In this work, we report an in-situ, fast, simple, and one step process that resulted in the reduction, transfer, and fabrication of reduced graphene oxide-based humidity sensors, using picosecond laser pulses. By tuning the laser illumination parameters, we managed to implement the sequential printing and reduction of graphene oxide flakes. The overall process lasted only a few seconds compared to a few hours that our group has previously published. DC current measurements, X-Ray Photoelectron Spectroscopy, X-Ray Diffraction, and Raman Spectroscopy were employed in order to assess the efficiency of our approach. To demonstrate the applicability and the potential of the technique, laser printed reduced graphene oxide humidity sensors with a limit of detection of 1700 ppm are presented. The results demonstrated in this work provide a selective, rapid, and low-cost approach for sequential transfer and photochemical reduction of graphene oxide micro-patterns onto various substrates for flexible electronics and sensor applications.

Triboluminesence multifunctional cementitious composites with in situ damage sensing capability

NASA Astrophysics Data System (ADS)

Olawale, David O.; Dickens, Tarik; Uddin, Mohammed J.; Okoli, Okenwa O.

2012-04-01

Structural health monitoring of civil infrastructure systems like concrete bridges and dams has become critical because of the aging and overloading of these CIS. Most of the available SHM methods are not in-situ and can be very expensive. The triboluminescence multifunctional cementitious composites (TMCC) have in-built crack detection mechanism that can enable bridge engineers to monitor and detect abnormal crack formation in concrete structures so that timely corrective action can be taken to prevent costly or catastrophic failures. This article reports the fabrication process and test result of the flexural characterization of the TMCC. Accelerated durability test indicated that the 0.5 ZnS:Mn/Epoxy weight fraction ITOF sensor configuration to be more desirable in terms of durability. The alkaline environment at the highest temperature investigated (45 °C) resulted in significant reduction in the mean glass transition and storage moduli of the tested ITOF thin films. Further work is ongoing to correlate the TL response of the TMCC with damage, particularly crack opening.

Improvement of spin-exchange optical pumping of xenon-129 using in situ NMR measurement in ultra-low magnetic field

NASA Astrophysics Data System (ADS)

Takeda, Shun; Kumagai, Hiroshi

2018-02-01

Hyperpolarized (HP) noble gas has attracted attention in NMR / MRI. In an ultra-low magnetic field, the effectiveness of signal enhancement by HP noble gas should be required because reduction of the signal intensity is serious. One method of generating HP noble gas is spin exchange optical pumping which uses selective excitation of electrons of alkali metal vapor and spin transfer to nuclear spin by collision to noble gas. Although SEOP does not require extreme cooling or strong magnetic field, generally it required large-scale equipment including high power light source to generate HP noble gas with high efficiency. In this study, we construct a simply generation system of HP xenon-129 by SEOP with an ultralow magnetic field (up to 1 mT) and small-scale light source (about 1W). In addition, we measure in situ NMR signal at the same time, and then examine efficient conditions for SEOP in ultra-low magnetic fields.

Biosorption and biotransformation of hexavalent chromium [Cr(VI)]: A comprehensive review.

PubMed

Jobby, Renitta; Jha, Pamela; Yadav, Anoop Kumar; Desai, Nitin

2018-05-09

Chromium (VI) is one of the most common environmental contaminant due to its tremendous industrial applications. It is non-biodegradable as it is a heavy metal, and hence, of major concern. Therefore, it is pertinent that the remediation method should be such that brings chromium within permissible limits before the effluent is discharged. Several different strategies are adopted by microorganisms for Cr (VI) removal mostly involving biosorption and biotransformation or both. These mechanisms are based on the surface nature of the biosorbent and the availability of reductants. This review article focuses on chromium pollution problem, its chemistry, sources, effects, remediation strategies by biological agents and detailed chromium detoxification mechanism in microbial cell. A summary of applied in situ and ex situ chromium bioremediation technologies is also listed. This can be helpful for developing technologies to be more efficient for Cr (VI) removal thereby bridging the gap between laboratory findings and industrial application for chromium remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Photocatalytic synthesis of urea from in situ generated ammonia and carbon dioxide.

PubMed

Srinivas, Basavaraju; Kumari, Valluri Durga; Sadanandam, Gullapelli; Hymavathi, Chilumula; Subrahmanyam, Machiraju; De, Bhudev Ranjan

2012-01-01

TiO(2) and Fe-titanate (different wt%) supported on zeolite were prepared by sol-gel and solid-state dispersion methods. The photocatalysts prepared were characterized by X-ray diffraction, scanning electron microscopy and ultraviolet (UV)-visible diffuse reflectance spectroscopy techniques. Photocatalytic reduction of nitrate in water and isopropanol/oxalic acid as hole scavengers are investigated in a batch reactor under UV illumination. The yield of urea increased notably when the catalysts were supported on zeolite. The Fe-titanate supported catalyst promotes the charge separation that contributes to an increase in selective formation of urea. The product formation is because of the high adsorption of in situ generated CO(2) and NH(3) over shape-selective property of the zeolite in the composite photocatalyst. The maximum yield of urea is found to be 18 ppm while 1% isopropanol containing solution over 10 wt% Fe-titanate/HZSM-5 photocatalyst was used. © 2011 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2011 The American Society of Photobiology.

The Third SeaWiFS HPLC Analysis Round-Robin Experiment (SeaHARRE-3)

NASA Technical Reports Server (NTRS)

Hooker, Stanford B.; VanHeukelem, Laurei; Thomas, Crystal S.; Claustre, Herve; Ras, Josephine; Schluter, Louise; Clementson, Lesley; vanderLinde, Dirk; Eker-Develi, Elif; Berthon, Jean-Francois;

Laser-induced contamination control for high-power lasers in space-based LIDAR missions

NASA Astrophysics Data System (ADS)

Alves, Jorge; Pettazzi, Federico; Tighe, Adrian; Wernham, Denny

2017-11-01

In the framework of the ADM-Aeolus satellite mission, successful test campaigns have been performed in ESTEC's laser laboratory, and the efficiency of several mitigation techniques against Laser-Induced Contamination (LIC) have been demonstrated for the ALADIN laser. These techniques include the standard contamination control methods of materials identification with particular tendency to cause LIC, reduction of the outgassing of organic materials by vacuum bake-out and shielding of optical surfaces from the contamination sources. Also novel mitigation methods such as in-situ cleaning via partial pressures, or the usage of molecular absorbers were demonstrated. In this context, a number of highly sensitive optical measurement techniques have been developed and tested to detect and monitor LIC deposits at nanometre level.

In-situ Tapering of Chalcogenide Fiber for Mid-infrared Supercontinuum Generation

PubMed Central

Rudy, Charles W.; Marandi, Alireza; Vodopyanov, Konstantin L.; Byer, Robert L.

2013-01-01

Supercontinuum generation (SCG) in a tapered chalcogenide fiber is desirable for broadening mid-infrared (or mid-IR, roughly the 2-20 μm wavelength range) frequency combs1, 2 for applications such as molecular fingerprinting, 3 trace gas detection, 4 laser-driven particle acceleration, 5 and x-ray production via high harmonic generation. 6 Achieving efficient SCG in a tapered optical fiber requires precise control of the group velocity dispersion (GVD) and the temporal properties of the optical pulses at the beginning of the fiber, 7 which depend strongly on the geometry of the taper. 8 Due to variations in the tapering setup and procedure for successive SCG experiments-such as fiber length, tapering environment temperature, or power coupled into the fiber, in-situ spectral monitoring of the SCG is necessary to optimize the output spectrum for a single experiment. In-situ fiber tapering for SCG consists of coupling the pump source through the fiber to be tapered to a spectral measurement device. The fiber is then tapered while the spectral measurement signal is observed in real-time. When the signal reaches its peak, the tapering is stopped. The in-situ tapering procedure allows for generation of a stable, octave-spanning, mid-IR frequency comb from the sub harmonic of a commercially available near-IR frequency comb. 9 This method lowers cost due to the reduction in time and materials required to fabricate an optimal taper with a waist length of only 2 mm. The in-situ tapering technique can be extended to optimizing microstructured optical fiber (MOF) for SCG10 or tuning of the passband of MOFs, 11 optimizing tapered fiber pairs for fused fiber couplers12 and wavelength division multiplexers (WDMs), 13 or modifying dispersion compensation for compression or stretching of optical pulses.14-16 PMID:23748947

Mechanistic analysis of Zein nanoparticles/PLGA triblock in situ forming implants for glimepiride.

PubMed

Ahmed, Osama Abdelhakim Aly; Zidan, Ahmed Samir; Khayat, Maan

2016-01-01

The study aims at applying pharmaceutical nanotechnology and D-optimal fractional factorial design to screen and optimize the high-risk variables affecting the performance of a complex drug delivery system consisting of glimepiride-Zein nanoparticles and inclusion of the optimized formula with thermoresponsive triblock copolymers in in situ gel. Sixteen nanoparticle formulations were prepared by liquid-liquid phase separation method according to the D-optimal fractional factorial design encompassing five variables at two levels. The responses investigated were glimepiride entrapment capacity (EC), particle size and size distribution, zeta potential, and in vitro drug release from the prepared nanoparticles. Furthermore, the feasibility of embedding the optimized Zein-based glimepiride nanoparticles within thermoresponsive triblock copolymers poly(lactide-co-glycolide)-block-poly(ethylene glycol)-block-poly(lactide-co-glycolide) in in situ gel was evaluated for controlling glimepiride release rate. Through the systematic optimization phase, improvement of glimepiride EC of 33.6%, nanoparticle size of 120.9 nm with a skewness value of 0.2, zeta potential of 11.1 mV, and sustained release features of 3.3% and 17.3% drug released after 2 and 24 hours, respectively, were obtained. These desirability functions were obtained at Zein and glimepiride loadings of 50 and 75 mg, respectively, utilizing didodecyldimethylammonium bromide as a stabilizer at 0.1% and 90% ethanol as a common solvent. Moreover, incorporating this optimized formulation in triblock copolymers-based in situ gel demonstrated pseudoplastic behavior with reduction of drug release rate as the concentration of polymer increased. This approach to control the release of glimepiride using Zein nanoparticles/triblock copolymers-based in situ gel forming intramuscular implants could be useful for improving diabetes treatment effectiveness.

Oxygen Extraction from Minerals

NASA Technical Reports Server (NTRS)

Muscatello, Tony

2017-01-01

Oxygen, whether used as part of rocket bipropellant or for astronaut life support, is a key consumable for space exploration and commercialization. In Situ Resource Utilization (ISRU) has been proposed many times as a method for making space exploration more cost effective and sustainable. On planetary and asteroid surfaces the presence of minerals in the regolith that contain oxygen is very common, making them a potential oxygen resource. The majority of research and development for oxygen extraction from minerals has been for lunar regolith although this work would generally be applicable to regolith at other locations in space. This presentation will briefly survey the major methods investigated for oxygen extraction from regolith with a focus on the current status of those methods and possible future development pathways. The major oxygen production methods are (1) extraction from lunar ilmenite (FeTiO3) with either hydrogen or carbon monoxide, (2) carbothermal reduction of iron oxides and silicates with methane, and (3) molten regolith electrolysis (MRE) of silicates. Methods (1) and (2) have also been investigated in a two-step process using CO reduction and carbon deposition followed by carbothermal reduction. All three processes have byproducts that could also be used as resources. Hydrogen or carbon monoxide reduction produce iron metal in small amounts that could potentially be used as construction material. Carbothermal reduction also makes iron metal along with silicon metal and a glass with possible applications. MRE produces iron, silicon, aluminum, titanium, and glass, with higher silicon yields than carbothermal reduction. On Mars and possibly on some moons and asteroids, water is present in the form of mineral hydrates, hydroxyl (-OH) groups on minerals, andor water adsorbed on mineral surfaces. Heating of the minerals can liberate the water which can be electrolyzed to provide a source of oxygen as well. The chemistry of these processes, some key development and demonstration projects, the challenges remaining to be overcome, and possible future directions will be discussed with a goal of increased understanding of these important ISRU technologies and their potential applications to space exploration and settlement.

Mild in situ growth of platinum nanoparticles on multiwalled carbon nanotube-poly (vinyl alcohol) hydrogel electrode for glucose electrochemical oxidation

NASA Astrophysics Data System (ADS)

Liu, Shumin; Zheng, Yudong; Qiao, Kun; Su, Lei; Sanghera, Amendeep; Song, Wenhui; Yue, Lina; Sun, Yi

2015-12-01

This investigation describes an effective strategy to fabricate an electrochemically active hybrid hydrogel made from platinum nanoparticles that are highly dense, uniformly dispersed, and tightly embedded throughout the conducting hydrogel network for the electrochemical oxidation of glucose. A suspension of multiwalled carbon nanotubes and polyvinyl alcohol aqueous was coated on glassy carbon electrode by electrophoretic deposition and then physically crosslinked to form a three-dimensional porous conductive hydrogel network by a process of freezing and thawing. The network offered 3D interconnected mass-transport channels (around 200 nm) and confined nanotemplates for in situ growth of uniform platinum nanoparticles via the moderate reduction agent, ascorbic acid. The resulting hybrid hydrogel electrode membrane demonstrates an effective method for loading platinum nanoparticles on multiwalled carbon nanotubes by the electrostatic adsorption between multiwalled carbon nanotubes and platinum ions within porous hydrogel network. The average diameter of platinum nanoparticles is 37 ± 14 nm, which is less than the particle size by only using the moderate reduction agent. The hybrid hydrogel electrode membrane-coated glassy carbon electrode showed excellent electrocatalytic activity and good long-term stability toward glucose electrochemical oxidation. The glucose oxidation current exhibited a linear relationship with the concentration of glucose in the presence of chloride ions, promising for potential applications of implantable biofuel cells, biosensors, and electronic devices.

Significant Artifact Reduction at 1.5T and 3T MRI by the Use of a Cochlear Implant with Removable Magnet: An Experimental Human Cadaver Study

PubMed Central

Wagner, Franca; Wimmer, Wilhelm; Leidolt, Lars; Vischer, Mattheus; Weder, Stefan; Wiest, Roland; Mantokoudis, Georgios; Caversaccio, Marco D.

2015-01-01

Objective Cochlear implants (CIs) are standard treatment for postlingually deafened individuals and prelingually deafened children. This human cadaver study evaluated diagnostic usefulness, image quality and artifacts in 1.5T and 3T magnetic resonance (MR) brain scans after CI with a removable magnet. Methods Three criteria (diagnostic usefulness, image quality, artifacts) were assessed at 1.5T and 3T in five cadaver heads with CI. The brain magnetic resonance scans were performed with and without the magnet in situ. The criteria were analyzed by two blinded neuroradiologists, with focus on image distortion and limitation of the diagnostic value of the acquired MR images. Results MR images with the magnet in situ were all compromised by artifacts caused by the CI. After removal of the magnet, MR scans showed an unequivocal artifact reduction with significant improvement of the image quality and diagnostic usefulness, both at 1.5T and 3T. Visibility of the brain stem, cerebellopontine angle, and parieto-occipital lobe ipsilateral to the CI increased significantly after magnet removal. Conclusions The results indicate the possible advantages for 1.5T and 3T MR scanning of the brain in CI carriers with removable magnets. Our findings support use of CIs with removable magnets, especially in patients with chronic intracranial pathologies. PMID:26200775

Parallel In Situ Screening of Remediation Strategies for Improved Decision Making, Remedial Design, and Cost Savings

DTIC Science & Technology

2013-02-01

November 2012 phosphorus, and vitamin B12. Additionally a reductant reacts directly with hexavalent chromium to reduce it to the trivalent state. SRS...being operated under continuous flow conditions in the laboratory. Entire assembly takes up approximately 5 sq. ft. in a fume hood. . 44 Figure 5-3...61 Figure 5-16. Hexavalent Chromium detected in ISMA effluent post in situ incubation

Enhancement of In Situ Bioremediation of Energetic Compounds by Coupled Abiotic/Biotic Processes

DTIC Science & Technology

2007-08-01

reduced in the laboratory and successfully treat energetics (RDX, TNT, CL-20, NDMA ), chlorinated solvents (PCE, TCE, TCA, 1,1-DCE, cis-DCE), and...Fruchter, M Williams, V Vermeul, H Fredrickson, and K Thompson. 2006. In situ chemical reduction of sediments for TCE, energetics, and NDMA remediation...sediments for TCE, energetics, and NDMA remediation, Remediation of Chlorinated and Recalcitrant Compounds, Monterey, California, May 2006. Szecsody J

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Rate Dependent Multi-Mechanism Discharge of Ag 0.50VOP 4·1.8H 2O: Insights from In Situ Energy Dispersive X-ray Diffraction

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

Huie, Matthew M.; Bock, David C.; Zhong, Zhong

Ag 0.50VOPO 4·1.8H 2O (silver vanadium phosphate, SVOP) demonstrates a counterintuitive higher initial loaded voltage under higher discharge current. Energy dispersive X-ray diffraction (EDXRD) from synchrotron radiation was used to create tomographic profiles of cathodes at various depths of discharge for two discharge rates. SVOP displays two reduction mechanisms, reduction of a vanadium center accompanied by lithiation of the structure, or reduction-displacement of a silver cation to form silver metal. In-situ EDXRD provides the opportunity to observe spatially resolved changes to the parent SVOP crystal and formation of Ag 0 during reduction. At a C/170 discharge rate V 5+ reductionmore » is the preferred initial reaction resulting in higher initial loaded voltage. At a discharge rate of C/400 reduction of Ag + with formation of conductive Ag 0 occurs earlier during discharge. Discharge rate also affects the spatial location of reduction products. The faster discharge rate initiates reduction close to the current collector with non-uniform distribution of silver metal resulting in isolated cathode areas. The slower rate develops a more homogenous distribution of reduced SVOP and silver metal. This study illuminates the roles of electronic and ionic conductivity limitations within a cathode at the mesoscale and how they impact the course of reduction processes and loaded voltage.« less

Rate Dependent Multi-Mechanism Discharge of Ag 0.50VOP 4·1.8H 2O: Insights from In Situ Energy Dispersive X-ray Diffraction

DOE PAGES

Huie, Matthew M.; Bock, David C.; Zhong, Zhong; ...

2016-09-01

Ag 0.50VOPO 4·1.8H 2O (silver vanadium phosphate, SVOP) demonstrates a counterintuitive higher initial loaded voltage under higher discharge current. Energy dispersive X-ray diffraction (EDXRD) from synchrotron radiation was used to create tomographic profiles of cathodes at various depths of discharge for two discharge rates. SVOP displays two reduction mechanisms, reduction of a vanadium center accompanied by lithiation of the structure, or reduction-displacement of a silver cation to form silver metal. In-situ EDXRD provides the opportunity to observe spatially resolved changes to the parent SVOP crystal and formation of Ag 0 during reduction. At a C/170 discharge rate V 5+ reductionmore » is the preferred initial reaction resulting in higher initial loaded voltage. At a discharge rate of C/400 reduction of Ag + with formation of conductive Ag 0 occurs earlier during discharge. Discharge rate also affects the spatial location of reduction products. The faster discharge rate initiates reduction close to the current collector with non-uniform distribution of silver metal resulting in isolated cathode areas. The slower rate develops a more homogenous distribution of reduced SVOP and silver metal. This study illuminates the roles of electronic and ionic conductivity limitations within a cathode at the mesoscale and how they impact the course of reduction processes and loaded voltage.« less

In situ X-ray diffraction study of reduction processes of Fe{sub 3}O{sub 4}- and Fe{sub 1-x}O-based ammonia-synthesis catalysts

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

Zheng Yifan, E-mail: zhengyifan@zjut.edu.c; Catalysis Institute, Zhejiang University of Technology, Hangzhou 310014; Liu Huazhang

2009-09-15

The temperature-programmed reduction process of two types of industrial ammonia-synthesis catalysts, A110 and ZA-5, which are, respectively, based on Fe{sub 3}O{sub 4} and Fe{sub 1-x}O precursors, were studied by in situ X-ray power diffraction (XRD). It has been found that the ZA-5 has lower reduction temperature and faster reduction rate, and its active phase alpha-Fe possesses a higher value of lattice microstrain than A110. The simulation based on Rietveld refinement has also shown that the shape of alpha-Fe grain of ZA-5 has a mixed shape of cube and sphere with more exposing (111) and (211) planes, while that of A110more » looks like a concave cube with more exposing (110) planes. Based on the results obtained, a growth model of alpha-Fe during the reduction of Fe{sub 3}O{sub 4}- and Fe{sub 1-x}O-based ammonia-synthesis catalysts is proposed, and the origins for the activity difference has been also discussed. - Graphical Abstract: A proposed growth model of active phase alpha-Fe during reduction. Due to H{sub 2} diffusing easily into the pores, reduction starts on outside and inside surface simultaneously to form 'microcrystalline film', and the particles shrink during reduction which results in breaking of the aggregated oxide particle.« less

Circulating and in situ lymphocyte subsets and Langerhans cells in patients with compositae oleoresin dermatitis and increased ultraviolet A sensitivity during treatment with azathioprine

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

Baadsgaard, O.

1986-04-01

Circulating and in situ lymphocyte subsets and Langerhans cells in four patients with compositae oleoresin dermatitis and increased ultraviolet A sensitivity before and during treatment with azathioprine were estimated. It was found that the number of Leu 6+ Langerhans cells decreased during therapy. This decrease was accompanied by a reduction in the number of Leu 2a+, Leu 3a+, Leu 4+, DR+, and Leu M2+ cells in the blood and a reduction in the number of Leu 2a+, Leu 3a+, Leu 4+, and DR+ cells in the skin. Concomitantly with the changes in the number of immunocompetent cells, the eczema cleared.

One-Pot Solvothermal in Situ Growth of 1D Single-Crystalline NiSe on Ni Foil as Efficient and Stable Transparent Conductive Oxide Free Counter Electrodes for Dye-Sensitized Solar Cells.

PubMed

Bao, Chao; Li, Faxin; Wang, Jiali; Sun, Panpan; Huang, Niu; Sun, Yihua; Fang, Liang; Wang, Lei; Sun, Xiaohua

2016-12-07

One-dimensional single-crystal nanostructural nickel selenides were successfully in situ grown on metal nickel foils by two simple one-step solvothermal methods, which formed NiSe/Ni counter electrodes (CEs) for dye-sensitized solar cells (DSSCs). The nickel foil acted as the nickel source in the reaction process, a supporting substrate, and an electron transport "speedway". Electrochemical testing indicated that the top 1D single-crystal NiSe exhibited prominent electrocatalytic activity for I 3 - reduction. Due to the metallic conductivity of Ni substrate and the outstanding electrocatalytic activity of single-crystal NiSe, the DSSC based on a NiSe/Ni CE exhibited higher fill factor (FF) and larger short-circuit current density (J sc ) than the DSSC based on Pt/FTO CE. The corresponding power conversion efficiency (6.75%) outperformed that of the latter (6.18%). Moreover, the NiSe/Ni CEs also showed excellent electrochemical stability in the I - /I 3 - redox electrolyte. These findings indicated that single-crystal NiSe in situ grown on Ni substrate was a potential candidate to replace Pt/TCO as a cheap and highly efficient counter electrode of DSSC.

Characterization and In-Situ Monitoring of ZnSe Crystal Growth by Seeded PVT for Microgravity Applications

NASA Technical Reports Server (NTRS)

Feth, Shari T.

2001-01-01

Crystal growth from the vapor phase continues to play a significant role in the production of II-VI semiconductor compounds (ZnO, ZnTe, CdTe, etc.) and SiC. As compared to melt growth methods (where available) the advantages are: (1) lower growth temperature(s); (2) reduction in defect concentration; (3) additional purification; and (4) enhanced crystal perfection. A powerful tool in determining the mechanism of PVT is microgravity. Under normal gravity conditions the transport mechanism is a superposition of diffusive and convective fluxes. Microgravity offers the possibility of studying the transport properties without the influence of convective effects. Research on the crystal growth of ZnSe by PVT (P.I.: Su of NASA/MSFC) will help to clarify the effects of convection on crystal growth. A crystal growth furnace with in-situ and real time optical monitoring capabilities was constructed and used to monitor the vapor composition and growing crystal surface morphology during the PVT growth of ZnSe. Using photoluminescence and SIMS, ex-situ, the incorporation of point defects (Zn vacancy) and impurities was found to be correlated to the gravity vector due to the influence of the convective flow. A summary of the results to date will be presented.

Determination of the NOx Loading of an Automotive Lean NOx Trap by Directly Monitoring the Electrical Properties of the Catalyst Material Itself

PubMed Central

Fremerey, Peter; Reiß, Sebastian; Geupel, Andrea; Fischerauer, Gerhard; Moos, Ralf

2011-01-01

Recently, it has been shown that the degree of loading of several types of automotive exhaust aftertreatment devices can be directly monitored in situ and in a contactless way by a microwave-based method. The goal of this study was to clarify whether this method can also be applied to NOx storage and reduction catalysts (lean NOx traps) in order to obtain further knowledge about the reactions occurring in the catalyst and to compare the results with those obtained by wirebound NOx loading sensors. It is shown that both methods are able to detect the different catalyst loading states. However, the sensitivity of the microwave-based method turned out to be small compared to that previously observed for other exhaust aftertreatment devices. This may limit the practical applicability of the microwave-based NOx loading detection in lean NOx traps. PMID:22164074

Effect of particle size on oral absorption of carvedilol nanosuspensions: in vitro and in vivo evaluation

PubMed Central

Liu, Dandan; Pan, Hao; He, Fengwei; Wang, Xiaoyu; Li, Jinyu; Yang, Xinggang; Pan, Weisan

2015-01-01

The purpose of this work was to explore the particle size reduction effect of carvedilol on dissolution and absorption. Three suspensions containing different sized particles were prepared by antisolvent precipitation method or in combination with an ultrasonication process. The suspensions were characterized for particle size, surface morphology, and crystalline state. The crystalline form of carvedilol was changed into amorphous form after antisolvent precipitation. The dissolution rate of carvedilol was significantly accelerated by a reduction in particle size. The intestinal absorption of carvedilol nanosuspensions was greatly improved in comparison with microsuspensions and solution in the in situ single-pass perfusion experiment. The in vivo evaluation demonstrated that carvedilol nanosuspensions and microsuspensions exhibited markedly increased Cmax (2.09- and 1.48-fold) and AUC0−t (2.11- and 1.51-fold), and decreased Tmax (0.34- and 0.48-fold) in contrast with carvedilol coarse suspensions. Moreover, carvedilol nanosuspensions showed good biocompatibility with the rat gastric mucosa in in vivo gastrointestinal irritation test. The entire results implicated that the dissolution rate and the oral absorption of carvedilol were significantly affected by the particle size. Particle size reduction to form nanosized particles was found to be an efficient method for improving the oral bioavailability of carvedilol. PMID:26508852

In Situ Study of Reduction Process of CuO Paste and Its Effect on Bondability of Cu-to-Cu Joints

NASA Astrophysics Data System (ADS)

Yao, Takafumi; Matsuda, Tomoki; Sano, Tomokazu; Morikawa, Chiaki; Ohbuchi, Atsushi; Yashiro, Hisashi; Hirose, Akio

2018-04-01

A bonding method utilizing redox reactions of metallic oxide microparticles achieves metal-to-metal bonding in air, which can be alternative to lead-rich high-melting point solder. However, it is known that the degree of the reduction of metallic oxide microparticles have an influence on the joint strength using this bonding method. In this paper, the reduction behavior of CuO paste and its effect on Cu-to-Cu joints were investigated through simultaneous microstructure-related x-ray diffraction and differential scanning calorimetry measurements. The CuO microparticles in the paste were gradually reduced to submicron Cu2O particles at 210-250°C. Subsequently, Cu nanoparticles were generated instantaneously at 300-315°C. There was a marked difference in the strengths of the joints formed at 300°C and 350°C. Thus, the Cu nanoparticles play a critical role in sintering-based bonding using CuO paste. Furthermore, once the Cu nanoparticles have formed, the joint strength increases with higher bonding temperature (from 350°C to 500°C) and pressure (5-15 MPa), which can exceed the strength of Pb-5Sn solder at higher temperature and pressure.

Manganese catalyzed reductive amination of aldehydes using hydrogen as a reductant.

PubMed

Wei, Duo; Bruneau-Voisine, Antoine; Valyaev, Dmitry A; Lugan, Noël; Sortais, Jean-Baptiste

2018-04-24

A one-pot two-step procedure was developed for the alkylation of amines via reductive amination of aldehydes using molecular dihydrogen as a reductant in the presence of a manganese pyridinyl-phosphine complex as a pre-catalyst. After the initial condensation step, the reduction of imines formed in situ is performed under mild conditions (50-100 °C) with 2 mol% of catalyst and 5 mol% of tBuOK under 50 bar of hydrogen. Excellent yields (>90%) were obtained for a large combination of aldehydes and amines (40 examples), including aliphatic aldehydes and amino-alcohols.

Solvothermal synthesis of selenium nano and microspheres deposited on silicon surface by microwave-assisted method

NASA Astrophysics Data System (ADS)

Ahmad, Muthanna

2016-10-01

This work describes a new application of the solvothermal method, based on the microwave heating, for the synthesis of nano and microparticles of selenium. The reaction of selenium with hydrofluoric acid on the silicon surface is induced by microwave irradiation under high pressure and temperature of 60 bar and 160 °C, respectively. This method allows the deposition of spherical-like particles on the in situ etched silicon surface. The size of deposited selenium spheres scales from tens of nanometers up to tens of micrometers. The morphology and composition of the deposited selenium were analyzed by various analytical techniques. The formation dynamic of spherical structure is explained on the base of reduction of selenium species by hydrogen inside gas bubbles which are generated on the silicon surface by the etching process.

Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

NASA Astrophysics Data System (ADS)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

Effect of Staged Dissolved Oxygen Optimization on In-situ sludge Reduction and Enhanced Nutrient Removal in an A2MMBR-M System

NASA Astrophysics Data System (ADS)

Yang, Shan-Shan; Pang, Ji-Wei; Jin, Xiao-Man; Wu, Zhong-Yang; Yang, Xiao-Yin; Guo, Wan-Qian; Zhao, Zhi-Qing; Ren, Nan-Qi

2018-03-01

Redundant excess sludge production and considerable non-standard wastewater discharge from existing activated sludge processes are facing more and more challenges. The investigations on lower sludge production and higher sewage treatment efficiency are urgently needed. In this study, an anaerobic/anoxic/micro-aerobic/oxic-MBR combining a micro-aerobic starvation sludge holding tank (A2MMBR-M) system is developed. Batch tests on the optimization of the staged dissolved oxygen (DO) in the micro-aerobic, the first oxic, and the second oxic tanks were carried out by a 3-factor and 3-level Box-Behnken design (BBD). The optimal actual values of X1 , X2 , and X3 were DO1 of 0.3-0.5 mg/L, DO2 of 3.5-4.5 mg/L, and DO3 of 3-4 mg/L. After the optimization tests, continuous-flow experiments of anaerobic/anoxic/oxic (AAO) and A2MMBR-M systems were further conducted. Compared to AAO system, a 37.45% reduction in discharged excess sludge in A2MMBR-M system was achieved. The COD, TN, and TP removal efficiencies in A2MMBR-M system were respective 4.06%, 2.68%, and 4.04% higher than AAO system. The A2MMBR-M system is proved a promising wastewater treatment technology possessing enhanced in-situ sludge reduction and improved effluent quality. The staged optimized DO concentrations are the key controlling parameters for the realization of simultaneous in-situ sludge reduction and nutrient removal.

Influence of ethnic traditional cultures on genetic diversity of rice landraces under on-farm conservation in southwest China.

PubMed

Wang, Yanjie; Wang, Yanli; Sun, Xiaodong; Caiji, Zhuoma; Yang, Jingbiao; Cui, Di; Cao, Guilan; Ma, Xiaoding; Han, Bing; Xue, Dayuan; Han, Longzhi

2016-10-27

Crop genetic resources are important components of biodiversity. However, with the large-scale promotion of mono-cropping, genetic diversity has largely been lost. Ex-situ conservation approaches were widely used to protect traditional crop varieties worldwide. However, this method fails to maintain the dynamic evolutionary processes of crop genetic resources in their original habitats, leading to genetic diversity reduction and even loss of the capacity of resistance to new diseases and pests. Therefore, on-farm conservation has been considered a crucial complement to ex-situ conservation. This study aimed at clarifying the genetic diversity differences between ex-situ conservation and on-farm conservation and to exploring the influence of traditional cultures on genetic diversity of rice landraces under on-farm conservation. The conservation status of rice landrace varieties, including Indica and Japonica, non-glutinous rice (Oryza sativa) and glutinous rice (Oryza sativa var. glutinosa Matsum), was obtained through ethno-biology investigation method in 12 villages of ethnic groups from Guizhou, Yunnan and Guangxi provinces of China. The genetic diversity between 24 pairs of the same rice landraces from different times were compared using simple sequence repeat (SSR) molecular markers technology. The landrace paris studied were collected in 1980 and maintained ex-situ, while 2014 samples were collected on-farm in southwest of China. The results showed that many varieties of rice landraces have been preserved on-farm by local farmers for hundreds or thousands of years. The number of alleles (Na), effective number of alleles (Ne), Nei genetic diversity index (He) and Shannon information index (I) of rice landraces were significantly higher by 12.3-30.4 % under on-farm conservation than under ex-situ conservation. Compared with the ex-situ conservation approach, rice landraces under on-farm conservation programs had more alleles and higher genetic diversity. In every site we investigated, ethnic traditional cultures play a positive influence on rice landrace variety diversity and genetic diversity. Most China's rice landraces were conserved in the ethnic areas of southwest China. On-farm conservation can effectively promote the allelic variation and increase the genetic diversity of rice landraces over the past 35 years. Moreover, ethnic traditional culture practices are a crucial foundation to increase genetic diversity of rice landraces and implement on-farm conservation.

On the cross-sensitivity between water vapor mixing ratio and stable isotope measurements of in-situ analyzers

NASA Astrophysics Data System (ADS)

Parkes, Stephen; Wang, Lixin; McCabe, Matthew

2015-04-01

In recent years there has been an increasing amount of water vapor stable isotope data collected using in-situ instrumentation. A number of papers have characterized the performance of these in-situ analyzers and suggested methods for calibrating raw measurements. The cross-sensitivity of the isotopic measurements on the mixing ratio has been shown to be a major uncertainty and a variety of techniques have been suggested to characterize this inaccuracy. However, most of these are based on relating isotopic ratios to water vapor mixing ratios from in-situ analyzers when the mixing ratio is varied and the isotopic composition kept constant. An additional correction for the span of the isotopic ratio scale is then applied by measuring different isotopic standards. Here we argue that the water vapor cross-sensitivity arises from different instrument responses (span and offset) of the parent H2O isotope and the heavier isotopes, rather than spectral overlap that could cause a true variation in the isotopic ratio with mixing ratio. This is especially relevant for commercial laser optical instruments where absorption lines are well resolved. Thus, the cross-sensitivity determined using more conventional techniques is dependent on the isotopic ratio of the standard used for the characterization, although errors are expected to be small. Consequently, the cross-sensitivity should be determined by characterizing the span and zero offset of each isotope mixing ratio. In fact, this technique makes the span correction for the isotopic ratio redundant. In this work we model the impact of changes in the span and offset of the heavy and light isotopes and illustrate the impact on the cross-sensitivity of the isotopic ratios on water vapor. This clearly shows the importance of determining the zero offset for the two isotopes. The cross-sensitivity of the isotopic ratios on water vapor is then characterized by determining the instrument response for the individual isotopes for a number of different in-situ analyzers that employ different optical methods. We compare this simplified calibration technique to more conventional characterization of both the cross-sensitivity determined in isotopic ratio space and the isotopic ratio span. Utilizing this simplified calibration approach with improved software control can lead to a significant reduction in time spent calibrating in-situ instrumentation or enable an increase in calibration frequency as required to minimize measurement uncertainty.

In situ expression of nifD in Geobacteraceae in subsurface sediments

USGS Publications Warehouse

Holmes, Dawn E.; Nevin, Kelly P.; Lovely, Derek R.

2004-01-01

In order to determine whether the metabolic state of Geobacteraceae involved in bioremediation of subsurface sediments might be inferred from levels of mRNA for key genes, in situ expression of nifD, a highly conserved gene involved in nitrogen fixation, was investigated. When Geobacter sulfurreducens was grown without a source of fixed nitrogen in chemostats with acetate provided as the limiting electron donor and Fe(III) as the electron acceptor, levels of nifD transcripts were 4 to 5 orders of magnitude higher than in chemostat cultures provided with ammonium. In contrast, the number of transcripts of recA and the 16S rRNA gene were slightly lower in the absence of ammonium. The addition of acetate to organic- and nitrogen-poor subsurface sediments stimulated the growth of Geobacteraceae and Fe(III) reduction, as well as the expression of nifD in Geobacteraceae. Levels of nifD transcripts in Geobacteraceae decreased more than 100-fold within 2 days after the addition of 100 μM ammonium, while levels of recA and total bacterial 16S rRNA in Geobacteraceae remained relatively constant. Ammonium amendments had no effect on rates of Fe(III) reduction in acetate-amended sediments or toluene degradation in petroleum-contaminated sediments, suggesting that other factors, such as the rate that Geobacteraceae could access Fe(III) oxides, limited Fe(III) reduction. These results demonstrate that it is possible to monitor one aspect of the in situ metabolic state of Geobacteraceae species in subsurface sediments via analysis of mRNA levels, which is the first step toward a more global analysis of in situ gene expression related to nutrient status and stress response during bioremediation by Geobacteraceae.

Is the timing of surgery associated with avascular necrosis after unstable slipped capital femoral epiphysis? A multicenter study.

PubMed

Kohno, Yusuke; Nakashima, Yasuharu; Kitano, Toshio; Irie, Taichi; Kita, Atsushi; Nakamura, Tomoyuki; Endo, Hirosuke; Fujii, Yosuke; Kuroda, Takayuki; Mitani, Shigeru; Kitoh, Hiroshi; Matsushita, Masaki; Hattori, Tadashi; Iwata, Koji; Iwamoto, Yukihide

2017-01-01

An unstable slipped capital femoral epiphysis (SCFE) is associated with a high rate of avascular necrosis (AVN). The etiology of AVN seems to be multifactorial, although it is not thoroughly known. The aims of our study were to determine the rate of AVN after an unstable SCFE and to investigate the risk factors for AVN, specifically evaluating the notion of an "unsafe window", during which medical interventions would increase the risk for AVN. This retrospective multicenter study included 60 patients with an unstable SCFE diagnosed between 1985 and 2014. Timing of surgery was evaluated for three time periods, from acute onset of symptoms to surgery: period I, <24 h; period II, between 24 h and 7 days; and period III, >7 days. Multivariate logistic regression analysis was used to identify risk factors for AVN. Closed reduction and pinning was performed in 43 patients and in situ pinning in 17. Among these cases, 16 patients (27%) developed AVN. The rate of AVN was significantly higher in patients treated by closed reduction and pinning (15/43, 35%) than in those treated by in situ pinning (1/17, 5.9%) (p = 0.022). In patients treated by closed reduction and pinning, the incidence of AVN was 2/11 (18%) in period I, 10/13 (77%) in period II and 3/15 (20%) in period III, showing the significantly higher rate in period II (p = 0.002). The surgery provided in period II was identified as an independent risk factor for the development of AVN. Our rate of AVN was 27% using two classical treatment methods. Time-to-surgery, between 24 h and 7 days, was independently associated with AVN, supporting the possible existence of an "unsafe window" in patients with unstable SCFE treated by closed reduction and pinning. Copyright © 2016 The Japanese Orthopaedic Association. Published by Elsevier B.V. All rights reserved.

Effects of damping-off caused by Rhizoctonia solani anastomosis group 2-1 on roots of wheat and oil seed rape quantified using X-ray Computed Tomography and real-time PCR

PubMed Central

Sturrock, Craig J.; Woodhall, James; Brown, Matthew; Walker, Catherine; Mooney, Sacha J.; Ray, Rumiana V.

2015-01-01

Rhizoctonia solani is a plant pathogenic fungus that causes significant establishment and yield losses to several important food crops globally. This is the first application of high resolution X-ray micro Computed Tomography (X-ray μCT) and real-time PCR to study host–pathogen interactions in situ and elucidate the mechanism of Rhizoctonia damping-off disease over a 6-day period caused by R. solani, anastomosis group (AG) 2-1 in wheat (Triticum aestivum cv. Gallant) and oil seed rape (OSR, Brassica napus cv. Marinka). Temporal, non-destructive analysis of root system architectures was performed using RooTrak and validated by the destructive method of root washing. Disease was assessed visually and related to pathogen DNA quantification in soil using real-time PCR. R. solani AG2-1 at similar initial DNA concentrations in soil was capable of causing significant damage to the developing root systems of both wheat and OSR. Disease caused reductions in primary root number, root volume, root surface area, and convex hull which were affected less in the monocotyledonous host. Wheat was more tolerant to the pathogen, exhibited fewer symptoms and developed more complex root systems. In contrast, R. solani caused earlier damage and maceration of the taproot of the dicot, OSR. Disease severity was related to pathogen DNA accumulation in soil only for OSR, however, reductions in root traits were significantly associated with both disease and pathogen DNA. The method offers the first steps in advancing current understanding of soil-borne pathogen behavior in situ at the pore scale, which may lead to the development of mitigation measures to combat disease influence in the field. PMID:26157449

Effects of damping-off caused by Rhizoctonia solani anastomosis group 2-1 on roots of wheat and oil seed rape quantified using X-ray Computed Tomography and real-time PCR.

PubMed

Sturrock, Craig J; Woodhall, James; Brown, Matthew; Walker, Catherine; Mooney, Sacha J; Ray, Rumiana V

2015-01-01

Rhizoctonia solani is a plant pathogenic fungus that causes significant establishment and yield losses to several important food crops globally. This is the first application of high resolution X-ray micro Computed Tomography (X-ray μCT) and real-time PCR to study host-pathogen interactions in situ and elucidate the mechanism of Rhizoctonia damping-off disease over a 6-day period caused by R. solani, anastomosis group (AG) 2-1 in wheat (Triticum aestivum cv. Gallant) and oil seed rape (OSR, Brassica napus cv. Marinka). Temporal, non-destructive analysis of root system architectures was performed using RooTrak and validated by the destructive method of root washing. Disease was assessed visually and related to pathogen DNA quantification in soil using real-time PCR. R. solani AG2-1 at similar initial DNA concentrations in soil was capable of causing significant damage to the developing root systems of both wheat and OSR. Disease caused reductions in primary root number, root volume, root surface area, and convex hull which were affected less in the monocotyledonous host. Wheat was more tolerant to the pathogen, exhibited fewer symptoms and developed more complex root systems. In contrast, R. solani caused earlier damage and maceration of the taproot of the dicot, OSR. Disease severity was related to pathogen DNA accumulation in soil only for OSR, however, reductions in root traits were significantly associated with both disease and pathogen DNA. The method offers the first steps in advancing current understanding of soil-borne pathogen behavior in situ at the pore scale, which may lead to the development of mitigation measures to combat disease influence in the field.

In Situ NAPL Modification for Contaminant Source-Zone Passivation, Mass Flux Reduction, and Remediation

NASA Astrophysics Data System (ADS)

Mateas, D. J.; Tick, G.; Carroll, K. C.

2016-12-01

A remediation method was developed to reduce the aqueous solubility and mass-flux of target NAPL contaminants through the in-situ creation of a NAPL mixture source-zone. This method was tested in the laboratory using equilibrium batch tests and two-dimensional flow-cell experiments. The creation of two different NAPL mixture source zones were tested in which 1) volumes of relatively insoluble n-hexadecane (HEX) or vegetable oil (VO) were injected into a trichloroethene (TCE) contaminant source-zone; and 2) pre-determined HEX-TCE and VO-TCE mixture ratio source zones were emplaced into the flow cell prior to water flushing. NAPL-aqueous phase batch tests were conducted prior to the flow-cell experiments to evaluate the effects of various NAPL mixture ratios on equilibrium aqueous-phase concentrations of TCE and toluene (TOL) and to design optimal NAPL (HEX or VO) injection volumes for the flow-cell experiments. Uniform NAPL mixture source-zones were able to quickly decrease contaminant mass-flux, as demonstrated by the emplaced source-zone experiments. The success of the HEX and VO injections to also decrease mass flux was dependent on the ability of these injectants to homogeneously mix with TCE source-zone. Upon injection, both HEX and VO migrated away from the source-zone, to some extent. However, the lack of a steady-state dissolution phase and the inefficient mass-flux-reduction/mass-removal behavior produced after VO injection suggest that VO was more effective than HEX for mixing and partitioning within the source-zone region to form a more homogeneous NAPL mixture with TCE. VO appears to be a promising source-zone injectant-NAPL due to its negligible long-term toxicity and lower mobilization potential.

Calcium hydroxide coating on highly reactive nanoscale zero-valent iron for in situ remediation application.

PubMed

Wei, Cai-Jie; Xie, Yue-Feng; Wang, Xiao-Mao; Li, Xiao-Yan

2018-05-23

Nano scale zero-valent iron (nZVI), a promising engineering technology for in situ remediation, has been greatly limited by quick self-corrosion and low mobility in porous media. Highly reactive nZVI particles produced from the borohydride reduction method were enclosed in a releasable Ca(OH) 2 layer by the chemical deposition method. The amount of Ca(OH) 2 coated on nZVI surface were well controlled by the precursor dosage. At moderate Ca(OH) 2 dosage (R Ca/TFe  = 0.25) condition, the increment of Fe 0 content for the obtained nZVI/Ca-0.25 sample was observed. The interfacial reactions between the iron oxide shell and the Ca(OH) 2 saturated environment were delicately elucidated by the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) spectrum. And the coverage of Ca(OH) 2 shell on spherical nZVI surface was found more complete and uniform for the nZVI/Ca sample obtained from the moderate precursor dosage condition (R Ca/TFe  = 0.25). The Ca(OH) 2 shell before dissolution was demonstrated owning the anti-corrosion capability to slow down the oxidation of Fe 0 core in air, during ethanol storage and in aqueous environment. The mechanism of anti-corrosion capability for nZVI/Ca-0.25 particle was interestingly found to be attributed to the Ca(OH) 2 shell isolation and also be potentially due to the iron oxide shell phase transformation mediated by the outer Ca(OH) 2 shell. An improved trichloroethylene reduction performance was observed for nZVI/Ca-0.25 than bare nZVI. The mobility of nZVI/Ca particles in water-saturated porous media was moderately improved before shell dissolution. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal-Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems.

PubMed

Tylus, Urszula; Jia, Qingying; Strickland, Kara; Ramaswamy, Nagappan; Serov, Alexey; Atanassov, Plamen; Mukerjee, Sanjeev

2014-05-01

Detailed understanding of the nature of the active centers in non-precious-metal-based electrocatalyst, and their role in oxygen reduction reaction (ORR) mechanistic pathways will have a profound effect on successful commercialization of emission-free energy devices such as fuel cells. Recently, using pyrolyzed model structures of iron porphyrins, we have demonstrated that a covalent integration of the Fe-N x sites into π-conjugated carbon basal plane modifies electron donating/withdrawing capability of the carbonaceous ligand, consequently improving ORR activity. Here, we employ a combination of in situ X-ray spectroscopy and electrochemical methods to identify the various structural and functional forms of the active centers in non-heme Fe/N/C catalysts. Both methods corroboratively confirm the single site 2e - × 2e - mechanism in alkaline media on the primary Fe 2+ -N 4 centers and the dual-site 2e - × 2e - mechanism in acid media with the significant role of the surface bound coexisting Fe/Fe x O y nanoparticles (NPs) as the secondary active sites.

Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal–Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems

PubMed Central

2015-01-01

Detailed understanding of the nature of the active centers in non-precious-metal-based electrocatalyst, and their role in oxygen reduction reaction (ORR) mechanistic pathways will have a profound effect on successful commercialization of emission-free energy devices such as fuel cells. Recently, using pyrolyzed model structures of iron porphyrins, we have demonstrated that a covalent integration of the Fe–Nx sites into π-conjugated carbon basal plane modifies electron donating/withdrawing capability of the carbonaceous ligand, consequently improving ORR activity. Here, we employ a combination of in situ X-ray spectroscopy and electrochemical methods to identify the various structural and functional forms of the active centers in non-heme Fe/N/C catalysts. Both methods corroboratively confirm the single site 2e– × 2e– mechanism in alkaline media on the primary Fe2+–N4 centers and the dual-site 2e– × 2e– mechanism in acid media with the significant role of the surface bound coexisting Fe/FexOy nanoparticles (NPs) as the secondary active sites. PMID:24817921

Réduction in situ des ions nitrate dans des eaux par les bactéries indigènes

NASA Astrophysics Data System (ADS)

Abdelouas, Abdesselam; Deng, Lijun; Nuttall, Eric; Lutze, Werner; Fritz, Bertrand; Crovisier, Jean-Louis

1999-02-01

We studied the possibility of cleaning groundwater contaminated with nitrate ions using indigenous bacteria. The groundwater occurs in a site located near a former vegetable farm near Albuquerque, New Mexico (USA) and contains up to 500 mg·L -1 of nitrate ion. Batch and column experiments using groundwater and local sediment showed that indigenous bacteria catalyzed the nitrate ions reduction. Sodium acetate was selected as the best carbon source for the in situ application. As expected, the best conditions for denitrification were encountered in situ. Nitrate ions and their byproducts were reduced to nitrogen gas within 5 days.

A novel molten-salt electrochemical cell for investigating the reduction of uranium dioxide to uranium metal by lithium using in situ synchrotron radiation

PubMed Central

Brown, Leon D.; Abdulaziz, Rema; Jervis, Rhodri; Bharath, Vidal; Mason, Thomas J.; Reinhard, Christina; Connor, Leigh D.; Inman, Douglas; Brett, Daniel J. L.; Shearing, Paul R.

2017-01-01

A novel electrochemical cell has been designed and built to allow for in situ energy-dispersive X-ray diffraction measurements to be made during reduction of UO2 to U metal in LiCl–KCl at 500°C. The electrochemical cell contains a recessed well at the bottom of the cell into which the working electrode sits, reducing the beam path for the X-rays through the molten-salt and maximizing the signal-to-noise ratio from the sample. Lithium metal was electrodeposited onto the UO2 working electrode by exposing the working electrode to more negative potentials than the Li deposition potential of the LiCl–KCl eutectic electrolyte. The Li metal acts as a reducing agent for the chemical reduction of UO2 to U, which appears to proceed to completion. All phases were fitted using Le Bail refinement. The cell is expected to be widely applicable to many studies involving molten-salt systems. PMID:28244437

A novel molten-salt electrochemical cell for investigating the reduction of uranium dioxide to uranium metal by lithium using in situ synchrotron radiation.

PubMed

Brown, Leon D; Abdulaziz, Rema; Jervis, Rhodri; Bharath, Vidal; Mason, Thomas J; Atwood, Robert C; Reinhard, Christina; Connor, Leigh D; Inman, Douglas; Brett, Daniel J L; Shearing, Paul R

2017-03-01

A novel electrochemical cell has been designed and built to allow for in situ energy-dispersive X-ray diffraction measurements to be made during reduction of UO 2 to U metal in LiCl-KCl at 500°C. The electrochemical cell contains a recessed well at the bottom of the cell into which the working electrode sits, reducing the beam path for the X-rays through the molten-salt and maximizing the signal-to-noise ratio from the sample. Lithium metal was electrodeposited onto the UO 2 working electrode by exposing the working electrode to more negative potentials than the Li deposition potential of the LiCl-KCl eutectic electrolyte. The Li metal acts as a reducing agent for the chemical reduction of UO 2 to U, which appears to proceed to completion. All phases were fitted using Le Bail refinement. The cell is expected to be widely applicable to many studies involving molten-salt systems.

Nitrogen Dioxide Trend over the United States: the View from the Ground, the View from Space

NASA Technical Reports Server (NTRS)

Lamsal, Lok N.; Duncan, Bryan N.; Yoshida, Yasuko; Krotkov, Nickolay A.

2014-01-01

Emissions of nitrogen oxides (NOx) are decreasing over the US due to environmental policies and technological change. We use observations of tropospheric nitrogen dioxide (NO2) columns from the Ozone Monitoring Instrument (OMI) satellite instrument and surface NO2 in-situ measurements from the air quality system (AQS) to quantify the trends, and to establish the relationship between the trends in tropospheric column and surface concentration. Both observations show substantial downward trends from 2005 to 2013, with an average reduction of 35 percent according to OMI and 38 percent according to AQS. The annual reduction rates are largest in 2005-2009: -6.2 percent per year and -7 percent per year observed by OMI and AQS, respectively. We examine various factors affecting the estimated trend in OMI NO2 columns and in-situ NO2 observations. An improved understanding of trend offers valuable insights about effectiveness of emission reduction regulations on state and federal level.

Reductive de-polymerization of kraft lignin for chemicals and fuels using formic acid as an in-situ hydrogen source.

PubMed

Huang, Shanhua; Mahmood, Nubla; Tymchyshyn, Matthew; Yuan, Zhongshun; Xu, Chunbao Charles

2014-11-01

In this study, formic acid (FA) was employed as an in-situ hydrogen donor for the reductive de-polymerization of kraft lignin (KL). Under the optimum operating conditions, i.e., 300 °C, 1 h, 18.6 wt.% substrate concentration, 50/50 (v/v) water-ethanol medium with FA at a FA-to-lignin mass ratio of 0.7, KL (Mw∼10,000 g/mol) was effectively de-polymerized, producing de-polymerized lignin (DL, Mw 1270 g/mol) at a yield of ∼90 wt.% and <1 wt.% yield of solid residue (SR). The MW of the DL products decreased with increasing reaction temperature, time and FA-to-lignin mass ratio. The sulfur contents of all DL products were remarkably lower than that in the original KL. It was also demonstrated that FA is a more reactive hydrogen source than external hydrogen for reductive de-polymerization of KL. Copyright © 2014 Elsevier Ltd. All rights reserved.

In-situ grown nanoporous Zn-Cu catalysts on brass foils for enhanced electrochemical reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Hu, Hanjun; Tang, Yang; Hu, Qing; Wan, Pingyu; Dai, Liming; Yang, Xiao Jin

2018-07-01

In-situ grown nanoporous Zn-Cu catalysts were prepared by simply annealing a commercial brass foil at 500 °C in air, followed by electrochemical reduction. During the annealing process, Zn preferentially melted and migrated out of the framework of the alloy to form a thin layer of ZnO on its surface. Subsequent electroreduction created nanoporous Zn-enriched surface. The Zn concentration increased from 36% to 50% by 10 min, to 81% by 3 h, and to 87% by 12 h annealing treatment while the average pore size decreased from 290 nm to 120 nm as the annealing time increased from 1 h to 12 h. Faradaic efficiency of CO2 reduction to CO and HCOOH was enhanced by nearly 4 and 6 times, respectively, as compared to untreated brass foils. The nanoporous Zn-Cu catalyst presented a stable ratio of CO/H2 and a steady working current density in a continuous electrolysis of 18 h in 0.5 M KHCO3 solution.

Plasma Jet Printing and in Situ Reduction of Highly Acidic Graphene Oxide.

PubMed

Dey, Avishek; Krishnamurthy, Satheesh; Bowen, James; Nordlund, Dennis; Meyyappan, M; Gandhiraman, Ram P

2018-05-23

Miniaturization of electronic devices and the advancement of Internet of Things pose exciting challenges to develop technologies for patterned deposition of functional nanomaterials. Printed and flexible electronic devices and energy storage devices can be embedded onto clothing or other flexible surfaces. Graphene oxide (GO) has gained much attention in printed electronics due its solution processability, robustness, and high electrical conductivity in the reduced state. Here, we introduce an approach to print GO films from highly acidic suspensions with in situ reduction using an atmospheric pressure plasma jet. Low-temperature plasma of a He and H 2 mixture was used successfully to reduce a highly acidic GO suspension (pH < 2) in situ during deposition. This technique overcomes the multiple intermediate steps required to increase the conductivity of deposited GO. X-ray spectroscopic studies confirmed that the reaction intermediates and the concentration of oxygen functionalities bonded to GO have been reduced significantly by this approach without any additional steps. Moreover, the reduced GO films showed enhanced conductivity. Hence, this technique has a strong potential for printing conducting patterns of GO for a range of large-scale applications.

Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts.

PubMed

Makio, Haruyuki; Prasad, Aitha Vishwa; Terao, Hiroshi; Saito, Junji; Fujita, Terunori

2013-07-07

Bis(phenoxy-imine) Zr and Hf complexes were activated with (i)Bu3Al or (i)Bu2AlH in conjunction with Ph3CB(C6F5)4 and tested as catalysts for propylene polymerization with emphasis on the enantioselectivity of the isospecific species and the single site polymerization characteristics. The isoselective species was identified as the in situ generated bis(phenoxy-amine) complex whose isoselectivity was sensitive to subtle changes in ligand structure. By employing specific substituents at certain key positions the isotacticity reached an extremely high level comparable to high-end commercial isotactic polypropylenes (Tm > 160 °C). Single site polymerization characteristics depended upon the efficiency and selectivity of the in situ imine reduction which is sensitive to the substituent on the imine nitrogen and the reaction conditions. By using (i)Bu2AlH as a reducing agent, quantitative imine reduction can be achieved with a stoichiometric amount of the reducing agent. This lower alkylaluminum loading is beneficial for the catalyst and significantly enhances the polymerization activity and the molecular weight of the resultant polymer.

Molten salt applications in materials processing

NASA Astrophysics Data System (ADS)

Mishra, Brajendra; Olson, David L.

2005-02-01

The science of molten salt electrochemistry for electrowinning of reactive metals, such as calcium, and its in situ application in pyro-reduction has been described. Calcium electrowinning has been performed in a 5 10 wt% calcium oxide calcium chloride molten salt by the electrolytic dissociation of calcium oxide. This electrolysis requires the use of a porous ceramic sheath around the anode to keep the cathodically deposited calcium and the anodic gases separate. Stainless steel cathode and graphite anode have been used in the temperature range of 850 950 °C. This salt mixture is produced as a result of the direct oxide reduction (DOR) of reactive metal oxides by calcium in a calcium chloride bath. The primary purpose of this process is to recover the expensive calcium reductant and to recycle calcium chloride. Experimental data have been included to justify the suitability as well as limitations of the electrowinning process. Transport of oxygen ions through the sheath is found to be the rate controlling step. Under the constraints of the reactor design, a calcium recovery rate of approx. 150 g/h was achieved. Feasibility of a process to produce metals by pyrometallurgical reduction, using the calcium reductant produced electrolytically within the same reactor, has been shown in a hybrid process. Several processes are currently under investigation to use this electrowon calcium for in situ reduction of metal oxides.

Dynamics of microbial community composition and function during in-situ bioremediation of a uranium-contaminated aquifer

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

Nostrand, J.D. Van; Wu, L.; Wu, W.M.

2010-08-15

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter{sup -1}). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed thatmore » Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process.« less

Dynamics of Microbial Community Composition and Function during In Situ Bioremediation of a Uranium-Contaminated Aquifer▿‡

PubMed Central

Van Nostrand, Joy D.; Wu, Liyou; Wu, Wei-Min; Huang, Zhijian; Gentry, Terry J.; Deng, Ye; Carley, Jack; Carroll, Sue; He, Zhili; Gu, Baohua; Luo, Jian; Criddle, Craig S.; Watson, David B.; Jardine, Philip M.; Marsh, Terence L.; Tiedje, James M.; Hazen, Terry C.; Zhou, Jizhong

2011-01-01

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter−1). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed that Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process. PMID:21498771

A Rigorous Statistical Approach to Determine Solar Wind Composition from ACE/SWICS Data, and New Ne/O Ratios

NASA Astrophysics Data System (ADS)

Shearer, P.; Jawed, M. K.; Raines, J. M.; Lepri, S. T.; Gilbert, J. A.; von Steiger, R.; Zurbuchen, T.

2013-12-01

The SWICS instruments aboard ACE and Ulysses have performed in situ measurements of individual solar wind ions for a period spanning over two decades. Solar wind composition is determined by accumulating the measurements into an ion count histogram in which each species appears as a distinct peak. Assigning counts to the appropriate species is a challenging statistical problem because of the limited counts for some species and overlap between some peaks. We show that the most commonly used count assignment methods can suffer from significant bias when a highly abundant species overlaps with a much less abundant one. For ACE/SWICS data, this bias results in an overestimated Ne/O ratio. Bias is greatly reduced by switching to a rigorous maximum likelihood count assignment method, resulting in a 30-50% reduction in the estimated Ne abundance. We will discuss the new Ne/O values and put them in context with the solar system abundances for Ne derived from other techniques, such as in situ collection from Genesis and its heritage instrument, the Solar Foil experiment during the Apollo era. The new count assignment method is currently being applied to reanalyze the archived ACE and Ulysses data and obtain revised abundances of C, N, O, Ne, Mg, Si, S, and Fe, leading to revised datasets that will be made publicly available.

2D Transition-Metal-Dichalcogenide-Nanosheet-Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions.

PubMed

Lu, Qipeng; Yu, Yifu; Ma, Qinglang; Chen, Bo; Zhang, Hua

2016-03-09

Hydrogen (H2) is one of the most important clean and renewable energy sources for future energy sustainability. Nowadays, photocatalytic and electrocatalytic hydrogen evolution reactions (HERs) from water splitting are considered as two of the most efficient methods to convert sustainable energy to the clean energy carrier, H2. Catalysts based on transition metal dichalcogenides (TMDs) are recognized as greatly promising substitutes for noble-metal-based catalysts for HER. The photocatalytic and electrocatalytic activities of TMD nanosheets for the HER can be further improved after hybridization with many kinds of nanomaterials, such as metals, oxides, sulfides, and carbon materials, through different methods including the in situ reduction method, the hot-injection method, the heating-up method, the hydro(solvo)thermal method, chemical vapor deposition (CVD), and thermal annealing. Here, recent progress in photocatalytic and electrocatalytic HERs using 2D TMD-based composites as catalysts is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combining in situ characterization methods in one set-up: looking with more eyes into the intricate chemistry of the synthesis and working of heterogeneous catalysts.

PubMed

Bentrup, Ursula

2010-12-01

Several in situ techniques are known which allow investigations of catalysts and catalytic reactions under real reaction conditions using different spectroscopic and X-ray methods. In recent years, specific set-ups have been established which combine two or more in situ methods in order to get a more detailed understanding of catalytic systems. This tutorial review will give a summary of currently available set-ups equipped with multiple techniques for in situ catalyst characterization, catalyst preparation, and reaction monitoring. Besides experimental and technical aspects of method coupling including X-ray techniques, spectroscopic methods (Raman, UV-vis, FTIR), and magnetic resonance spectroscopies (NMR, EPR), essential results will be presented to demonstrate the added value of multitechnique in situ approaches. A special section is focussed on selected examples of use which show new developments and application fields.

Reduction Expansion Synthesis as Strategy to Control Nitrogen Doping Level and Surface Area in Graphene

PubMed Central

Canty, Russell; Gonzalez, Edwin; MacDonald, Caleb; Osswald, Sebastian; Zea, Hugo; Luhrs, Claudia C.

2015-01-01

Graphene sheets doped with nitrogen were produced by the reduction-expansion (RES) method utilizing graphite oxide (GO) and urea as precursor materials. The simultaneous graphene generation and nitrogen insertion reactions are based on the fact that urea decomposes upon heating to release reducing gases. The volatile byproducts perform two primary functions: (i) promoting the reduction of the GO and (ii) providing the nitrogen to be inserted in situ as the graphene structure is created. Samples with diverse urea/GO mass ratios were treated at 800 °C in inert atmosphere to generate graphene with diverse microstructural characteristics and levels of nitrogen doping. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to study the microstructural features of the products. The effects of doping on the samples structure and surface area were studied by X-ray diffraction (XRD), Raman Spectroscopy, and Brunauer Emmet Teller (BET). The GO and urea decomposition-reduction process as well as nitrogen-doped graphene stability were studied by thermogravimetric analysis (TGA) coupled with mass spectroscopy (MS) analysis of the evolved gases. Results show that the proposed method offers a high level of control over the amount of nitrogen inserted in the graphene and may be used alternatively to control its surface area. To demonstrate the practical relevance of these findings, as-produced samples were used as electrodes in supercapacitor and battery devices and compared with conventional, thermally exfoliated graphene. PMID:28793618

Methodology for dynamic biaxial tension testing of pregnant uterine tissue.

PubMed

Manoogian, Sarah; Mcnally, Craig; Calloway, Britt; Duma, Stefan

2007-01-01

Placental abruption accounts for 50% to 70% of fetal losses in motor vehicle crashes. Since automobile crashes are the leading cause of traumatic fetal injury mortality in the United States, research of this injury mechanism is important. Before research can adequately evaluate current and future restraint designs, a detailed model of the pregnant uterine tissues is necessary. The purpose of this study is to develop a methodology for testing the pregnant uterus in biaxial tension at a rate normally seen in a motor vehicle crash. Since the majority of previous biaxial work has established methods for quasi-static testing, this paper combines previous research and new methods to develop a custom designed system to strain the tissue at a dynamic rate. Load cells and optical markers are used for calculating stress strain curves of the perpendicular loading axes. Results for this methodology show images of a tissue specimen loaded and a finite verification of the optical strain measurement. The biaxial test system dynamically pulls the tissue to failure with synchronous motion of four tissue grips that are rigidly coupled to the tissue specimen. The test device models in situ loading conditions of the pregnant uterus and overcomes previous limitations of biaxial testing. A non-contact method of measuring strains combined with data reduction to resolve the stresses in two directions provides the information necessary to develop a three dimensional constitutive model of the material. Moreover, future research can apply this method to other soft tissues with similar in situ loading conditions.

Limits to the use of highly compacted bentonite as a deterrent for microbiologically influenced corrosion in a nuclear fuel waste repository

NASA Astrophysics Data System (ADS)

Stroes-Gascoyne, Simcha; Hamon, Connie J.; Maak, Peter

Recent studies have suggested that microbial activity in highly compacted bentonite (⩾1600 kg/m 3) is severely suppressed. Therefore, it appears that the dry density of emplaced bentonite barriers in a geological repository for nuclear waste may be tailored such that a microbiologically unfavorable environment can be created adjacent to used fuel containers. This would ensure that microbiologically influenced corrosion is a negligible contributor to the overall corrosion process. However, this premise is valid only as long as the emplaced bentonite maintains a uniform high dry density (⩾1600 kg/m 3) because it has been shown that high dry density only suppresses microbial activity but not necessarily eliminates the viable microbial population in bentonite. In a repository, a reduction in the dry density of highly compacted bentonite may occur at a number of interface locations, such as placement gaps, contact regions with materials of different densities and contact points with water-carrying fractures in the rock. Experiments were carried out in our laboratory to examine the effects of a reduction in dry density (from 1600 kg/m 3 to about 1000 kg/m 3) on the recovery of microbial culturability in compacted bentonite. Results showed that upon expansion of compacted bentonite into a void, the resulting reduction in dry density stimulated or restored culturability of indigenous microbes. In a repository this would increase the possibility of in situ activity, which might be detrimental for the longevity of waste containers. Reductions in dry density, therefore, should be minimized or eliminated by adequate design and placement methods of compacted bentonite. Materials compliance models can be used to determine the required as-placed dry densities of bentonite buffer and gap fillings to achieve specific targets for long-term equilibrium dry densities for various container placement room designs. Locations where flowing fractures could be in contact with highly compacted bentonite should either be avoided or grouted adequately to limit contact between bentonite and flowing water. Even if localized enhanced microbial activity at interfaces remains of concern, despite adequate engineering and placement methods, the potential consequences can be assessed and quantified adequately by a combination of in situ activity measurements and modeling calculations.

Electrochemical and spectroscopic evidence on the one-electron reduction of U(VI) to U(V) on magnetite

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

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(IV) on mineral surfaces has been considered as a one-step two electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one electron reduction to U(V) without further progression to U(IV). We investigated the mechanisms of uranium reduction by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4 . The one electron reduction of U(VI) was first confirmed using the cyclic voltammetry method. Formation of nano-size uranium precipitates on the surface of magnetite at reducing potentials and dissolution of the solids at oxidizing potentials were observedmore » by in situ electrochemical AFM. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from 0.1 ~ 0.9 V (vs. Ag/AgCl) showed the presence of only U(V) and U(VI). The highest amount of U(V) relative to U(VI) was prepared at 0.7 V, where the longest average U–Oaxial distance of 2.05 ± 0.01 Å was evident in the same sample revealed by EXAFS analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of 0.9 V, which favors the one-electron reduction mechanism. U(V) did not disproportionate but stabilized on magnetite through precipitation of mixed-valence state U(VI)/U(V) solids.« less

A view of aqueous electrochemical carbon dioxide reduction to formate at indium electrodes, and the reversible electrodeposition of silver in ionic liquids through the lens of fundamental surface science

NASA Astrophysics Data System (ADS)

Detweiler, Zachary M.

Two systems were studied using in situ measurement techniques, demonstrating the importance of creative experimental design. The electroreduction of CO2 at heterogeneous indium electrodes in aqueous solution was analyzed by cyclic voltammetry. Bulk electrolyses showed that increased indium oxide presence prior to electrolysis improved the Faradaic efficiency of CO 2 reduction to formate in 0.5 M K2SO2 aqueous solutions at a pH of 4.4. In order to more accurately assign speciation at the electrode surface ex situ O2 and H2O dosing of metallic indium under UHV was studied with XPS, HREELS and TPD. Ambient pressure XPS showed that the ratio of oxide to hydroxide at the indium interface is strongly dependent on the partial pressure of water; decreasing as P(H2O) increases. Using this information, a qualitative picture of the indium interface could be generated. In situ ATR-FTIR with an indium thin film as the working electrode showed that bulk oxide quickly reduces with applied potential, but an interfacial oxide is still present at high reductive overpotential. Additionally, an adsorbed carbonate at the thin film interface was observed upon introducing CO 2 to the cell. The implication of a surface bound carbonate as the CO 2 reduction intermediate draws on a mechanism that has not previously been discussed in the electrochemical reduction of CO2. The previous study of this mechanism from Ficscher-Tropsch literature helps to predict the further reduced products found at more electropositive metals, such as copper or magnesium, the latter of which is described here. Additionaly described here is a series of ILs that were employed as electrolyte for reversible silver deposition. BMIM N(TfO)2 was found to be the most promising of those studied, intrinsically giving a more uniform deposit that was bright and reversible. Deposit formation was studied using SEM and EDX as a function of deposition potential and deposition time. In situ reflectometry was employed to get a direct measure of deposit reflectivity on ITO coated glass as a function of time. A promising device system has been elucidated as a result and future considerations have been identified from coincident electrochemical and spectroscopic measurements.

Fabrication of Bendable Circuits on a Polydimethylsiloxane (PDMS) Surface by Inkjet Printing Semi-Wrapped Structures

PubMed Central

Sun, Jiazhen; Jiang, Jieke; Bao, Bin; Wang, Si; He, Min; Zhang, Xingye; Song, Yanlin

2016-01-01

In this work, an effective method was developed to fabricate bendable circuits on a polydimethylsiloxane (PDMS) surface by inkjet printing semi-wrapped structures. It is demonstrated that the precured PDMS liquid film could influence the depositing morphology of coalesced silver precursor inkjet droplets. Accordingly, continuous and uniform lines with a semi-wrapped structure were fabricated on the PDMS surface. When the printed silver precursor was reduced to Ag nanoparticles, the fabricated conductive film exhibited good transparency and high bendability. This work presented a facile way to fabricate flexible patterns on a PDMS surface without any complicated modification or special equipment. Meanwhile, an in situ hydrazine reduction of Ag has been reported using the vapor phase method in the fabricating process. PMID:28773374

Si-H induced synthesis of Si/Cu2O nanowire arrays for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Zhang, Shaoyang; She, Guangwei; Li, Shengyang; Mu, Lixuan; Shi, Wensheng

2018-01-01

We report a facile and low-cost method to synthesize Si/Cu2O heterojunction nanowire arrays, without SiOx, at the Si/Cu2O interface. The reductive Si-H bonds on the surface of Si nanowires plays a key role in situ by reducing Cu(II) ions to Cu2O nanocubes and avoiding the SiOx interface layer. Different pH values would vary the electrochemical potential of reactions and as a result, different products would be formed. Utilized as a photoanode for water splitting, Si/Cu2O nanowire arrays exhibit good photoelectrochemical performance.

A portable battery-powered flow injection monitor for the in situ analysis of nitrate in natural waters

PubMed Central

Blundell, N. J.; Hopkins, A.; Worsfold, P. J.; Casey, H.

1993-01-01

The design and performance of a portable, automated flow injection (FI)-based photometric monitor are described. The system is controlled by an in-house microcomputer system that enables the monitor (including a solid state detector) to operate from a 12 V battery supply. The monitor uses the cadmium reduction/diazotization method to analyse for nitrate with a linear range of 0 to 12 mg l-1 and a limit of detection of 0.05 mg l-1 (NO3-N). The hardware and software design, monitor performance and results obtained during unattended operation are presented. PMID:18924971

Accumulation of dechlorination daughter products: A valid metric of chloroethene biodegradation

USGS Publications Warehouse

Bradley, Paul M.; Chapelle, Frank H.

2007-01-01

In situ reductive dechlorination of perchloroethene (PCE) and trichloroethene (TCE) generates characteristic chlorinated (cis-dichloroethene [cis-DCE] and vinyl chloride [VC]) and nonchlorinated (ethene and ethane) products. The accumulation of these daughter products is commonly used as a metric for ongoing biodegradation at field sites. However, this interpretation assumes that reductive dechlorination is the only chloroethene degradation process of any significance in situ and that the characteristic daughter products of chloroethene reductive dechlorination persist in the environment. Laboratory microcosms, prepared with aquifer and surface-water sediments from hydrologically diverse sites throughout the United States and amended with [1,2-14C] TCE, [1,2-14C] DCE, [1,2-14C] DCA, or [1,2-14C] VC, demonstrated widely variable patterns of intermediate and final product accumulation. In predominantly methanogenic sediment treatments, accumulation of 14C-DCE, 14C-VC, 14C-ethene, and 14C-ethane predominated. Treatments characterized by significant Fe(III) and/or Mn(IV) reduction, on the other hand, demonstrated substantial, and in some cases exclusive, accumulation of 14CO2and 14CH4. These results suggest that relying on the accumulation of cis-DCE, VC, ethene, and ethane may substantially underestimate overall chloroethene biodegradation at many sites.

Investigation of polymer electrolyte membrane chemical degradation and degradation mitigation using in situ fluorescence spectroscopy

PubMed Central

Prabhakaran, Venkateshkumar; Arges, Christopher G.; Ramani, Vijay

2012-01-01

A fluorescent molecular probe, 6-carboxy fluorescein, was used in conjunction with in situ fluorescence spectroscopy to facilitate real-time monitoring of degradation inducing reactive oxygen species within the polymer electrolyte membrane (PEM) of an operating PEM fuel cell. The key requirements of suitable molecular probes for in situ monitoring of ROS are presented. The utility of using free radical scavengers such as CeO2 nanoparticles to mitigate reactive oxygen species induced PEM degradation was demonstrated. The addition of CeO2 to uncatalyzed membranes resulted in close to 100% capture of ROS generated in situ within the PEM for a period of about 7 h and the incorporation of CeO2 into the catalyzed membrane provided an eightfold reduction in ROS generation rate. PMID:22219367

Volumetric muscle loss injury repair using in situ fibrin gel cast seeded with muscle-derived stem cells (MDSCs).

PubMed

Matthias, Nadine; Hunt, Samuel D; Wu, Jianbo; Lo, Jonathan; Smith Callahan, Laura A; Li, Yong; Huard, Johnny; Darabi, Radbod

2018-03-01

Volumetric muscle defect, caused by trauma or combat injuries, is a major health concern leading to severe morbidity. It is characterized by partial or full thickness loss of muscle and its bio-scaffold, resulting in extensive fibrosis and scar formation. Therefore, the ideal therapeutic option is to use stem cells combined with bio-scaffolds to restore muscle. For this purpose, muscle-derived stem cells (MDSCs) are a great candidate due to their unique multi-lineage differentiation potential. In this study, we evaluated the regeneration potential of MDSCs for muscle loss repair using a novel in situ fibrin gel casting. Muscle defect was created by a partial thickness wedge resection in the tibialis anterior (TA) muscles of NSG mice which created an average of 25% mass loss. If untreated, this defect leads to severe muscle fibrosis. Next, MDSCs were delivered using a novel in situ fibrin gel casting method. Our results demonstrated MDSCs are able to engraft and form new myofibers in the defect when casted along with fibrin gel. LacZ labeled MDSCs were able to differentiate efficiently into new myofibers and significantly increase muscle mass. This was also accompanied by significant reduction of fibrotic tissue in the engrafted muscles. Furthermore, transplanted cells also contributed to new vessel formation and satellite cell seeding. These results confirmed the therapeutic potential of MDSCs and feasibility of direct in situ casting of fibrin/MDSC mixture to repair muscle mass defects. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Generating CO(2)-credits through landfill in situ aeration.

PubMed

Ritzkowski, M; Stegmann, R

2010-04-01

Landfills are some of the major anthropogenic sources of methane emissions worldwide. The installation and operation of gas extraction systems for many landfills in Europe and the US, often including technical installations for energy recovery, significantly reduced these emissions during the last decades. Residual landfill gas, however, is still continuously produced after the energy recovery became economically unattractive, thus resulting in ongoing methane emissions for many years. By landfill in situ aeration these methane emissions can be widely avoided both, during the aeration process as well as in the subsequent aftercare period. Based on model calculations and online monitoring data the amount of avoided CO(2-eq). can be determined. For an in situ aerated landfill in northern Germany, acting as a case study, 83-95% (depending on the kind and quality of top cover) of the greenhouse gas emission potential could be reduced under strictly controlled conditions. Recently the United Nations Framework Convention on Climate Change (UNFCCC) has approved a new methodology on the "Avoidance of landfill gas emissions by in situ aeration of landfills" (UNFCCC, 2009). Based on this methodology landfill aeration projects might be considered for generation of Certified Emission Reductions (CERs) in the course of CDM projects. This paper contributes towards an evaluation of the potential of landfill aeration for methane emissions reduction. Copyright 2009 Elsevier Ltd. All rights reserved.

Calculation of in situ acoustic sediment attenuation using off-the-shelf horizontal ADCPs in low concentration settings

USGS Publications Warehouse

Haught, Dan; Venditti, Jeremy G.; Wright, Scott A.

2017-01-01

The use of “off-the-shelf” acoustic Doppler velocity profilers (ADCPs) to estimate suspended sediment concentration and grain-size in rivers requires robust methods to estimate sound attenuation by suspended sediment. Theoretical estimates of sediment attenuation require a priori knowledge of the concentration and grain-size distribution (GSD), making the method impractical to apply in routine monitoring programs. In situ methods use acoustic backscatter profile slope to estimate sediment attenuation, and are a more attractive option. However, the performance of in situ sediment attenuation methods has not been extensively compared to theoretical methods. We used three collocated horizontally mounted ADCPs in the Fraser River at Mission, British Columbia and 298 observations of concentration and GSD along the acoustic beams to calculate theoretical and in situ sediment attenuation. Conversion of acoustic intensity from counts to decibels is influenced by the instrument noise floor, which affects the backscatter profile shape and therefore in situ attenuation. We develop a method that converts counts to decibels to maximize profile length, which is useful in rivers where cross-channel acoustic profile penetration is a fraction of total channel width. Nevertheless, the agreement between theoretical and in situ attenuation is poor at low concentrations because cross-stream gradients in concentration, sediment size or GSD can develop, which affect the backscatter profiles. We establish threshold concentrations below which in situ attenuation is unreliable in Fraser River. Our results call for careful examination of cross-stream changes in suspended sediment characteristics and acoustic profiles across a range of flows before in situ attenuation methods are applied in river monitoring programs.

In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study

DOE PAGES

Hallac, Basseem B.; Brown, Jared C.; Stavitski, Eli; ...

2018-02-04

Here, the extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt %) lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe 3O 4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible lightmore » using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe 2O 3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe +2.57 for the catalyst with no lanthana and Fe +2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe +2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe +2.57. The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. Furthermore, the paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.« less

In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study

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

Hallac, Basseem B.; Brown, Jared C.; Stavitski, Eli

Here, the extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt %) lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe 3O 4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible lightmore » using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe 2O 3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe +2.57 for the catalyst with no lanthana and Fe +2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe +2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe +2.57. The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. Furthermore, the paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.« less

In Situ Wetland Restoration Demonstration

DTIC Science & Technology

2016-06-01

conditions may differ from subaqueous sediment beds (e.g., moisture content, oxidation-reduction potential, temperature , dissolved oxygen ) and as such...13 3.1.1 Determine Remediation Effectiveness ...20 3.1.6 Cost Effectiveness

Monitoring reservoir response to earthquakes and fluid extraction, Salton Sea geothermal field, California

PubMed Central

Taira, Taka’aki; Nayak, Avinash; Brenguier, Florent; Manga, Michael

2018-01-01

Continuous monitoring of in situ reservoir responses to stress transients provides insights into the evolution of geothermal reservoirs. By exploiting the stress dependence of seismic velocity changes, we investigate the temporal evolution of the reservoir stress state of the Salton Sea geothermal field (SSGF), California. We find that the SSGF experienced a number of sudden velocity reductions (~0.035 to 0.25%) that are most likely caused by openings of fractures due to dynamic stress transients (as small as 0.08 MPa and up to 0.45 MPa) from local and regional earthquakes. Depths of velocity changes are estimated to be about 0.5 to 1.5 km, similar to the depths of the injection and production wells. We derive an empirical in situ stress sensitivity of seismic velocity changes by relating velocity changes to dynamic stresses. We also observe systematic velocity reductions (0.04 to 0.05%) during earthquake swarms in mid-November 2009 and late-December 2010. On the basis of volumetric static and dynamic stress changes, the expected velocity reductions from the largest earthquakes with magnitude ranging from 3 to 4 in these swarms are less than 0.02%, which suggests that these earthquakes are likely not responsible for the velocity changes observed during the swarms. Instead, we argue that velocity reductions may have been induced by poroelastic opening of fractures due to aseismic deformation. We also observe a long-term velocity increase (~0.04%/year) that is most likely due to poroelastic contraction caused by the geothermal production. Our observations demonstrate that seismic interferometry provides insights into in situ reservoir response to stress changes. PMID:29326977

Oxygen Reduction Reaction on Graphene in an Electro-Fenton System: In Situ Generation of H2 O2 for the Oxidation of Organic Compounds.

PubMed

Chen, Chen-Yu; Tang, Cheng; Wang, Hao-Fan; Chen, Cheng-Meng; Zhang, Xiaoyuan; Huang, Xia; Zhang, Qiang

2016-05-23

Fenton oxidation using an aqueous mixture of Fe(2+) and H2 O2 is a promising environmental remediation strategy. However, the difficulty of storage and shipment of concentrated H2 O2 and the generation of iron sludge limit its broad application. Therefore, highly efficient and cost-effective electrocatalysts are in great need. Herein, a graphene catalyst is proposed for the electro-Fenton process, in which H2 O2 is generated in situ by the two-electron reduction of the dissolved O2 on the cathode and then decomposes to generate (.) OH in acidic solution with Fe(2+) . The π bond of the oxygen is broken whereas the σ bond is generally preserved on the metal-free reduced graphene oxide owing to the high free energy change. Consequently, the oxygen is reduced to H2 O2 through a two-electron pathway. The thermally reduced graphene with a high specific surface area (308.8 m(2)  g(-1) ) and a large oxygen content (10.3 at %) exhibits excellent reactivity for the two-electron oxygen reduction reaction to H2 O2 . A highly efficient peroxide yield (64.2 %) and a remarkable decolorization of methylene blue (12 mg L(-1) ) of over 97 % in 160 min are obtained. The degradation of methylene blue with hydroxyl radicals generated in situ is described by a pseudo first-order kinetics model. This provides a proof-of-concept of an environmentally friendly electro-Fenton process using graphene for the oxygen reduction reaction in an acidic solution to generate H2 O2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring reservoir response to earthquakes and fluid extraction, Salton Sea geothermal field, California.

PubMed

Taira, Taka'aki; Nayak, Avinash; Brenguier, Florent; Manga, Michael

2018-01-01

Continuous monitoring of in situ reservoir responses to stress transients provides insights into the evolution of geothermal reservoirs. By exploiting the stress dependence of seismic velocity changes, we investigate the temporal evolution of the reservoir stress state of the Salton Sea geothermal field (SSGF), California. We find that the SSGF experienced a number of sudden velocity reductions (~0.035 to 0.25%) that are most likely caused by openings of fractures due to dynamic stress transients (as small as 0.08 MPa and up to 0.45 MPa) from local and regional earthquakes. Depths of velocity changes are estimated to be about 0.5 to 1.5 km, similar to the depths of the injection and production wells. We derive an empirical in situ stress sensitivity of seismic velocity changes by relating velocity changes to dynamic stresses. We also observe systematic velocity reductions (0.04 to 0.05%) during earthquake swarms in mid-November 2009 and late-December 2010. On the basis of volumetric static and dynamic stress changes, the expected velocity reductions from the largest earthquakes with magnitude ranging from 3 to 4 in these swarms are less than 0.02%, which suggests that these earthquakes are likely not responsible for the velocity changes observed during the swarms. Instead, we argue that velocity reductions may have been induced by poroelastic opening of fractures due to aseismic deformation. We also observe a long-term velocity increase (~0.04%/year) that is most likely due to poroelastic contraction caused by the geothermal production. Our observations demonstrate that seismic interferometry provides insights into in situ reservoir response to stress changes.

Influence of processing factors over concrete strength.

NASA Astrophysics Data System (ADS)

Kara, K. A.; Dolzhenko, A. V.; Zharikov, I. S.

2018-03-01

Construction of facilities of cast in-situ reinforced concrete poses additional requirements to quality of material, peculiarities of the construction process may sometimes lead to appearance of lamination planes and inhomogeneity of concrete, which reduce strength of the material and structure as a whole. Technology compliance while working with cast in-situ concrete has a significant impact onto the concrete strength. Such process factors as concrete curing, vibration and compaction of the concrete mixture, temperature treatment, etc., when they are countered or inadequately followed lead to a significant reduction in concrete strength. Here, the authors experimentally quantitatively determine the loss of strength in in-situ cast concrete structures due to inadequate following of process requirements, in comparison with full compliance.

High-throughput imaging method for direct assessment of GM1 ganglioside levels in mammalian cells

PubMed Central

Acosta, Walter; Martin, Reid; Radin, David N.; Cramer, Carole L.

2016-01-01

GM1-gangliosidosis is an inherited autosomal recessive disorder caused by mutations in the gene GLB1, which encodes acid β-galactosidase (β-gal). The lack of activity in this lysosomal enzyme leads to accumulation of GM1 gangliosides (GM1) in cells. We have developed a high-content-imaging method to assess GM1 levels in fibroblasts that can be used to evaluate substrate reduction in treated GLB1−/− cells [1]. This assay allows fluorescent quantification in a multi-well system which generates unbiased and statistically significant data. Fluorescently labeled Cholera Toxin B subunit (CTXB), which specifically binds to GM1 gangliosides, was used to detect in situ GM1 levels in a fixed monolayer of fibroblasts. This sensitive, rapid, and inexpensive method facilitates in vitro drug screening in a format that allows a high number of replicates using low working volumes. PMID:26958633

High-throughput imaging method for direct assessment of GM1 ganglioside levels in mammalian cells.

PubMed

Acosta, Walter; Martin, Reid; Radin, David N; Cramer, Carole L

2016-03-01

GM1-gangliosidosis is an inherited autosomal recessive disorder caused by mutations in the gene GLB1, which encodes acid β-galactosidase (β-gal). The lack of activity in this lysosomal enzyme leads to accumulation of GM1 gangliosides (GM1) in cells. We have developed a high-content-imaging method to assess GM1 levels in fibroblasts that can be used to evaluate substrate reduction in treated GLB1(-/-) cells [1]. This assay allows fluorescent quantification in a multi-well system which generates unbiased and statistically significant data. Fluorescently labeled Cholera Toxin B subunit (CTXB), which specifically binds to GM1 gangliosides, was used to detect in situ GM1 levels in a fixed monolayer of fibroblasts. This sensitive, rapid, and inexpensive method facilitates in vitro drug screening in a format that allows a high number of replicates using low working volumes.

Electrochemical activation and inhibition of neuromuscular systems through modulation of ion concentrations with ion-selective membranes

NASA Astrophysics Data System (ADS)

Song, Yong-Ak; Melik, Rohat; Rabie, Amr N.; Ibrahim, Ahmed M. S.; Moses, David; Tan, Ara; Han, Jongyoon; Lin, Samuel J.

2011-12-01

Conventional functional electrical stimulation aims to restore functional motor activity of patients with disabilities resulting from spinal cord injury or neurological disorders. However, intervention with functional electrical stimulation in neurological diseases lacks an effective implantable method that suppresses unwanted nerve signals. We have developed an electrochemical method to activate and inhibit a nerve by electrically modulating ion concentrations in situ along the nerve. Using ion-selective membranes to achieve different excitability states of the nerve, we observe either a reduction of the electrical threshold for stimulation by up to approximately 40%, or voluntary, reversible inhibition of nerve signal propagation. This low-threshold electrochemical stimulation method is applicable in current implantable neuroprosthetic devices, whereas the on-demand nerve-blocking mechanism could offer effective clinical intervention in disease states caused by uncontrolled nerve activation, such as epilepsy and chronic pain syndromes.

In situ green synthesis and characterization of sericin-silver nanoparticle composite with effective antibacterial activity and good biocompatibility.

PubMed

He, Huawei; Tao, Gang; Wang, Yejing; Cai, Rui; Guo, Pengchao; Chen, Liqun; Zuo, Hua; Zhao, Ping; Xia, Qingyou

2017-11-01

Silver nanoparticle has been widely applied to a variety of fields for its outstanding antimicrobial activity. However, the stability of silver nanoparticle limits its application under certain conditions. Thus, improving the stability of silver nanoparticle via biosynthesis is a promising shortcut to expand its application. Sericin from silkworm cocoon has good hydrophilicity, reaction activity, biocompatibility and biodegradability. In this study, we developed a novel, simple, one-step biosynthesis method to prepare sericin-silver nanoparticle composite in situ in solution. Sericin served as the reductant of silver ion, the dispersant and stabilizer of the prepared sericin-silver nanoparticle composite. Natural light was the only power source used to catalyze the synthesis of silver nanoparticle in situ in solution. The novel sericin-silver nanoparticle composite was characterized by ultraviolet-visible and fluorescence spectroscopy, X-ray diffraction, transmission electron microscopy and fourier transform infrared spectroscopy. The results showed silver nanoparticle could be synthesized through the reduction of AgNO 3 by the phenolic hydroxyl group of tyrosine residues of sericin under the catalysis of natural light. The synthesized silver nanoparticle had good crystalline, size distribution and long-term stability at room temperature. Light irradiation was essential for the preparation of sericin-silver nanoparticle composite. The antibacterial activity assay showed 25mg/L and 100mg/L were the minimum concentrations of sericin-silver nanoparticle composite required to inhibit the growth of Staphylococcus aureus and kill this bacterium, respectively. The cytotoxicity assay showed cell viability and cell growth were almost not affected by sericin-silver nanoparticle composite under the concentration of 25mg/L. Our study suggested the preparation of sericin-silver nanoparticle composite was environmentally friendly and energy conservation, and the prepared sericin-silver nanoparticle composite had long-term stability, effective antibacterial activity and good biocompatibility. This novel sericin-silver nanoparticle composite has shown great potentials for biomedical application such as antibacterial agent and wound care. Copyright © 2017 Elsevier B.V. All rights reserved.

Citizen`s guide to phytoremediation. Technology fact sheet

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

NONE

1998-08-01

Phytoremediation is the direct use of living green plants for in situ, or in place, risk reduction for contaminated soil, sludges, sediments, and ground water, through contaminant removal, degradation, or containment.

The SENSEI Generic In Situ Interface

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

Ayachit, Utkarsh; Whitlock, Brad; Wolf, Matthew

The SENSEI generic in situ interface is an API that promotes code portability and reusability. From the simulation view, a developer can instrument their code with the SENSEI API and then make make use of any number of in situ infrastructures. From the method view, a developer can write an in situ method using the SENSEI API, then expect it to run in any number of in situ infrastructures, or be invoked directly from a simulation code, with little or no modification. This paper presents the design principles underlying the SENSEI generic interface, along with some simplified coding examples.

Fabrication and Performance of Zirconia Electrolysis Cells for Carbon Dioxide Reduction for Mars In Situ Resource Utilization Applications

NASA Technical Reports Server (NTRS)

Minh, N. Q.; Chung, B. W.; Doshi, R.; Lear, G. R.; Montgomery, K.; Ong, E. T.

1999-01-01

The use of the Martian atmosphere (95% CO2) to produce oxygen (for propellant and life support) can significantly lower the required launch mass and dramatically reduce the total cost for Mars missions. Zirconia electrolysis cells are one of the technologies being considered for oxygen generation from carbon dioxide in Mars In Situ Resource Utilization (ISRU) production plants. The attractive features of the zirconia cell for this application include simple operation and lightweight, low volume system.

Knölker's iron complex: an efficient in situ generated catalyst for reductive amination of alkyl aldehydes and amines.

PubMed

Pagnoux-Ozherelyeva, Anastassiya; Pannetier, Nicolas; Mbaye, Mbaye Diagne; Gaillard, Sylvain; Renaud, Jean-Luc

2012-05-14

An aminated series: a well-defined iron-catalyzed reductive amination reaction of aldehydes and ketones with aliphatic amines using molecular hydrogen is presented. Under mild conditions, good yields for a broad range of alkyl ketones as well as aldehydes were achieved. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hexavalent chromium reduction by bacterial consortia and pure strains from an alkaline industrial effluent.

PubMed

Piñón-Castillo, H A; Brito, E M S; Goñi-Urriza, M; Guyoneaud, R; Duran, R; Nevarez-Moorillon, G V; Gutiérrez-Corona, J F; Caretta, C A; Reyna-López, G E

2010-12-01

To characterize the bacterial consortia and isolates selected for their role in hexavalent chromium removal by adsorption and reduction. Bacterial consortia from industrial wastes revealed significant Cr(VI) removal after 15 days when incubated in medium M9 at pH 6·5 and 8·0. The results suggested chromium reduction. The bacterial consortia diversity (T-RFLP based on 16S rRNA gene) indicated a highest number of operational taxonomic units in an alkaline carbonate medium mimicking in situ conditions. However, incubations under such conditions revealed low Cr(VI) removal. Genomic libraries were obtained for the consortia exhibiting optimal Cr(VI) removal (M9 medium at pH 6·5 and 8·0). They revealed the dominance of 16S rRNA gene sequences related to the genera Pseudomonas/Stenotrophomonas or Enterobacter/Halomonas, respectively. Isolates related to Pseudomonas fluorescens and Enterobacter aerogenes were efficient in Cr(VI) reduction and adsorption to the biomass. Cr(VI) reduction was better at neutral pH rather than under in situ conditions (alkaline pH with carbonate). Isolated strains exhibited significant capacity for Cr(VI) reduction and adsorption. Bacterial communities from chromium-contaminated industrial wastes as well as isolates were able to remove Cr(VI). The results suggest a good potential for bioremediation of industrial wastes when optimal conditions are applied. Journal of Applied Microbiology © 2010 The Society for Applied Microbiology. No claim to Mexican Government works.

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

DOE PAGES

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan; ...

2016-12-16

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

Method for characterization of the redox condition of cementitious materials

DOEpatents

Almond, Philip M.; Langton, Christine A.; Stefanko, David B.

2015-12-22

Disclosed are methods for determining the redox condition of cementitious materials. The methods are leaching methods that utilize an in situ redox indicator that is present in the cementitious materials as formed. The in situ redox indicator leaches from cementitious material and, when the leaching process is carried out under anaerobic conditions can be utilized to determine the redox condition of the material. The in situ redox indicator can exhibit distinct characteristics in the leachate depending upon the redox condition of the indicator.

In situ monitoring of atomic layer controlled pore reduction in alumina tubular membranes using sequential surface reactions

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

Berland, B.S.; Gartland, I.P.; Ott, A.W.

1998-12-01

The pore diameter in alumina tubular membranes with an initial diameter of 50 {angstrom} was systematically reduced using the atomic layer controlled deposition of Al{sub 2}O{sub 3}. The Al{sub 2}O{sub 3} was deposited using sequential exposures of Al(CH{sub 3}){sub 3} (trimethylaluminum, TMA) and H{sub 2}O in an ABAB... binary reaction sequence. The pore diameter reduction was monitored using in situ N{sub 2} and Ar conductance measurements. The conductance, C = Q/{Delta}P, was measured using a mass flow controller to define a constant gas throughput, Q, and a pair of capacitance manometers to monitor the transmembrane pressure drop, {Delta}P. Conductance measurementsmore » were periodically obtained at 298 K as a function of AB binary reaction cycles. These conductance measurements were consistent with a pore diameter reduction from 50 {angstrom} to {approximately}5--10 {angstrom} at a rate of {approximately}2.5 {angstrom} for each AB cycle. Conductance measurements were also performed during the Al{sub 2}O{sub 3} deposition at 500 K after each half-reaction in the binary reaction sequence. These in situ conductance measurements demonstrate that the pore diameters in mesoporous membranes can be reduced to molecular dimensions with atomic layer control using sequential surface reactions. Poe diameters can be tailored for specific applications by varying the number of AB cycles and changing the nature of the terminating surface functional groups.« less

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

Woodstove Emission Sampling Methods Comparability Analysis and In-situ Evaluation of New Technology Woodstoves.

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

Simons, Carl A.

1988-06-01

One major objective of this study was to compare several woodstove particulate emission sampling methods under laboratory and in-situ conditions. The laboratory work compared the EPA Method 5H, EPA Method 5G, and OMNI Automated Woodstove Emission Sampler (AWES)/Data LOG'r particulate emission sampling systems. A second major objective of the study was to evaluate the performance of two integral catalytic, two low emission non-catalytic, and two conventional technology woodstoves under in-situ conditions with AWES/Data LOG'r system. The AWES/Data LOG'r and EPA Method 5G sampling systems were also compared in an in-situ test on one of the integral catalytic woodstove models. 7more » figs., 12 tabs.« less

Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts

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

Han, Jun; Zhan, Yiqiu; Street, Jason

A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO 2 (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni 10CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH 4 and CO 2 decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni10CeAl catalyst was performed using BET, H 2-TPR, in-situ XRD, TEM,more » and TGA-DTG techniques. The in-situ XRD results revealed that Ce 2O 3, CeO 2 and CeAlO 3 coexisted in the Ni10CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.« less

In Situ Immobilization of Uranium in Structured Porous Media (Invited)

NASA Astrophysics Data System (ADS)

Brooks, S. C.; Gu, B.; Wu, W.; Spalding, B. P.; Watson, D. B.; Jardine, P.

2009-12-01

Defense related activities have resulted in broad areas of uranium contaminated groundwater across the U. S. Department of Energy complex. For example, past waste disposal practices at the DOE’s Y-12 site generated a plume of uranium and nitrate contamination in the underlying vadose and saturated zones which extends more than 120 meters deep and thousands of meters along geologic strike. Several DOE sponsored research programs have enabled the study of multiple biotic and abiotic methods of immobilizing uranium in situ at the site. These include biostimulation of metal reducing bacteria to promote reduction of the more soluble U(VI) to the sparingly soluble U(IV) and pH manipulation to immobilize U(VI) through its interactions (e.g., sorption, coprecipitation) with incipient aluminum oxyhydroxide minerals. The application of laboratory based results to the field site must also account for (i) the structured media which can impose incomplete mixing conditions and (ii) steep geochemical gradients or transition zones which differ significantly from the typically well mixed laboratory conditions. In this presentation results of several of these studies will be reviewed and lessons learned summarized.

Fluorescence technique for on-line monitoring of state of hydrogen-producing microorganisms

DOEpatents

Seibert, Michael [Lakewood, CO; Makarova, Valeriya [Golden, CO; Tsygankov, Anatoly A [Pushchino, RU; Rubin, Andrew B [Moscow, RU

2007-06-12

In situ fluorescence method to monitor state of sulfur-deprived algal culture's ability to produce H.sub.2 under sulfur depletion, comprising: a) providing sulfur-deprived algal culture; b) illuminating culture; c) measuring onset of H.sub.2 percentage in produced gas phase at multiple times to ascertain point immediately after anerobiosis to obtain H.sub.2 data as function of time; and d) determining any abrupt change in three in situ fluorescence parameters; i) increase in F.sub.t (steady-state level of chlorophyll fluorescence in light adapted cells); ii) decrease in F.sub.m', (maximal saturating light induced fluorescence level in light adapted cells); and iii) decrease in .DELTA.F/F.sub.m'=(F.sub.m'-F.sub.t)/F.sub.m' (calculated photochemical activity of photosystem II (PSII) signaling full reduction of plastoquinone pool between PSII and PSI, which indicates start of anaerobic conditions that induces synthesis of hydrogenase enzyme for subsequent H.sub.2 production that signal oxidation of plastoquinone pool asmain factor to regulate H.sub.2 under sulfur depletion.

A New Platform for Investigating In-Situ NIR Reflectance in Snow

NASA Astrophysics Data System (ADS)

Johnson, M.; Taubenheim, J. R. L.; Stevenson, R.; Eldred, D.

2017-12-01

In-situ near infrared (NIR) reflectance measurements of the snowpack have been shown to have correlations to valuable snowpack properties. To-date many studies take these measurements by digging a pit and setting up a NIR camera to take images of the wall. This setup is cumbersome, making it challenging to investigate things like spatial variability. Over the course of 3 winters, a new device has been developed capable of mitigating some of the downfalls of NIR open pit photography. This new instrument is a NIR profiler capable of taking NIR reflectance measurements without digging a pit, with most measurements taking less than 30 seconds to retrieve data. The latest prototype is built into a ski pole and automatically transfers data wirelessly to the users smartphone. During 2016-2017 winter, the device was used by 37 different users resulting in over 4000 measurements in the Western United States, demonstrating a dramatic reduction in time to data when compared to other methods. Presented here are some initial findings from a full winter of using the ski pole version of this device.

3D architecture constructed via the confined growth of MoS2 nanosheets in nanoporous carbon derived from metal-organic frameworks for efficient hydrogen production.

PubMed

Liu, Yun; Zhou, Xiaoli; Ding, Tao; Wang, Chunde; Yang, Qing

2015-11-21

The design and synthesis of robust, high-performance and low-cost three-dimensional (3D) hierarchical structured materials for the electrochemical reduction of water to generate hydrogen is of great significance for practical water splitting applications. In this study, we develop an in situ space-confined method to synthesize an MoS2-based 3D hierarchical structure, in which the MoS2 nanosheets grow in the confined nanopores of metal-organic frameworks (MOFs)-derived 3D carbons as electrocatalysts for efficient hydrogen production. Benefiting from its unique structure, which has more exposed active sites and enhanced conductivity, the as-prepared MoS2/3D nanoporous carbon (3D-NPC) composite exhibits remarkable electrocatalytic activity for the hydrogen evolution reaction (HER) with a small onset overpotential of ∼0.16 V, large cathodic currents, small Tafel slope of 51 mV per decade and good durability. We anticipate that this in situ confined growth provides new insights into the construction of high performance catalysts for energy storage and conversion.

In situ stabilization of NAPL contaminant source-zones as a remediation technique to reduce mass discharge and flux to groundwater.

PubMed

Mateas, Douglas J; Tick, Geoffrey R; Carroll, Kenneth C

2017-09-01

Widely used flushing and in-situ destruction based remediation techniques (i.e. pump-and treat, enhanced-solubilization, and chemical oxidation/reduction) for sites contaminated by nonaqueous phase liquid (NAPL) contaminant sources have been shown to be ineffective at complete mass removal and reducing aqueous-phase contaminant of concern (COC) concentrations to levels suitable for site closure. A remediation method was developed to reduce the aqueous solubility and mass-flux of COCs within NAPL through the in-situ creation of a NAPL mixture source-zone. In contrast to remediation techniques that rely on the rapid removal of contaminant mass, this technique relies on the stabilization of difficult-to-access NAPL sources to reduce COC mass flux to groundwater. A specific amount (volume) of relatively insoluble n-hexadecane (HEXDEC) or vegetable oil (VO) was injected into a trichloroethene (TCE) contaminant source-zone through a bench-scale flow cell port (i.e. well) to form a NAPL mixture of targeted mole fraction (TCE:HEXDEC or TCE:VO). NAPL-aqueous phase batch tests were conducted prior to the flow-cell experiments to evaluate the effects of various NAPL mixture ratios on equilibrium aqueous-phase concentrations of TCE to design optimal NAPL (HEXDEC or VO) injection volumes for the flow-cell experiments. The NAPL-stabilization flow-cell experiments initiated and sustained significant reductions in COC concentration and mass flux due to a combination of both reduced relative permeability (increased NAPL-saturation) and via modification of NAPL composition (decreased TCE mole fraction). Variations in remediation performance (i.e. impacts on TCE concentration and mass flux reduction) between the different HEXDEC injection volumes were relatively minor, and therefore inconsistent with Raoult's Law predictions. This phenomenon likely resulted from non-uniform mixing of the injected HEXDEC with TCE in the source-zone. VO injection caused TCE concentrations and mass-flux to decrease more rapidly than with HEXDEC injections. This phenomenon occurred because the injected VO was observed to mix more uniformly with TCE in the source-zone due to a lower mobilization potential. The relative lower density differences (buoyancy effects) between VO and the flushing solution (water) was the primary factor contributing to the lower mobilization potential for VO. Overall, this study indicated that the delivery of HEXDEC or VO into the toxic TCE source-zone was effective in significantly reducing contaminant aqueous-phase concentration and mass-flux. However, the effectiveness of this in-situ NAPL stabilization technique depends on source delivery, uniform mixing of amendment, and that the amendment remains immobilized within and around the NAPL contaminant source. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel green approach for reduction of free standing graphene oxide: electrical and electronic structural investigations.

PubMed

Saravanan, K; Panigrahi, B K; Suresh, K; Sundaravel, B; Magudapathy, P; Gupta, Mukul

2018-08-24

Ion beam irradiation technique has been proposed, for efficient, fast and eco-friendly reduction of graphene oxide (GO), as an alternative to the conventional methods. 5 MeV, Au + ion beam has been used to reduce the free standing GO flake. Both electronic and nuclear energy loss mechanisms of the irradiation process play a major role in removal of oxygen moieties and recovery of graphene network. Atomic resolution scanning tunnelling microscopy analysis of the irradiated GO flake shows the characteristic honeycomb structure of graphene. X-ray absorption near edge structure analysis at C K-edge reveals that the features of the irradiated GO flake resemble the few layer graphene. Resonant Rutherford backscattering spectrometry analysis evidenced an enhanced C/O ratio of ∼23 in the irradiated GO. In situ sheet resistance measurements exhibit a sharp decrease of resistance (few 100 s of Ω) at a fluence of 6.5 × 10 14 ions cm -2 . Photoluminescence spectroscopic analysis of irradiated GO shows a sharp blue emission, while pristine GO exhibits a broad emission in the visible-near IR region. Region selective reduction, tunable electrical and optical properties by controlling C/O ratio makes ion irradiation as a versatile tool for the green reduction of GO for diverse applications.

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

Singh, Aadesh P.; Kodan, Nisha; Mehta, Bodh R., E-mail: brmehta@physics.iitd.ac.in

Highlights: • Growth of TiO{sub 2} thin films with in-situ plasma hydrogenation. • Presence of Ti{sup 2+} states in addition to Ti{sup 3+} states present in pristine TiO{sub 2}. • Change in VBM, work function and band gap in iH:TiO{sub 2}. • Enhanced photocurrent density as compared to pristine TiO{sub 2} films. - Abstract: In this paper, we report the effect of in-situ plasma hydrogenation of TiO{sub 2} (iH:TiO{sub 2}) thin films by the incorporation of known amount of hydrogen in the Ar plasma during rf-sputter deposition of TiO{sub 2} films. As compared to pristine TiO{sub 2} films (∼0.43 mA/cm2more » at 0.23 V vs Ag/AgCl), hydrogenated TiO{sub 2} showed enhanced photoelectrochemical activity in terms of improved photocurrent density of ∼1.08 mA/cm2 (at 0.23 V vs Ag/AgCl). These results are explained in terms of reduction in band gap energy, shift in valence band maximum away from the Fermi level, improved donor density and more negative flat band potential in iH:TiO{sub 2} sample. The presence of Ti{sup 2+} states in iH:TiO{sub 2} films in addition to Ti{sup 3+} states in pristine TiO{sub 2} act as additional electronic states in the TiO{sub 2} band gap and increases the optical absorption in the visible region. This method of in-situ hydrogenation can be used as a general method for improving the properties of metal oxide thin films for photoelectrochemical and photocatalytic applications.« less

Influence of Gridded Standoff Measurement Resolution on Numerical Bathymetric Inversion

NASA Astrophysics Data System (ADS)

Hesser, T.; Farthing, M. W.; Brodie, K.

2016-02-01

The bathymetry from the surfzone to the shoreline incurs frequent, active movement due to wave energy interacting with the seafloor. Methodologies to measure bathymetry range from point-source in-situ instruments, vessel-mounted single-beam or multi-beam sonar surveys, airborne bathymetric lidar, as well as inversion techniques from standoff measurements of wave processes from video or radar imagery. Each type of measurement has unique sources of error and spatial and temporal resolution and availability. Numerical bathymetry estimation frameworks can use these disparate data types in combination with model-based inversion techniques to produce a "best-estimate of bathymetry" at a given time. Understanding how the sources of error and varying spatial or temporal resolution of each data type affect the end result is critical for determining best practices and in turn increase the accuracy of bathymetry estimation techniques. In this work, we consider an initial step in the development of a complete framework for estimating bathymetry in the nearshore by focusing on gridded standoff measurements and in-situ point observations in model-based inversion at the U.S. Army Corps of Engineers Field Research Facility in Duck, NC. The standoff measurement methods return wave parameters computed using linear wave theory from the direct measurements. These gridded datasets can range in temporal and spatial resolution that do not match the desired model parameters and therefore could lead to a reduction in the accuracy of these methods. Specifically, we investigate the affect of numerical resolution on the accuracy of an Ensemble Kalman Filter bathymetric inversion technique in relation to the spatial and temporal resolution of the gridded standoff measurements. The accuracies of the bathymetric estimates are compared with both high-resolution Real Time Kinematic (RTK) single-beam surveys as well as alternative direct in-situ measurements using sonic altimeters.

Electroless silver plating on PET fabric initiated by in situ reduction of polyaniline

NASA Astrophysics Data System (ADS)

Mu, Shipeng; Xie, Huayang; Wang, Wei; Yu, Dan

2015-10-01

Novel electroless silver plating poly(ethylene terephthalate) (PET) fabric was prepared by a two-step procedure. In the first step, the in situ polymerized polyaniline (PANI) occurred on the fabric surface in the presence of ammonium persulfate (APS). Then, Ag(0) species reduced from silver nitrate (AgNO3) by in situ reduction of PANI were used as catalyst to initiate electroless silver plating. Hence, this composite material was prepared by conductive polymer combined with electroless plating. The silver layer on PET fabric surface was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDX) as well as X-ray photoelectron spectroscopy (XPS). The results showed that the silver layer was plated uniformly and compactly with surface resistance about 0.1 Ω/sq on average. The shielding effectiveness (SE) of silver-plated PET fabric was around 50-90 dB, which was considered to have potential applications in electromagnetic shielding materials. Thermogravimetric (TG) analysis was carried out to study thermal stability. The antibacterial tests demonstrated that the silver-plated fabric exhibited excellent antibacterial activity against Staphylococcus aureus and Escherichia coli both with 100%.

In situ X-ray absorption fine structure analysis of redox reactions of nickel species with variable particle sizes supported on silica

NASA Astrophysics Data System (ADS)

Yamamoto, Yusaku; Suzuki, Atsushi; Tsutsumi, Naoki; Katagiri, Masaki; Yamashita, Shohei; Niwa, Yasuhiro; Katayama, Misaki; Inada, Yasuhiro

2018-02-01

The chemical states of Ni species were systematically investigated using an in situ XAFS technique for a series of SiO2-supported Ni catalysts with different Ni particle sizes. The Ni particles were refined by varying the Ni loading in the range between 0.10 and 5 wt% and by adding citric acid into the precursor solution. An in situ observation cell for fluorescence-yield XAFS measurements was developed for the dilute Ni catalysts. The chemical state of the supported Ni species converted between Ni(0) and NiO, and no other stable species were formed during the temperature-programmed oxidation and reduction processes. Refinement of the Ni particles resulted in decreasing the oxidation temperature and increasing the reduction temperature. These shifts were explained by the affinity of NiO to SiO2, and more effective stabilization was thus anticipated for flattened small NiO particles with an increased contact area. In addition, the inhomogeneous distribution of small Ni particles observed for dilute catalysts was explained in terms of the precursor solution volume when nuclei of the precursor compound precipitated on SiO2 during the drying process.

Facile synthesis of sewage sludge-derived in-situ multi-doped nanoporous carbon material for electrocatalytic oxygen reduction

NASA Astrophysics Data System (ADS)

Yuan, Shi-Jie; Dai, Xiao-Hu

2016-06-01

Developing efficient, low-cost, and stable carbon-based catalysts for oxygen reduction reaction (ORR) to replace the expensive platinum-based electrocatalysts remains a major challenge that hamper the practical application of fuel cells. Here, we report that N, Fe, and S co-doped nanoporous carbon material, derived via a facile one-step pyrolysis of sewage sludge, the major byproduct of wastewater treatment, can serve as an effective electrocatalyst for ORR. Except for the comparable catalytic activity with commercial 20% Pt/C via a nearly four-electron transfer pathway in both alkaline and acid medium, the as-synthesized co-doped electrocatalyst also exhibits excellent methanol crossover resistance and outstanding long-term operation stability. The organic compounds in sewage sludge act as the carbon source and the in-situ N and S dopant in the fabrication, while the inorganic compounds serve as the in-built template and the in-situ Fe dopant. Our protocol demonstrates a new approach in the economic and eco-friendly benign reuse of sewage sludge, and also provides a straightforward route for synthesizing excellent carbon-based electrocatalysts as promising candidates for ORR directly from a type of waste/pollution.

In situ treatability testing of reductive dechlorination in wetland sediments

USGS Publications Warehouse

Lorah, M.M.; Majcher, E.; Jones, E.; Driedger, G.; Dworatzek, S.; Graves, D.

2005-01-01

In situ treatability testing was conducted in the discharge wetlands along West Branch Canal Creek at Aberdeen Proving Ground, MD. The potential for stimulating reductive dechlorination of 1,1,2,2-tetrachloroethane, tetrachloroethylene, trichloroethylene, and carbon tetrachloride in areas of preferential discharge or seeps was evaluated. Geological Survey that degrades chlorinated ethanes and ethylenes was tested using MICRO-Trac??? devices. At seep 3-4W, results of the C and BA MICRO-Trac??? treatments showed essentially no biodegradation of chlorinated solvents occurring under natural and bioaugmented conditions. Results of geochemical samples at this site indicated predominantly iron- and sulfate-reducing conditions consistent with the rapid discharge rates previously measured. The biostimulated treatment showed stimulation of methanogenic conditions and partial degradation of the parent chlorinated VOC to intermediate chlorinated compounds. The bioaugmented and bistimulated treatment showed the highest production of methane, the highest removal of parent compounds and intermediate daughter products, and the highest production of the non-chlorinated end product ethylene. This is an abstract of a paper presented at the proceedings of the 8th International In Situ and On-Site Bioremediation Symposium (Baltimore, MD 6/6-9/2005).

In Situ Fabrication and Reactivation of Highly Selective and Stable Ag Catalysts for Electrochemical CO2 Conversion.

PubMed

Ma, Ming; Liu, Kai; Shen, Jie; Kas, Recep; Smith, Wilson A

2018-06-08

In this work, the highly selective and stable electrocatalytic reduction of CO 2 to CO on nanostructured Ag electrocatalysts is presented. The Ag electrocatalysts are synthesized by the electroreduction of Ag 2 CO 3 formed by in situ anodic-etching of Ag foil in a KHCO 3 electrolyte. After 3 min of this etching treatment, the Ag 2 CO 3 -derived nanostructured Ag electrocatalysts are capable of producing CO with up to 92% Faradaic efficiency at an overpotential as low as 290 mV, which surpasses all of the reported Ag catalysts at identical conditions to date. In addition, the anodic-etched Ag retained ∼90% catalytic selectivity in the electroreduction of CO 2 to CO for more than 100 h. The Ag 2 CO 3 -derived Ag is able to facilitate the activation of CO 2 via reduction of the activation energy barrier of the initial electron transfer and provide an increased number of active sites, resulting in the dramatically improved catalytic activity for the reduction of CO 2 to CO.

In situ loading of gold nanoparticles on Fe3O4@SiO2 magnetic nanocomposites and their high catalytic activity.

PubMed

Zheng, Jinmin; Dong, Yalei; Wang, Weifeng; Ma, Yanhua; Hu, Jing; Chen, Xiaojiao; Chen, Xingguo

2013-06-07

In this work, a facile approach was successfully developed for in situ catalyzing Au nanoparticles loaded on Fe3O4@SiO2 magnetic nanospheres via Sn(2+) linkage and reduction. After the Fe3O4@SiO2 MNPs were first prepared via a sol-gel process, only one step was needed to synthesize the Fe3O4@SiO2-Au magnetic nanocomposites (Fe3O4@SiO2-Au MNCs), so that both the synthesis step and the reaction cost were remarkably decreased. Significantly, the as-synthesized Fe3O4@SiO2-Au MNCs showed high performance in the catalytic reduction of 4-nitrophenol to 4-aminophenol and could be reused for several cycles with convenient magnetic separability. This approach provided a useful platform based on Fe3O4@SiO2 MNPs for the fabrication of Au or other noble metal magnetic nanocatalysts, which would be very useful in various catalytic reductions.

An In-Situ XAS Study of the Structural Changes in a CuO-CeO2/Al2O3 Catalyst during Total Oxidation of Propane

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

Silversmith, Geert; Poelman, Hilde; Poelman, Dirk

2007-02-02

A CuOx-CeOx/Al2O3 catalyst was studied with in-situ transmission Cu K XAS for the total oxidation of propane as model reaction for the catalytic elimination of volatile organic compounds. The local Cu structure was determined for the catalyst as such, after pre-oxidation and after reduction with propane. The catalyst as such has a local CuO structure. No structural effect was observed upon heating in He up to 600 deg. C or after pre-oxidation at 150 deg. C. A full reduction of the Cu2+ towards metallic Cu0 occurred, when propane was fed to the catalyst. The change in local Cu structure duringmore » propane reduction was followed with a time resolution of 1 min. The {chi}(k) scans appeared as linear combinations of start and end spectra, CuO and Cu structure, respectively. However, careful examination of the XANES edge spectra indicates the presence of a small amount of additional Cu1+ species.« less

In situ methods for Li-ion battery research: A review of recent developments

NASA Astrophysics Data System (ADS)

Harks, P. P. R. M. L.; Mulder, F. M.; Notten, P. H. L.

2015-08-01

A considerable amount of research is being directed towards improving lithium-ion batteries in order to meet today's market demands. In particular in situ investigations of Li-ion batteries have proven extremely insightful, but require the electrochemical cell to be fully compatible with the conditions of the testing method and are therefore often challenging to execute. Advantageously, in the past few years significant progress has been made with new, more advanced, in situ techniques. Herein, a comprehensive overview of in situ methods for studying Li-ion batteries is given, with the emphasis on new developments and reported experimental highlights.

Metal Selenides as Efficient Counter Electrodes for Dye-Sensitized Solar Cells.

PubMed

Jin, Zhitong; Zhang, Meirong; Wang, Min; Feng, Chuanqi; Wang, Zhong-Sheng

2017-04-18

Solar energy is the most abundant renewable energy available to the earth and can meet the energy needs of humankind, but efficient conversion of solar energy to electricity is an urgent issue of scientific research. As the third-generation photovoltaic technology, dye-sensitized solar cells (DSSCs) have gained great attention since the landmark efficiency of ∼7% reported by O'Regan and Grätzel. The most attractive features of DSSCs include low cost, simple manufacturing processes, medium-purity materials, and theoretically high power conversion efficiencies. As one of the key materials in DSSCs, the counter electrode (CE) plays a crucial role in completing the electric circuit by catalyzing the reduction of the oxidized state to the reduced state for a redox couple (e.g., I 3 - /I - ) in the electrolyte at the CE-electrolyte interface. To lower the cost caused by the typically used Pt CE, which restricts the large-scale application because of its low reserves and high price, great effort has been made to develop new CE materials alternative to Pt. A lot of Pt-free electrocatalysts, such as carbon materials, inorganic compounds, conductive polymers, and their composites with good electrocatalytic activity, have been applied as CEs in DSSCs in the past years. Metal selenides have been widely used as electrocatalysts for the oxygen reduction reaction and light-harvesting materials for solar cells. Our group first expanded their applications to the DSSC field by using in situ-grown Co 0.85 Se nanosheet and Ni 0.85 Se nanoparticle films as CEs. This finding has inspired extensive studies on developing new metal selenides in order to seek more efficient CE materials for low-cost DSSCs, and a lot of meaningful results have been achieved in the past years. In this Account, we summarize recent advances in binary and mutinary metal selenides applied as CEs in DSSCs. The synthetic methods for metal selenides with various morphologies and stoichiometric ratios and deposition methods for CE films are described. We emphasize that the in situ growth method exhibits advantages over other methods for fabricating stable and efficient CEs. We focus on the effect of morphology on the electocatalytic and photovoltaic performance. Application of transparent metal selenide CEs in bifacial DSSCs and the superiority of in situ-grown metal selenide nanosheet fiber CEs used for fiber DSSCs are presented. In addition, we show that metal selenides with a hollow sphere structure can function not only as an efficient electrocatalyst but also as a light-scattering layer. Finally, we present our views on the current challenges and future development of metal selenide CE materials.

A safer, urea-based in situ hybridization method improves detection of gene expression in diverse animal species.

PubMed

Sinigaglia, Chiara; Thiel, Daniel; Hejnol, Andreas; Houliston, Evelyn; Leclère, Lucas

2018-02-01

In situ hybridization is a widely employed technique allowing spatial visualization of gene expression in fixed specimens. It has greatly advanced our understanding of biological processes, including developmental regulation. In situ protocols are today routinely followed in numerous laboratories, and although details might change, they all include a hybridization step, where specific antisense RNA or DNA probes anneal to the target nucleic acid sequence. This step is generally carried out at high temperatures and in a denaturing solution, called hybridization buffer, commonly containing 50% (v/v) formamide - a hazardous chemical. When applied to the soft-bodied hydrozoan medusa Clytia hemisphaerica, we found that this traditional hybridization approach was not fully satisfactory, causing extensive deterioration of morphology and tissue texture which compromised our observation and interpretation of results. We thus tested alternative solutions for in situ detection of gene expression and, inspired by optimized protocols for Northern and Southern blot analysis, we substituted the 50% formamide with an equal volume of 8M urea solution in the hybridization buffer. Our new protocol not only yielded better morphologies and tissue consistency, but also notably improved the resolution of the signal, allowing more precise localization of gene expression and reducing aspecific staining associated with problematic areas. Given the improved results and reduced manipulation risks, we tested the urea protocol on other metazoans, two brachiopod species (Novocrania anomala and Terebratalia transversa) and the priapulid worm Priapulus caudatus, obtaining a similar reduction of aspecific probe binding. Overall, substitution of formamide by urea during in situ hybridization offers a safer alternative, potentially of widespread use in research, medical and teaching contexts. We encourage other workers to test this approach on their study organisms, and hope that they will also obtain better sample preservation, more precise expression patterns and fewer problems due to aspecific staining, as we report here for Clytia medusae and Novocrania and Terebratalia developing larvae. Copyright © 2017 Elsevier Inc. All rights reserved.

Evaluation of TCDD biodegradability under different redox conditions.

PubMed

Kao, C M; Chen, S C; Liu, J K; Wu, M J

2001-09-01

Polychlorinated dibenzo-p-dioxins have been generated as unwanted by-products in many industrial processes. Although their widespread distribution in different environmental compartments has been recognized, little is known about their fate in the ultimate environment sinks. The highly stable dioxin isomer 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been called the most toxic compound known to man. In this laboratory microcosm study, TCDD bioavailability was evaluated under five reduction/oxidation (redox) conditions including aerobic biodegradation, aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Activated sludge and aquifer sediments from a TCDD and a pentachlorophenol (PCP) contaminated site were used as the inocula. Acetate, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in cometabolism and reductive dechlorination microcosms. After a 90-day incubation period, microcosms constructed under reductive dechlorination conditions were the only treatment showing promising remediation results. The highest TCDD degradation rate [up to 86% of TCDD removal (with an initial concentration of 96 microg/kg of soil)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cakes as the primary substrates. Except for reductive dechlorination microcosms, no significant TCDD removal was observed in the microcosms prepared under other conditions. Thus, application of an effective primary substrate to enhance the reductive dechlorination process is a feasible method for TCDD bioremediation. Bioremediation expense can be significantly reduced by the supplement of some less expensive alternative substrates (e.g., sludge cakes, cane molasses). Results would be useful in designing a scale-up in situ or on-site bioremediation system such as bioslurry reactor for field application.

Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

PubMed

Nesselberger, Markus; Ashton, Sean J; Wiberg, Gustav K H; Arenz, Matthias

2013-07-01

We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring

PubMed Central

Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

2016-01-01

We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ. PMID:27297893

In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring.

PubMed

Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

2016-06-25

We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ.

Two new Cu{sup I} compounds with zwitterionic tetrazolate ligand: In situ synthesis, crystal structures, luminescence and photocatalytic properties

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

Zhang, Jian-Yong; Xing, Yuan-Yuan; Wang, Qing-Wei

2015-12-15

Two 2D new Cu(I) coordination polymers, namely [Cu{sub 2}(mpTZ){sub 2}Br{sub 2}]·H{sub 2}O (1), and [Cu{sub 2}(mpTZ){sub 2}N{sub 3}]ClO{sub 4} (2) (mpTZ=N-methyl-4-pyridinium tetrazolate) have been synthesized under solvothermal conditions, in which the mpTZ ligands and Cu{sup I} ions were obtained through in situ [2+3] cycloaddition reaction and reduction reaction of Cu{sup II} salts, respectively. Both compounds have been structural characterized by single crystal X-ray diffraction, FT-IR, PXRD and EA. Compound 1 exhibits a 2D neutral coordination network, in which the Cu{sup I} ions are bridged by η{sub 3}−1, 2, 4-tetrazolate into 2D sheet. In compound 2, the Cu{sup I} ions aremore » linked by azide (in µ{sub 3}−1, 1, 3 bridging mode) and tetrazolate (in η{sub 3}−1, 2, 3 bridging mode) anions into 2D positively charged sheet, extended along the bc plane. Both compounds 1 and 2 exhibit intense bluish green luminescence in the solid state. Photocatalytic performances of the two compounds for the degradation of methylene blue (MB) under visible light were also investigated and the MB degradation in the presence of 1 was nearly complete (99%) after 150 min. - Graphical abstract: Two Cu{sup I}CPs have been solvothermally synthesized through the in situ [2+3] cycloaddition and metal reduction reaction. Both compounds exhibit intense luminescence and high photocatalytic degradation under visible light. - Highlights: • Two new Cu{sup I}-based CPs are solvothermally synthesized through in situ [2+3] cycloaddition reaction and metal reduction reaction. • Both compounds exhibit strong luminescence and photocatalytic degradation of methylene blue (MB) under visible light. • The MB degradation in the presence of 1 is nearly complete (99%) after 150 min.« less

Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis

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

Mohr, Stephan; Masella, Michel; Ratcliff, Laura E.

We present, within Kohn-Sham Density Functional Theory calculations, a quantitative method to identify and assess the partitioning of a large quantum mechanical system into fragments. We then introduce a simple and efficient formalism (which can be written as generalization of other well-known population analyses) to extract, from first principles, electrostatic multipoles for these fragments. The corresponding fragment multipoles can in this way be seen as reliable (pseudo-) observables. By applying our formalism within the code BigDFT, we show that the usage of a minimal set of in-situ optimized basis functions is of utmost importance for having at the same timemore » a proper fragment definition and an accurate description of the electronic structure. With this approach it becomes possible to simplify the modeling of environmental fragments by a set of multipoles, without notable loss of precision in the description of the active quantum mechanical region. Furthermore, this leads to a considerable reduction of the degrees of freedom by an effective coarsegraining approach, eventually also paving the way towards efficient QM/QM and QM/MM methods coupling together different levels of accuracy.« less

Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis

DOE PAGES

Mohr, Stephan; Masella, Michel; Ratcliff, Laura E.; ...

2017-07-21

We present, within Kohn-Sham Density Functional Theory calculations, a quantitative method to identify and assess the partitioning of a large quantum mechanical system into fragments. We then introduce a simple and efficient formalism (which can be written as generalization of other well-known population analyses) to extract, from first principles, electrostatic multipoles for these fragments. The corresponding fragment multipoles can in this way be seen as reliable (pseudo-) observables. By applying our formalism within the code BigDFT, we show that the usage of a minimal set of in-situ optimized basis functions is of utmost importance for having at the same timemore » a proper fragment definition and an accurate description of the electronic structure. With this approach it becomes possible to simplify the modeling of environmental fragments by a set of multipoles, without notable loss of precision in the description of the active quantum mechanical region. Furthermore, this leads to a considerable reduction of the degrees of freedom by an effective coarsegraining approach, eventually also paving the way towards efficient QM/QM and QM/MM methods coupling together different levels of accuracy.« less

Part I: In-situ fluorometric quantification of microalgal neutral lipids. Part II: Thermal degradation behavior of investment casting polymer patterns

NASA Astrophysics Data System (ADS)

Zhao, Hongfang

Research described in this dissertation covers two topics. Part-I is focused on in-situ determination of neutral lipid content of microalgae using a lipophilic fluorescent dye. The traditional Nile red stain-based method for detecting microalgal intracellular lipids is limited due to varying composition and thickness of rigid cell walls. In this study, the addition of dilute acid and heating of solution, were found to greatly enhance staining efficiency of Nile red for microalgal species evaluated. Oil-in-water (O/W) microemulsion stabilized by a non-ionic surfactant was employed as a pseudo-standard that mimics lipid-bearing microalgal cells suspended in water. The average neutral lipid contents determined were very close to the results obtained by traditional gravimetric method and solid phase extraction. Part II of the dissertation explores thermo-physico-chemical properties of polymeric pattern materials, including expanded polystyrene (EPS) foam, polyurethane foam, and epoxy stereolithography (SLA) patterns, that are used in investment casting. Density, elastic modulus, expansion coefficient, thermal degradation behavior, etc. were experimentally investigated for their effects on metal casting quality. The reduction in toxic hydrogen cyanide (HCN) generated during thermal decomposition of polyurethane pattern was achieved by increasing either oxidant level or residence time in heated zone. Thermal degradation kinetics of the pattern materials were examined with a thermogravimetric analysis and activation energies were determined by Kissinger and Flynn-Wall-Ozawa methods.

Changes in Keratocyte Density and Visual Function Five Years After Laser In Situ Keratomileusis: Femtosecond Laser Versus Mechanical Microkeratome.

PubMed

McLaren, Jay W; Bourne, William M; Maguire, Leo J; Patel, Sanjay V

2015-07-01

To determine the effects of keratocyte loss on optical properties and vision after laser in situ keratomileusis (LASIK) with the flap created with a femtosecond laser or a mechanical microkeratome. Randomized clinical paired-eye study. Both eyes of 21 patients received LASIK for myopia or myopic astigmatism. One eye of each patient was randomized by ocular dominance to flap creation with a femtosecond laser and the other eye to flap creation with a mechanical microkeratome. Before LASIK and at 1, 3, and 6 months and 1, 3, and 5 years after LASIK, keratocyte density was measured using confocal microscopy, and high-contrast visual acuity and anterior corneal wavefront aberrations were measured by standard methods. At each visit, all variables were compared between methods of creating the flap and to the same variable before treatment using paired tests with Bonferroni correction for multiple comparisons. Keratocyte density in the flap decreased by 20% during the first year after LASIK and remained low through 5 years (P < .001). High-order wavefront aberrations increased and uncorrected visual acuity improved immediately after surgery, but these variables did not change further to 5 years. There were no differences in any variables between treatments. A sustained reduction in keratocyte density does not affect vision or optical properties of the cornea through 5 years after LASIK. The method of creating a LASIK flap does not influence the changes in keratocyte density in the flap. Copyright © 2015 Elsevier Inc. All rights reserved.

Fabrication of MgB2 monofilament wire by in-situ using powder-in-tube (PIT) method

NASA Astrophysics Data System (ADS)

Rasyadi, Muhammad Emir Hanif; Yudanto, Sigit Dwi; Imaduddin, Agung; Sawitri, Dyah

2018-04-01

In this research we have studied the making of MgB2 superconducting monofilament wire using powder-in-tube method with variation of Mg composition to B ie 0.90, 1.00 and 1.10, while Boron remains The precursor used is Mg powder (98%) and powder B (95%) Both materials are mixed and then crushed with agate mortar for 30 minutes and then put into stainless steel tube 316. The tube is then subjected to a mechanical treatment of rolling to form its monofilament wire. The wire is then cut and sintered at a temperature of 800o C for 2 hours. After that we measure the critical temperature then characterize the samples by XRD and SEM. From the result of this research it was found that in-situ wire-making by powder-in-tube method can make MgB2 superconducting monofilament wire with MgB2 as the dominant phase around 95% and MgO as the impurity phase around 5%. MgO is formed due to the oxidation occurring in the MgB2 powder inside the wire. The optimal Mg:B composition to make this wire is in the 1:2 composition Because it has a good resistivity curve with a high enough Tc Onset that is 41,67 K and Tc Zero 40,89 K. However, there is a porosity in the wire due to the volume reduction of the Mg + 2B reaction plus the evaporation of Mg.

Total synthesis of fluoxetine and duloxetine through an in situ imine formation/borylation/transimination and reduction approach.

PubMed

Calow, Adam D J; Fernández, Elena; Whiting, Andrew

2014-08-28

We report efficient, catalytic, asymmetric total syntheses of both (R)-fluoxetine and (S)-duloxetine from α,β-unsaturated aldehydes conducting five sequential one-pot steps (imine formation/copper mediated β-borylation/transimination/reduction/oxidation) followed by the specific ether group formation which deliver the desired products (R)-fluoxetine in 45% yield (96% ee) and (S)-duloxetine in 47% yield (94% ee).

A comparison of in situ methods for measuring net nitrogen mineralization rates of organic soil amendments.

PubMed

Hanselman, Travis A; Graetz, Donald A; Obreza, Thomas A

2004-01-01

In situ incubation methods may help provide site-specific estimates of N mineralization from land-applied wastes. However, there are concerns about the reliability of the data generated by the various methods due to containment artifacts. We amended a sandy soil with either poultry manure, biosolids, or yard-waste compost and incubated the mixtures using four in situ methods (buried bags, covered cylinders, standard resin traps, and "new" soil-resin traps) and a conventional laboratory technique in plastic bags. Each incubation device was destructively sampled at 45-d intervals for 180 d and net N mineralization was determined by measuring the amount of inorganic N that accumulated in the soil or soil plus resin traps. Containment effects were evaluated by comparing water content of the containerized soil to a field-reference soil column. In situ incubation methods provided reasonable estimates of short-term (< 45 d) N mineralization, but long-term (> 45 d) mineralization data were not accurate due to a variety of problems specific to each technique. Buried bags and covered cylinders did not retain mineralized N due to water movement into and out of the containers. Neither resin method captured all of the mineralized N that leached through the soil columns, but the new soil-resin trap method tracked field soil water content better than all other in situ methods evaluated. With further refinement and validation, the new soil-resin trap method may be a useful in situ incubation technique for measuring net N mineralization rates of organic soil amendments.

Changes in Keratocyte Density and Visual Function Five Years after Laser in situ Keratomileusis: Femtosecond Laser vs Mechanical Microkeratome

PubMed Central

McLaren, Jay W.; Bourne, William M.; Maguire, Leo J.; Patel, Sanjay V.

2015-01-01

Purpose To determine the effects of keratocyte loss on optical properties and vision after laser in situ keratomileusis (LASIK) with the flap created with a femtosecond laser or a mechanical microkeratome. Design Randomized clinical paired-eye study. Methods Both eyes of 21 patients received LASIK for myopia or myopic astigmatism. One eye of each patient was randomized by ocular dominance to flap creation with a femtosecond laser and the other eye to flap creation with a mechanical microkeratome. Before LASIK and at 1, 3, 6 months and 1, 3, and 5 years after LASIK, keratocyte density was measured by using confocal microscopy, and high-contrast visual acuity and anterior corneal wavefront aberrations were measured by standard methods. At each visit, all variables were compared between methods of creating the flap and to the same variable before treatment by using paired tests with Bonferroni correction for multiple comparisons. Results Keratocyte density in the flap decreased by 20% during the first year after LASIK and remained low through 5 years (p<0.001). High-order wavefront aberrations increased and uncorrected visual acuity improved immediately after surgery but these variables did not change further to five years. There were no differences in any variables between treatments. Conclusions A sustained reduction in keratocyte density does not affect vision or optical properties of the cornea through 5 years after LASIK. The method of creating a LASIK flap does not influence the changes in keratocyte density in the flap. PMID:25868758

A novel reduction approach to fabricate quantum-sized SnO₂-conjugated reduced graphene oxide nanocomposites as non-enzymatic glucose sensors.

PubMed

Ye, Yixing; Wang, Panpan; Dai, Enmei; Liu, Jun; Tian, Zhenfei; Liang, Changhao; Shao, Guosheng

2014-05-21

Quantum-sized SnO2 nanocrystals can be well dispersed on reduced graphene oxide (rGO) nanosheets through a convenient one-pot in situ reduction route without using any other chemical reagent or source. Highly reactive metastable tin oxide (SnO(x)) nanoparticles (NPs) were used as reducing agents and composite precursors derived by the laser ablation in liquid (LAL) technique. Moreover, the growth and phase transition of LAL-induced SnO(x) NPs and graphene oxide (GO) were examined by optical absorption, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and high-resolution transmission electron microscopy. Highly dispersed SnO(x) NPs can also prevent rGO from being restacked into a multilayer structure during GO reduction. Given the good electron transfer ability and unsaturated dangling bonds of rGO, as well as the ample electrocatalytic active sites of quantum-sized SnO2 NPs on unfolded rGO sheets, the fabricated SnO2-rGO nanocomposite exhibited excellent performance in the non-enzymatic electrochemical detection of glucose molecules. The use of LAL-induced reactive NPs for in situ GO reduction is also expected to be a universal and environmentally friendly approach for the formation of various rGO-based nanocomposites.

3D-Hydrogel Based Polymeric Nanoreactors for Silver Nano-Antimicrobial Composites Generation.

PubMed

Soto-Quintero, Albanelly; Romo-Uribe, Ángel; Bermúdez-Morales, Víctor H; Quijada-Garrido, Isabel; Guarrotxena, Nekane

2017-08-01

This study underscores the development of Ag hydrogel nanocomposites, as smart substrates for antibacterial uses, via innovative in situ reactive and reduction pathways. To this end, two different synthetic strategies were used. Firstly thiol-acrylate (PSA) based hydrogels were attained via thiol-ene and radical polymerization of polyethylene glycol (PEG) and polycaprolactone (PCL). As a second approach, polyurethane (PU) based hydrogels were achieved by condensation polymerization from diisocyanates and PCL and PEG diols. In fact, these syntheses rendered active three-dimensional (3D) hydrogel matrices which were used as nanoreactors for in situ reduction of AgNO₃ to silver nanoparticles. A redox chemistry of stannous catalyst in PU hydrogel yielded spherical AgNPs formation, even at 4 °C in the absence of external reductant; and an appropriate thiol-functionalized polymeric network promoted spherical AgNPs well dispersed through PSA hydrogel network, after heating up the swollen hydrogel at 103 °C in the presence of citrate-reductant. Optical and swelling behaviors of both series of hydrogel nanocomposites were investigated as key factors involved in their antimicrobial efficacy over time. Lastly, in vitro antibacterial activity of Ag loaded hydrogels exposed to Pseudomona aeruginosa and Escherichia coli strains indicated a noticeable sustained inhibitory effect, especially for Ag-PU hydrogel nanocomposites with bacterial inhibition growth capabilities up to 120 h cultivation.

Novel RNA hybridization method for the in situ detection of ETV1, ETV4, and ETV5 gene fusions in prostate cancer.

PubMed

Kunju, Lakshmi P; Carskadon, Shannon; Siddiqui, Javed; Tomlins, Scott A; Chinnaiyan, Arul M; Palanisamy, Nallasivam

2014-09-01

The genetic basis of 50% to 60% of prostate cancer (PCa) is attributable to rearrangements in E26 transformation-specific (ETS) (ERG, ETV1, ETV4, and ETV5), BRAF, and RAF1 genes and overexpression of SPINK1. The development and validation of reliable detection methods are warranted to classify various molecular subtypes of PCa for diagnostic and prognostic purposes. ETS gene rearrangements are typically detected by fluorescence in situ hybridization and reverse-transcription polymerase chain reaction methods. Recently, monoclonal antibodies against ERG have been developed that detect the truncated ERG protein in immunohistochemical assays where staining levels are strongly correlated with ERG rearrangement status by fluorescence in situ hybridization. However, specific antibodies for ETV1, ETV4, and ETV5 are unavailable, challenging their clinical use. We developed a novel RNA in situ hybridization-based assay for the in situ detection of ETV1, ETV4, and ETV5 in formalin-fixed paraffin-embedded tissues from prostate needle biopsies, prostatectomy, and metastatic PCa specimens using RNA probes. Further, with combined RNA in situ hybridization and immunohistochemistry we identified a rare subset of PCa with dual ETS gene rearrangements in collisions of independent tumor foci. The high specificity and sensitivity of RNA in situ hybridization provides an alternate method enabling bright-field in situ detection of ETS gene aberrations in routine clinically available PCa specimens.

A Novel Early Warning System Based on a Sediment Microbial Fuel Cell for In Situ and Real Time Hexavalent Chromium Detection in Industrial Wastewater.

PubMed

Zhao, Shuai; Liu, Pu; Niu, Yongyan; Chen, Zhengjun; Khan, Aman; Zhang, Pengyun; Li, Xiangkai

2018-02-22

Hexavalent chromium (Cr(VI)) is a well-known toxic heavy metal in industrial wastewater, but in situ and real time monitoring cannot be achieved by current methods used during industrial wastewater treatment processes. In this study, a Sediment Microbial Fuel Cell (SMFC) was used as a biosensor for in situ real-time monitoring of Cr(VI), which was the organic substrate is oxidized in the anode and Cr(VI) is reduced at the cathode simultaneously. The pH 6.4 and temperature 25 °C were optimal conditions for the operation. Under the optimal conditions, linearity (R² = 0.9935) of the generated voltage was observed in the Cr(VI) concentration range from 0.2 to 0.7 mg/L. The system showed high specificity for Cr(VI), as other co-existing ions such as Cu 2+ , Zn 2+ , and Pb 2+ did not interfere with Cr(VI) detection. In addition, when the sediment MFC-based biosensor was applied for measuring Cr(VI) in actual wastewater samples, a low deviation (<8%) was obtained, which indicated its potential as a reliable biosensor device. MiSeq sequencing results showed that electrochemically active bacteria ( Geobacter and Pseudomonas ) were enriched at least two-fold on the biofilm of the anode in the biosensor as compared to the SMFC without Cr(VI). Cyclic voltammetry curves indicated that a pair of oxidation/reduction peaks appeared at -111 mV and 581 mV, respectively. These results demonstrated that the proposed sediment microbial fuel cell-based biosensor can be applied as an early warning device for real time in situ detection of Cr(VI) in industrial wastewaters.

In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

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

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

2016-11-07

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Satellite SAR applied in offhore wind resource mapping: possibilities and limitations

NASA Astrophysics Data System (ADS)

Hasager, C. B.

Satellite remote sensing of ocean wind fields from Synthetic Aperture Radar (SAR) observations is presented. The study is based on a series of more than 60 ERS-2 SAR satellite scenes from the Horns Rev in the North Sea. The wind climate from the coastline and 80 km offshore is mapped in detail with a resolution of 400 m by 400 m grid cells. Spatial variations in wind speed as a function of wind direction and fetch are observed and discussed. The satellite wind fields are compared to in-situ observations from a tall offshore meteorological mast at which wind speed at 4 levels are analysed. The mast is located 14 km offshore and the wind climate is observed continously since May 1999. For offshore wind resource mapping the SAR-based wind field maps can constitute an alternative to in-situ observations and a practical method is developed for applied use in WAsP (Wind Atlas Analysis and Application Program). The software is the de facto world standard tool used for prediction of wind climate and power production from wind turbines and wind farms. The possibilities and limitations on achieving offshore wind resource estimates using SAR-based wind fields in lieu of in-situ data are discussed. It includes a presentation of the footprint area-averaging techniques tailored for SAR-based wind field maps. Averaging techniques are relevant for the reduction of noise apparent in SAR wind speed maps. Acknowledgments: Danish Research Agency (SAT-WIND Sagsnr. 2058-03-0006) for funding, ESA (EO-1356, AO-153) for ERS-2 SAR scenes, and Elsam Engineering A/S for in-situ met-data.

A Novel Early Warning System Based on a Sediment Microbial Fuel Cell for In Situ and Real Time Hexavalent Chromium Detection in Industrial Wastewater

PubMed Central

Zhao, Shuai; Liu, Pu; Niu, Yongyan; Chen, Zhengjun; Khan, Aman; Zhang, Pengyun; Li, Xiangkai

2018-01-01

Hexavalent chromium (Cr(VI)) is a well-known toxic heavy metal in industrial wastewater, but in situ and real time monitoring cannot be achieved by current methods used during industrial wastewater treatment processes. In this study, a Sediment Microbial Fuel Cell (SMFC) was used as a biosensor for in situ real-time monitoring of Cr(VI), which was the organic substrate is oxidized in the anode and Cr(VI) is reduced at the cathode simultaneously. The pH 6.4 and temperature 25 °C were optimal conditions for the operation. Under the optimal conditions, linearity (R2 = 0.9935) of the generated voltage was observed in the Cr(VI) concentration range from 0.2 to 0.7 mg/L. The system showed high specificity for Cr(VI), as other co-existing ions such as Cu2+, Zn2+, and Pb2+ did not interfere with Cr(VI) detection. In addition, when the sediment MFC-based biosensor was applied for measuring Cr(VI) in actual wastewater samples, a low deviation (<8%) was obtained, which indicated its potential as a reliable biosensor device. MiSeq sequencing results showed that electrochemically active bacteria (Geobacter and Pseudomonas) were enriched at least two-fold on the biofilm of the anode in the biosensor as compared to the SMFC without Cr(VI). Cyclic voltammetry curves indicated that a pair of oxidation/reduction peaks appeared at −111 mV and 581 mV, respectively. These results demonstrated that the proposed sediment microbial fuel cell-based biosensor can be applied as an early warning device for real time in situ detection of Cr(VI) in industrial wastewaters. PMID:29470394

A novel wood flour-filled composite based on microfibrillar high-density polyethylene (HDPE)/Nylon-6 blends.

PubMed

Liu, Hongzhi; Yao, Fei; Xu, Yanjun; Wu, Qinglin

2010-05-01

A novel wood flour (WF)-filled composite based on the microfibrillar high-density polyethylene (HDPE) and Nylon-6 co-blend, in which both in situ formed Nylon-6 microfibrils and WF acted as reinforcing elements, was successfully developed using a two-step extrusion method. At the 30wt.% WF loading level, WF-filled composite based on the microfibrillized HDPE/Nylon-6 blend exhibited higher strengths and moduli than the corresponding HDPE-based composite. The incorporation of WF reduced short-term creep response of HDPE matrix and the presence of Nylon-6 microfibrils further contributed to the creep reduction. Copyright 2009 Elsevier Ltd. All rights reserved.

Performance Indicators for Uranium Bioremediation in the Subsurface: Basis and Assessment

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

Long, Philip E.; Yabusaki, Steven B.

2006-12-29

The purpose of this letter report is to identify performance indicators for in situ engineered bioremediation of subsurface uranium (U) contamination. This report focuses on in situ treatment of groundwater by biostimulation of extant in situ microbial populations (see http://128.3.7.51/NABIR/generalinfo/primers_guides/03_NABIR_primer.pdf for background information on bioremediation of metals and radionuclides). The treatment process involves amendment of the subsurface with an electron donor such as acetate, lactate, ethanol or other organic compound such that in situ microorganisms mediate the reduction of U(VI) to U(IV). U(VI) precipitates as uraninite or other insoluble U phase. Uranium is thus immobilized in place by such processesmore » and is subject to reoxidation that may remobilize the reduced uranium. Related processes include augmenting the extant subsurface microbial populations, addition of electron acceptors, and introduction of chemically reducing materials such as zero-valent Fe. While metrics for such processes may be similar to those for in situ biostimulation, these related processes are not directly in the scope of this letter report.« less

Preparation and antibacterial properties of Ag@polydopamine/graphene oxide sheet nanocomposite

NASA Astrophysics Data System (ADS)

Zhou, Hao; Liu, Yunfang; Chi, Weidong; Yu, Changyuan; Yu, Yingjie

2013-10-01

Immobilization of silver nanoparticles (Ag NPs) on poly-dopamine (PDA) functionalized graphene oxide sheets (GOSs) were carried out by an easy in situ reduction method. The PDA layer was coated on the surface of the GOSs via the self-polymerization of dopamine under atmosphere condition. The PDA layer not only works as the chemisorption and reduction sites for silver ions to form Ag NPs but also stabilizes them. High-resolution transmission electron microscopy observation shows that the average size of the Ag NPs anchored on the PDA/GOS composite is about 2.8 nm. The inhibition zone diameter of the Ag@PDA/GOS nanocomposite is about 23.7 mm, whereas said diameter of the Ag NPs is only 18.5 mm. The minimum bactericidal concentration of the Ag@PDA/GOS nanocomposite is about 25 μg/ml that is only half of said concentration of the Ag NPs. The Ag@PDA/GOS nanocomposite exhibits an excellent antibacterial property.

Fast and sensitive optical toxicity bioassay based on dual wavelength analysis of bacterial ferricyanide reduction kinetics.

PubMed

Pujol-Vila, F; Vigués, N; Díaz-González, M; Muñoz-Berbel, X; Mas, J

2015-05-15

Global urban and industrial growth, with the associated environmental contamination, is promoting the development of rapid and inexpensive general toxicity methods. Current microbial methodologies for general toxicity determination rely on either bioluminescent bacteria and specific medium solution (i.e. Microtox(®)) or low sensitivity and diffusion limited protocols (i.e. amperometric microbial respirometry). In this work, fast and sensitive optical toxicity bioassay based on dual wavelength analysis of bacterial ferricyanide reduction kinetics is presented, using Escherichia coli as a bacterial model. Ferricyanide reduction kinetic analysis (variation of ferricyanide absorption with time), much more sensitive than single absorbance measurements, allowed for direct and fast toxicity determination without pre-incubation steps (assay time=10 min) and minimizing biomass interference. Dual wavelength analysis at 405 (ferricyanide and biomass) and 550 nm (biomass), allowed for ferricyanide monitoring without interference of biomass scattering. On the other hand, refractive index (RI) matching with saccharose reduced bacterial light scattering around 50%, expanding the analytical linear range in the determination of absorbent molecules. With this method, different toxicants such as metals and organic compounds were analyzed with good sensitivities. Half maximal effective concentrations (EC50) obtained after 10 min bioassay, 2.9, 1.0, 0.7 and 18.3 mg L(-1) for copper, zinc, acetic acid and 2-phenylethanol respectively, were in agreement with previously reported values for longer bioassays (around 60 min). This method represents a promising alternative for fast and sensitive water toxicity monitoring, opening the possibility of quick in situ analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

In situ assembly of well-dispersed Ni nanoparticles on silica nanotubes and excellent catalytic activity in 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Zhang, Shenghuan; Gai, Shili; He, Fei; Ding, Shujiang; Li, Lei; Yang, Piaoping

2014-09-01

The easy aggregation nature of ferromagnetic nanoparticles (NPs) prepared by conventional routes usually leads to a large particle size and low loading, which greatly limits their applications to the reduction of 4-nitrophenol (4-NP). Herein, we developed a novel in situ thermal decomposition and reduction strategy to prepare Ni nanoparticles/silica nanotubes (Ni/SNTs), which can markedly prevent the aggregation and growth of Ni NPs, resulting in an ultra-small particle size (about 6 nm), good dispersion and especially high loading of Ni NPs. It was found that Ni/SNTs, which have a high specific surface area (416 m2 g-1), exhibit ultra-high catalytic activity in the 4-NP reduction (complete reduction of 4-NP within only 60 s at room temperature), which is superior to most noble metal (Au, Pt, and Pd) supported catalysts. Ni/SNTs still showed high activity even after re-use for several cycles, suggesting good stability. In particular, the magnetic property of Ni/SNTs makes it easy to recycle for reuse.The easy aggregation nature of ferromagnetic nanoparticles (NPs) prepared by conventional routes usually leads to a large particle size and low loading, which greatly limits their applications to the reduction of 4-nitrophenol (4-NP). Herein, we developed a novel in situ thermal decomposition and reduction strategy to prepare Ni nanoparticles/silica nanotubes (Ni/SNTs), which can markedly prevent the aggregation and growth of Ni NPs, resulting in an ultra-small particle size (about 6 nm), good dispersion and especially high loading of Ni NPs. It was found that Ni/SNTs, which have a high specific surface area (416 m2 g-1), exhibit ultra-high catalytic activity in the 4-NP reduction (complete reduction of 4-NP within only 60 s at room temperature), which is superior to most noble metal (Au, Pt, and Pd) supported catalysts. Ni/SNTs still showed high activity even after re-use for several cycles, suggesting good stability. In particular, the magnetic property of Ni/SNTs makes it easy to recycle for reuse. Electronic supplementary information (ESI) available: XRD pattern and TEM image of SNTs after calcination, XRD pattern and EDS of NiSNTs, SEM images of a single SNT, NiSNTs and Ni/SNTs, enlarged HRTEM of Ni/SNTs, XRD pattern of NiO/SNTs, UV-vis spectra of the catalytic reduction of 4-NP to 4-AP over Ni/SNTs with different loading amounts, Ni/SNTs synthesized by wet impregnation and Ni/CNTs, TEM images of Ni/SNTs synthesized by wet impregnation and Ni/CNTs. See DOI: 10.1039/c4nr02096k

ADVANTAGES/DISADVANTAGES FOR ISCO METHODS IN-SITU FENTON OXIDATION IN-SITU PERMANGANATE OXIDATION

EPA Science Inventory

The advantages and disadvantages of in-situ Fenton oxidation and in-situ permanganate oxidation will be presented. This presentation will provide a brief overview of each technology and a detailed analysis of the advantages and disadvantages of each technology. Included in the ...

Gas injection to inhibit migration during an in situ heat treatment process

DOEpatents

Kuhlman, Myron Ira; Vinegar; Harold J.; Baker, Ralph Sterman; Heron, Goren

2010-11-30

Methods of treating a subsurface formation are described herein. Methods for treating a subsurface treatment area in a formation may include introducing a fluid into the formation from a plurality of wells offset from a treatment area of an in situ heat treatment process to inhibit outward migration of formation fluid from the in situ heat treatment process.

In situ measurements of dissolved oxygen, pH and redox potential of biocathode microenvironments using microelectrodes.

PubMed

Wang, Zejie; Deng, Huan; Chen, Lihui; Xiao, Yong; Zhao, Feng

2013-03-01

Biofilms are the core component of bioelectrochemical systems (BESs). To understand the polarization effects on biocathode performance of BES, dissolved oxygen concentrations, pHs and oxidation-reduction potentials of biofilm microenvironments were determined in situ. The results showed that lower polarization potentials resulted in the generation of larger currents and higher pH values, as well as the consumption of more oxygen. Oxidation-reduction potentials of biofilms were mainly affected by polarization potentials of the electrode rather than the concentration of dissolved oxygen or pH value, and its changes in the potentials corresponded to the electric field distribution of the electrode surface. The results demonstrated that a sufficient supply of dissolved oxygen and pH control of the biocathode are necessary to obtain optimal performance of BESs; a lower polarization potential endowed microorganisms with a higher electrochemical activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Stimulation of waste decomposition in an old landfill by air injection.

PubMed

Wu, Chuanfu; Shimaoka, Takayuki; Nakayama, Hirofumi; Komiya, Teppei; Chai, Xiaoli

2016-12-01

Three pilot-scale lysimeters were operated for 4.5years to quantify the change in the carbon and nitrogen pool in an old landfill under various air injection conditions. The results indicate that air injection at the bottom layer facilitated homogeneous distribution of oxygen in the waste matrix. Substantial total organic carbon (TOC) decomposition and methane generation reduction were achieved. Considerable amount of nitrogen was removed, suggesting that in situ nitrogen removal via the effective simultaneous nitrification and denitrification mechanism is viable. Moreover, material mass change measurements revealed a slight mass reduction of aged MSW (by approximately 4.0%) after 4.5years of aeration. Additionally, experiments revealed that intensive aeration during the final stage of the experiment did not further stimulate the degradation of the aged MSW. Therefore, elimination of the labile fraction of aged MSW should be considered the objective of in situ aeration. Copyright © 2016 Elsevier Ltd. All rights reserved.

High performance, inexpensive solar cell process capable of a high degree of automation

NASA Technical Reports Server (NTRS)

Shah, P.; Fuller, C. R.

1976-01-01

This paper proposes a process for inexpensive high performance solar cell fabrication that can be automated for further cost reduction and higher throughputs. The unique feature of the process is the use of oxides as doping sources for simultaneous n(+) junction formation and back p(+) layer, as a mask for metallization and as an in situ AR coating for spectrum matching. Cost analysis is performed to show that significant cost reductions over the conventional process is possible using the proposed scheme and the cost intensive steps are identified which can be further reduced to make the process compatible with the needed price goals of 50 cents/watt. The process was demonstrated by fabricating n(+)-p cells using Arsenic doped oxides. Simple n(+)-p structure cells showed corrected efficiencies of 14.5% (AMO) and 12% with doped oxide as an in situ antireflection coating.

Bioremediation of uranium-contaminated groundwater: a systems approach to subsurface biogeochemistry.

PubMed

Williams, Kenneth H; Bargar, John R; Lloyd, Jonathan R; Lovley, Derek R

2013-06-01

Adding organic electron donors to stimulate microbial reduction of highly soluble U(VI) to less soluble U(IV) is a promising strategy for immobilizing uranium in contaminated subsurface environments. Studies suggest that diagnosing the in situ physiological status of the subsurface community during uranium bioremediation with environmental transcriptomic and proteomic techniques can identify factors potentially limiting U(VI) reduction activity. Models which couple genome-scale in silico representations of the metabolism of key microbial populations with geochemical and hydrological models may be able to predict the outcome of bioremediation strategies and aid in the development of new approaches. Concerns remain about the long-term stability of sequestered U(IV) minerals and the release of co-contaminants associated with Fe(III) oxides, which might be overcome through targeted delivery of electrons to select microorganisms using in situ electrodes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18 O Labeling.

PubMed

Lum, Yanwei; Ager, Joel W

2018-01-08

Oxide-derived (OD) Cu catalysts have high selectivity towards the formation of multi-carbon products (C 2 /C 3 ) for aqueous electrochemical CO 2 reduction (CO 2 R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing 18 O-enriched OD Cu catalysts and testing them for CO 2 R. These catalysts maintain a high selectivity towards C 2 /C 3 products (ca. 60 %) for up to 5 h in 0.1 m KHCO 3 at -1.0 V vs. RHE. However, secondary-ion mass spectrometry measurements show that only a small fraction (<1 %) of the original 18 O content remains, showing that residual oxides are not present in significant amounts during CO 2 R. Furthermore, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of the environmental impact of Brownfield remediation options: comparison of two life cycle assessment-based evaluation tools.

PubMed

Cappuyns, Valérie; Kessen, Bram

2012-01-01

The choice between different options for the remediation of a contaminated site traditionally relies on economical, technical and regulatory criteria without consideration of the environmental impact of the soil remediation process itself. In the present study, the environmental impact assessment of two potential soil remediation techniques (excavation and off-site cleaning and in situ steam extraction) was performed using two life cycle assessment (LCA)-based evaluation tools, namely the REC (risk reduction, environmental merit and cost) method and the ReCiPe method. The comparison and evaluation of the different tools used to estimate the environmental impact of Brownfield remediation was based on a case study which consisted of the remediation of a former oil and fat processing plant. For the environmental impact assessment, both the REC and ReCiPe methods result in a single score for the environmental impact of the soil remediation process and allow the same conclusion to be drawn: excavation and off-site cleaning has a more pronounced environmental impact than in situ soil remediation by means of steam extraction. The ReCiPe method takes into account more impact categories, but is also more complex to work with and needs more input data. Within the routine evaluation of soil remediation alternatives, a detailed LCA evaluation will often be too time consuming and costly and the estimation of the environmental impact with the REC method will in most cases be sufficient. The case study worked out in this paper wants to provide a basis for a more sounded selection of soil remediation technologies based on a more detailed assessment of the secondary impact of soil remediation.

Assessing the potential of spectral induced polarization to detect in situ changes in iron reduction

NASA Astrophysics Data System (ADS)

Rosier, C. L.; Price, A.; Sharma, S.; Atekwana, E. A.

2016-12-01

The near surface geophysical technique Spectral Induced Polarization (SIP), provides promise as an effective method measuring in situ biofilm formation/development. Yet, potential mechanisms responsible for observed shifts in SIP response due to biofilm are not clearly understood. In order to address possible mechanisms we assessed the influence of Shewanella oneidensis (MR1) cell density (colony forming units; CFU), biofilm production (Bradford assay) and iron reduction metabolism (colorimetric assay) on SIP response. Laboratory measurements were collected over three months on columns packed with either iron-coated or iron-free sands and amended with artificial ground water and acetate in order to stimulate biofilm production and microbial iron reduction. Additionally, scanning electron microscopy (SEM) was used to confirm the presence of S. oneidensis cells and biofilm. Our results suggest that during early/initial stage (<30 days) of the iron-coated column incubations, both phase and imaginary conductivity response increased 4-fold as concentrations of reduced iron increased from 0-50 mM. In the later stages (>75 days) of column incubation, SIP measurements revealed that phase and imaginary conductivity responses decreased as the concentration of reduced iron decreased below 2.0 mM. In contrast, we observed only a moderate increase in phase and imaginary conductivity ( 30%) within iron-free columns as a result of increases in S. oneidensis cells (CFU 1.5 x 1011) and biofilm production (7.0 mg ml-1). SEM analysis confirmed the presence of biofilm and cells within both iron-coated and iron-free columns. We hypothesize that the production of microbial metabolic byproducts is a potential mechanism explaining large phase shits observed in previous studies ( 50 mrads) rather than the conductivity of cells or biofilm. Our findings provide support for the following: i) ratio of cells to biofilm production only moderately influences both phase and imaginary conductivity response and ii) largest phase and imaginary conductivity response resulted from microbial metabolism (i.e. iron reduction) and potentially biofilm trapping of conductive materials (i.e. cations).

Implementing an integrated in-situ coaching, observational audit, and story-telling intervention to support safe surgery.

PubMed

Carthey, Jane; McCormack, Katie; Coombes, Julie; Gilbert, Douglas; Farrar, Daniel

2016-12-01

This article describes an intervention that combined in-situ coaching, observational audits and story-telling to educate theatre teams at University College London Hospitals about the Five steps to safer surgery (NPSA 2010). Our philosophy was to educate theatre teams about 'what goes right' (good catches, exemplary leadership etc) as well as 'what could be improved'. Results showed improvements on 'behavioural reliability' metrics, a 68% increase in near miss reporting and a reduction in surgical harm incidents. Copyright the Association for Perioperative Practice.

Removal of amino groups from anilines through diazonium salt-based reactions.

PubMed

He, Linman; Qiu, Guanyinsheng; Gao, Yueqiu; Wu, Jie

2014-09-28

This minireview describes the applications of in situ generated diazonium salts from anilines in organic synthesis. In situ generation of diazonium salts from anilines represents an efficient and practical pathway, leading to a series of useful structures. In these transformations, the amino group of aniline formally acts as a leaving group. Two distinctive kinds of mechanisms, including transition metal (especially palladium)-catalyzed oxidative addition-reductive elimination and a radical process, are involved in the removal of amino groups from anilines, and both catalytic processes are described in this minireview.

In situ chemical degradation of DNAPLS in contaminated soils and sediments

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

Gates, D.D.; Korte, N.E.; Siegrist, R.L.

1996-08-01

An emerging approach to in situ treatment of organic contaminants is chemical degradation. The specific processes discussed in this chapter are in situ chemical oxidation using either hydrogen peroxide (H{sub 2}O{sub 2}) or potassium permanganate (KMnO{sub 4}) and in situ dechlorination of halogenated hydrocarbons using zero-valence base metals such as iron. These technologies are primarily chemical treatment processes, where the treatment goal is to manipulate the chemistry of the subsurface environment in such a manner that the contaminants of interest are destroyed and/or rendered non-toxic. Chemical properties that can be altered include pH, ionic strength, oxidation and reduction potential, andmore » chemical equilibria. In situ contaminant destruction processes alter or destroy contaminants in place and are typically applied to compounds that can be either converted to innocuous species such as CO{sub 2} and water, or can be degraded to species that are non-toxic or amenable to other in situ processes (i.e., bioremediation). With in situ chemical oxidation, the delivery and distribution of chemical reagents are critical to process effectiveness. In contrast, published approaches for the use of zero valence base metals suggest passive approaches in which the metals are used in a permeable reaction wall installed in situ in the saturated zone. Both types of processes are receiving increasing attention and are being applied both in technology demonstration and as final solutions to subsurface contaminant problems. 43 refs., 9 figs., 1 tab.« less

Determining the area of influence of depression cone in the vicinity of lignite mine by means of triangle method and LANDSAT TM/ETM+ satellite images.

PubMed

Zawadzki, Jarosław; Przeździecki, Karol; Miatkowski, Zygmunt

2016-01-15

Problems with lowering of water table are common all over the world. Intensive pumping of water from aquifers for consumption, irrigation, industrial or mining purposes often causes groundwater depletion and results in the formation of cone of depression. This can severely decrease water pressure, even over vast areas, and can create severe problems such as degradation of agriculture or natural environment sometimes depriving people and animals of water supply. In this paper, the authors present a method for determining the area of influence of a groundwater depression cone resulting from prolonged drainage, by means of satellite images in optical, near infrared and thermal infrared bands from TM sensor (Thematic Mapper) and ETM+ sensor (Enhanced Thematic Mapper +) placed on Landsat 5 and Landsat 7 satellites. The research area was Szczercowska Valley (Pol. Kotlina Szczercowska), Central Poland, located within a range of influence of a groundwater drainage system of the lignite coal mine in Belchatow. It is the biggest lignite coal mine in Poland and one of the largest in Europe exerting an enormous impact on the environment. The main method of satellite data analysis for determining soil moisture, was the so-called triangle method. This method, based on TVDI (Temperature Vegetation Dryness Index) was supported by additional spatial analysis including ordinary kriging used in order to combine fragmentary information obtained from areas covered by meadows. The results obtained are encouraging and confirm the usefulness of the triangle method not only for soil moisture determination but also for assessment of the temporal and spatial changes in the area influenced by the groundwater depression cone. The range of impact of the groundwater depression cone determined by means of above-described remote sensing analysis shows good agreement with that determined by ground measurements. The developed satellite method is much faster and cheaper than in-situ measurements, and allows for systematic monitoring of the vast area in the vicinity of Belchatow lignite mine. Besides, this method could be useful as a helper in in-situ measurement allowing a significant reduction of the number of in-situ measurements by performing them only within problematic areas. Hence, the triangle method can be used as an effective supplement to field measurements. Although the research area is located in Poland, in the vicinity of lignite mine, the method of observation of depression cones provided in this study is universal and effective, and therefore could also be useful to an international audience. Copyright © 2015 Elsevier Ltd. All rights reserved.

High strength-high conductivity Cu--Fe composites produced by powder compaction/mechanical reduction

DOEpatents

Verhoeven, John D.; Spitzig, William A.; Gibson, Edwin D.; Anderson, Iver E.

1991-08-27

A particulate mixture of Cu and Fe is compacted and mechanically reduced to form an "in-situ" Cu-Fe composite having high strength and high conductivity. Compaction and mechanical reduction of the particulate mixture are carried out at a temperature and time at temperature selected to avoid dissolution of Fe into the Cu matrix particulates to a harmful extent that substantially degrades the conductivity of the Cu-Fe composite.

Measurement of benzenethiol adsorption to nanostructured Pt, Pd, and PtPd films using Raman spectroelectrochemistry.

PubMed

Pomfret, Michael B; Pietron, Jeremy J; Owrutsky, Jeffrey C

2010-05-04

Raman spectroscopy and electrochemical methods were used to study the behavior of the model adsorbate benzenethiol (BT) on nanostructured Pt, Pd, and PtPd electrodes as a function of applied potential. Benzenethiol adsorbs out of ethanolic solutions as the corresponding thiolate, and voltammetric stripping data reveal that BT is oxidatively removed from all of the nanostructured metals upon repeated oxidative and reductive cycling. Oxidative stripping potentials for BT increase in the order Pt < PtPd < Pd, indicating that BT adsorbs most strongly to nanoscale Pd. Yet, BT Raman scattering intensities, measured in situ over time scales of minutes to hours, are most persistent on the film of nanostructured Pt. Raman spectra indicate that adsorbed BT desorbs from nanoscale Pt at oxidizing potentials via cleavage of the Pt-S bond. In contrast, on nanoscale Pd and PtPd, BT is irreversibly lost due to cleavage of BT C-S bonds at oxidizing potentials, which leaves adsorbed sulfur oxides on Pd and PtPd films and effects the desulfurization of BT. While Pd and PtPd films are less sulfur-resistant than Pt films, palladium oxides, which form at higher potentials than Pt oxides, oxidatively desulfurize BT. In situ spectroelectrochemical Raman spectroscopy provides real-time, chemically specific information that complements the cyclic voltammetric data. The combination of these techniques affords a powerful and convenient method for guiding the development of sulfur-tolerant PEMFC catalysts.

Green synthesis of silver nanoparticles using Stevia leaves extracts

NASA Astrophysics Data System (ADS)

Laguta, Iryna; Stavinskaya, Oksana; Kazakova, Olga; Fesenko, Tetiana; Brychka, Sergey

2018-02-01

Three extracts of Stevia rebaudiana (Bertoni) were prepared using different types of raw materials: leaves of plants grown ex situ, leaves of plants grown in vitro, callus culture formed on damaged leaves. Composition of the extracts was studied by means of high-performance liquid chromatography and laser desorption/ionization mass spectrometry; total phenol content was estimated using Folin-Ciocalteau method. Flavonoids and hydroxycinnamic acids were found to be the main groups of phenol antioxidants available in the Stevia leaves, with the amount of these compounds in the extract being dependent on the type of raw material. The reducing properties of phenol compounds identified in the extracts were characterized using quantum chemical method; flavonoids and hydroxycinnamic acids were found to have similar redox parameters. Silver nanoparticles (AgNPs) colloids were synthesized using three Stevia extracts; AgNPs size distribution were characterized by means of scanning electron microscopy. All the extracts revealed significant activity in AgNPs synthesis; the nanoparticles of predominantly spherical shape with the average sizes of 16-25 nm were formed. The reducing properties of the extracts were found to correlate with total phenol content; the activity of extracts from the leaves of plants grown ex situ and from callus culture in Ag+ ions reduction was similar to each other and exceeded the activity of extract from the leaves of plants grown in vitro.

Reactive transport model for bioremediation of nitrate using fumarate in groundwater system: verification and field application

NASA Astrophysics Data System (ADS)

Lee, S.; Yeo, I. W.; Yeum, Y.; Kim, Y.

2016-12-01

Previous studies showed that groundwater of rural areas in Korea is often contaminated with nitrate highly exceeding the drinking water standard of 10 mg/L (NO3-N), which poses a major threat in human and livestock health. In-situ bioremediation method has been developed to reduce high nitrate-nitrogen concentration in groundwater using slowly released encapsulated carbon source. Collaborative research of this study revealed that fumarate was found to be a very effective carbon source in terms of cost and nitrate reduction against formate, propionate, and lactate. For reactive transport modeling of the bioremediation of nitrate using fumarate, the BTEX module of RT3D incorporated in GMS, a commercial groundwater modeling software developed by AQUAVEO, was adopted, where BTEX was replaced with fumarate as a carbon source. Column tests were carried out to determine transport and reaction parameters for numerical modeling such as dispersity and first order degradation rate of nitrate by fumarate. The calibration of the numerical model against column tests strongly indicated that nitrate, known to be not reactive in groundwater system, appeared to be retarded due to sorption by fumarate. The calibrated model was tested for field-scale application to the composting facility in Gimje, Korea. The numerical results showed that the model could simulate the nitrate reduction by fumarate in field scale groundwater system. The reactive transport model for nitrate can be used as a tool for optimum design of in-situ nitrate bioremediation system, such as released depth and amount of fumarate and the spacing of wells that encapsulated fumarate is released through.

Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

DOE PAGES

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; ...

2016-05-19

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil

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

Choi, Jae-Soon; Zacher, Alan H.; Wang, Huamin

We assessed molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60-h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt% andmore » 0.01 mg KOH g-1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60-h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are promising catalytic materials which could lead to a significant cost reduction in hydroprocessing bio-oils. This paper highlights areas for future research which will be needed to further understand carbide structure-function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

On the Mechanism of In Nanoparticle Formation by Exposing ITO Thin Films to Hydrogen Plasmas.

PubMed

Fan, Zheng; Maurice, Jean-Luc; Chen, Wanghua; Guilet, Stéphane; Cambril, Edmond; Lafosse, Xavier; Couraud, Laurent; Merghem, Kamel; Yu, Linwei; Bouchoule, Sophie; Roca I Cabarrocas, Pere

2017-10-31

We present our systematic work on the in situ generation of In nanoparticles (NPs) from the reduction of ITO thin films by hydrogen (H 2 ) plasma exposure. In contrast to NP deposition from the vapor phase (i.e., evaporation), the ITO surface can be considered to be a solid reservoir of In atoms thanks to H 2 plasma reduction. On one hand, below the In melting temperature, solid In NP formation is governed by the island-growth mode, which is a self-limiting process because the H 2 plasma/ITO interaction will be gradually eliminated by the growing In NPs that cover the ITO surface. On the other hand, we show that above the melting temperature In droplets prefer to grow along the grain boundaries on the ITO surface and dramatic coalescence occurs when the growing NPs connect with each other. This growth-connection-coalescence behavior is even strengthened on In/ITO bilayers, where In particles larger than 10 μm can be formed, which are made of evaporated In atoms and in situ released ones. Thanks to this understanding, we manage to disperse dense evaporated In NPs under H 2 plasma exposure when inserting an ITO layer between them and substrate like c-Si wafer or glass by modifying the substrate surface chemistry. Further studies are needed for more precise control of this self-assembling method. We expect that our findings are not limited to ITO thin films but could be applicable to various metal NPs generation from the corresponding metal oxide thin films.

Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

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

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

Microbial Manganese and Sulfate Reduction in Black Sea Shelf Sediments

PubMed Central

Thamdrup, Bo; Rosselló-Mora, Ramón; Amann, Rudolf

2000-01-01

The microbial ecology of anaerobic carbon oxidation processes was investigated in Black Sea shelf sediments from mid-shelf with well-oxygenated bottom water to the oxic-anoxic chemocline at the shelf-break. At all stations, organic carbon (Corg) oxidation rates were rapidly attenuated with depth in anoxically incubated sediment. Dissimilatory Mn reduction was the most important terminal electron-accepting process in the active surface layer to a depth of ∼1 cm, while SO42− reduction accounted for the entire Corg oxidation below. Manganese reduction was supported by moderately high Mn oxide concentrations. A contribution from microbial Fe reduction could not be discerned, and the process was not stimulated by addition of ferrihydrite. Manganese reduction resulted in carbonate precipitation, which complicated the quantification of Corg oxidation rates. The relative contribution of Mn reduction to Corg oxidation in the anaerobic incubations was 25 to 73% at the stations with oxic bottom water. In situ, where Mn reduction must compete with oxygen respiration, the contribution of the process will vary in response to fluctuations in bottom water oxygen concentrations. Total bacterial numbers as well as the detection frequency of bacteria with fluorescent in situ hybridization scaled to the mineralization rates. Most-probable-number enumerations yielded up to 105 cells of acetate-oxidizing Mn-reducing bacteria (MnRB) cm−3, while counts of Fe reducers were <102 cm−3. At two stations, organisms affiliated with Arcobacter were the only types identified from 16S rRNA clone libraries from the highest positive MPN dilutions for MnRB. At the third station, a clone type affiliated with Pelobacter was also observed. Our results delineate a niche for dissimilatory Mn-reducing bacteria in sediments with Mn oxide concentrations greater than ∼10 μmol cm−3 and indicate that bacteria that are specialized in Mn reduction, rather than known Mn and Fe reducers, are important in this niche. PMID:10877783

The effect of flap thickness on corneal biomechanics after myopic laser in situ keratomileusis using the M-2 microkeratome

PubMed Central

Goussous, Iyad A; El-Agha, Mohamed-Sameh; Awadein, Ahmed; Hosny, Mohamed H; Ghaith, Alaa A; Khattab, Ahmed L

2017-01-01

Purpose The purpose of this study was to determine the effect of flap thickness on corneal biomechanics after myopic laser in situ keratomileusis (LASIK). Methods This is a prospective controlled non-randomized, institutional study. Patients underwent either epi-LASIK with mitomycin (advanced surface ablation [ASA]), thin-flap LASIK (90 µm head), or thick-flap LASIK (130 µm head). In ASA, the Moria Epi-K hydroseparator was used. LASIK flaps were created using the Moria M-2 mechanical microkeratome. The corneal hysteresis (CH) and corneal resistance factor (CRF) were measured preoperatively and 3 months after surgery, using the Ocular Response Analyzer®. Results Ten patients (19 eyes) underwent ASA, 11 patients (16 eyes) underwent thin-flap LASIK, and 11 patients (16 eyes) underwent thick-flap LASIK. The mean preoperative CH was 10.47±0.88, 10.52±1.4, and 11.28±1.4 mmHg (p=0.043), respectively, decreasing after surgery by 1.75±1.02, 1.66±1.00, and 2.62±1.03 mmHg (p=0.017). The mean reduction of CH per micron of central corneal ablation was 0.031, 0.023, and 0.049 mmHg/µm (p=0.005). Mean preoperative CRF was 10.11±1.28, 10.34±1.87, and 10.62±1.76 mmHg (p=0.66), decreasing after surgery by 2.33±1.35, 2.77±1.03, and 2.92±1.10 mmHg (p=0.308). The mean reduction of CRF per micron of central corneal ablation was 0.039, 0.040, and 0.051 mmHg/µm (p=0.112). Conclusion Thick-flap LASIK caused a greater reduction of CH and CRF than thin-flap LASIK and ASA, although this was statistically significant only for CH. ASA and thin-flap LASIK were found to be biomechanically similar. PMID:29200820

Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid

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

Jia, Qingying; Ramaswamy, Nagappan; Tylus, Urszula

Developing efficient and inexpensive catalysts for the sluggish oxygen reduction reaction (ORR) constitutes one of the grand challenges in the fabrication of commercially viable fuel cell devices and metal–air batteries for future energy applications. Despite recent achievements in designing advanced Pt-based and Pt-free catalysts, current progress primarily involves an empirical approach of trial-and-error combination of precursors and synthesis conditions, which limits further progress. Rational design of catalyst materials requires proper understanding of the mechanistic origin of the ORR and the underlying surface properties under operating conditions that govern catalytic activity. Herein, several different groups of iron-based catalysts synthesized via differentmore » methods and/or precursors were systematically studied by combining multiple spectroscopic techniques under ex situ and in situ conditions in an effort to obtain a comprehensive understanding of the synthesis-products correlations, nature of active sites, and the reaction mechanisms. These catalysts include original macrocycles, macrocycle-pyrolyzed catalysts, and Fe-N–C catalysts synthesized from individual Fe, N, and C precursors including polymer-based catalysts, metal organic framework (MOF)-based catalysts, and sacrificial support method (SSM)-based catalysts. The latter group of catalysts is most promising as not only they exhibit exceptional ORR activity and/or durability, but also the final products are controllable. We show that the high activity observed for most pyrolyzed Fe-based catalysts can mainly be attributed to a single active site: non-planar Fe–N 4 moiety embedded in distorted carbon matrix characterized by a high potential for the Fe 2+/3+ redox transition in acidic electrolyte/environment. The high intrinsic ORR activity, or turnover frequency (TOF), of this site is shown to be accounted for by redox catalysis mechanism that highlights the dominant role of the site-blocking effect. Moreover, a highly active MOF-based catalyst without Fe–N moieties was developed, and the active sites were identified as nitrogen-doped carbon fibers with embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this second site, as demonstrated in fuel cell, are attributed to the high density of active sites and the elimination or reduction of Fenton-type processes. The latter are initiated by hydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals.« less

Probing the formation mechanism and chemical states of carbon-supported Pt-Ru nanoparticles by in situ X-ray absorption spectroscopy.

PubMed

Hwang, Bing Joe; Chen, Ching-Hsiang; Sarma, Loka Subramanyam; Chen, Jiun-Ming; Wang, Guo-Rung; Tang, Mau-Tsu; Liu, Din-Goa; Lee, Jyh-Fu

2006-04-06

The understanding of the formation mechanism of nanoparticles is essential for the successful particle design and scaling-up process. This paper reports findings of an X-ray absorption spectroscopy (XAS) investigation, comprised of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions, to understand the mechanism of the carbon-supported Pt-Ru nanoparticles (NPs) formation process. We have utilized Watanabe's colloidal reduction method to synthesize Pt-Ru/C NPs. We slightly modified the Watanabe method by introducing a mixing and heat treatment step of Pt and Ru oxidic species at 100 degrees C for 8 h with a view to enhance the mixing efficiency of the precursor species, thereby one can achieve improved homogeneity and atomic distribution in the resultant Pt-Ru/C NPs. During the reduction process, in situ XAS measurements allowed us to follow the evolution of Pt and Ru environments and their chemical states. The Pt LIII-edge XAS indicates that when H2PtCl6 is treated with NaHSO3, the platinum compound is found to be reduced to a Pt(II) form corresponding to the anionic complex [Pt(SO3)4]6-. Further oxidation of this anionic complex with hydrogen peroxide forms dispersed [Pt(OH)6]2- species. Analysis of Ru K-edge XAS results confirms the reduction of RuIIICl3 to [RuII(OH)4]2- species upon addition of NaHSO3. Addition of hydrogen peroxide to [RuII(OH)4]2- causes dehydrogenation and forms RuOx species. Mixing of [Pt(OH)6]2- and RuOx species and heat treatment at 100 degrees C for 8 h produced a colloidal sol containing both Pt and Ru metallic as well as ionic contributions. The reduction of this colloidal mixture at 300 degrees C in hydrogen atmosphere for 2 h forms Pt-Ru nanoparticles as indicated by the presence of Pt and Ru atoms in the first coordination shell. Determination of the alloying extent or atomic distribution of Pt and Ru atoms in the resulting Pt-Ru/C NPs reveals that the alloying extent of Ru (JRu) is greater than that of the alloying extent of Pt (JPt). The XAS results support the Pt-rich core and Ru-rich shell structure with a considerable amount of segregation in the Pt region and with less segregation in the Ru region for the obtained Pt-Ru/C NPs.

Acute deep vein thrombosis and endovascular techniques: It is time for a new aggiornamento!

PubMed

Pernès, J-M; Auguste, M; Kovarski, S; Borie, H; Renaudin, J-M; Coppe, G

2012-10-01

The stated aims of treating acute deep vein thrombosis (DVT) are to prevent a pulmonary embolism, stop the clot from spreading, reduce the risk of a recurrence; they are less concerned with the late morbidity associated with post-thrombotic syndrome (PTS). In accordance with the French (Afssaps, 2009) and North American (ACCP, 2008) recommendations, anticoagulants (LMWH, heparin, AVK) form the cornerstone for treating DVT. These treatments appear to be far less effective in preventing post-thrombotic syndrome (PTS), associated with venous hypertension, residual occlusion, and with reflux caused by valve incompetence. Given that, the new aim is to optimise the prevention of PTS, the ACCP guidelines, unlike those of Afssaps, "suggest" for selected patients suffering from acute iliofemoral DVT, the use of both classic anticoagulants, and in situ percutaneous administration of thrombolytic drugs (recommendation grade 2B) and simultaneous correction of any underlying anatomical anomalies using angioplasty and stenting (recommendation 2C). Contemporary endovascular methods, referred to collectively as "facilitated" thrombolysis, combine low doses of rtPa or Urokinase administered locally, and the removal of the clot using various mechanical, rotating, rheolytic systems, or using ultrasound. The results of non-randomised, heterogeneous studies objectivised a lysis rate of 80%, a 50% lower risk of haemorrhage complications compared with systemic thrombolysis (<4%), and a clear reduction in treatment time (one-shot methods possible for procedures lasting less than 2 hours). This data ties in with the modern "open vein" concept which underpins the hope of an improvement in the late prognosis of acute DVT, through the removal of a clot, thereby improving permeability and valve integrity; this hypothesis is supported by the results at 24 months of a randomised CaVent objectifying absolute risk reduction of 15% in the thrombolysis in situ. The current randomised study (ATTRACT trial) comparing the combination of "facilitated thrombolysis" in addition to the usual treatment with the traditional treatment alone for acute iliofemoral DVT, the statistical power of which has been established (600 patients) to authenticate a reduction by a third in the number of PTS (CaVent trial, showing a 15% reduction rate of 24 months PTS in the thrombolysed group results expected in 2016), might, if the results are positive, lead to a profound change in the paradigms for the treatment of acute iliofemoral DVT. Copyright © 2012 Éditions françaises de radiologie. Published by Elsevier Masson SAS. All rights reserved.

In-situ polymerization PLOT columns I: divinylbenzene

NASA Technical Reports Server (NTRS)

Shen, T. C.

1992-01-01

A novel method for preparation of porous-layer open-tubular (PLOT) columns is described. The method involves a simple and reproducible, straight-forward in-situ polymerization of monomer directly on the metal tube.

High-pressure hydrogen respiration in hydrothermal vent samples from the deep biosphere

NASA Astrophysics Data System (ADS)

Morgan-Smith, D.; Schrenk, M. O.

2013-12-01

Cultivation of organisms from the deep biosphere has met with many challenges, chief among them the ability to replicate this extreme environment in a laboratory setting. The maintenance of in situ pressure levels, carbon sources, and gas concentrations are important, intertwined factors which may all affect the growth of subsurface microorganisms. Hydrogen in particular is of great importance in hydrothermal systems, but in situ hydrogen concentrations are largely disregarded in attempts to culture from these sites. Using modified Hungate-type culture tubes (Bowles et al. 2011) within pressure-retaining vessels, which allow for the dissolution of higher concentrations of gas than is possible with other culturing methods, we have incubated hydrothermal chimney and hydrothermally-altered rock samples from the Lost City and Mid-Cayman Rise hydrothermal vent fields. Hydrogen concentrations up to 15 mmol/kg have been reported from Lost City (Kelley et al. 2005), but data are not yet available from the recently-discovered Mid-Cayman site, and the elevated concentration of 30 mmol/kg is being used in all incubations. We are using a variety of media types to enrich for various metabolic pathways including iron and sulfur reduction under anoxic or microaerophilic conditions. Incubations are being carried out at atmospheric (0.1 MPa), in situ (9, 23, or 50 MPa, depending on site), and elevated (50 MPa) pressure levels. Microbial cell concentrations, taxonomic diversity, and metabolic activities are being monitored during the course of these experiments. These experiments will provide insight into the relationships between microbial activities, pressure, and gas concentrations typical of deep biosphere environments. Results will inform further culturing studies from both fresh and archived samples. References cited: Bowles, M.W., Samarkin, V.A., Joye, S.B. 2011. Improved measurement of microbial activity in deep-sea sediments at in situ pressure and methane concentration. Limnology and Oceanography Methods 9:499-506 Kelley, D.S., Karson, J.A., Früh-Green, G.L., Yoerger, D.R., Shank, T.M., et al. 2005. A Serpentinite-Hosted Ecosystem: The Lost City Hydrothermal Field. Science 307:1428-1434

Emulsification of hydrocarbons by subsurface bacteria

USGS Publications Warehouse

Francy, D.S.; Thomas, J.M.; Raymond, R.L.; Ward, C.H.

1991-01-01

Biosurfactants have potential for use in enhancement of in situ biorestoration by increasing the bioavailability of contaminants. Microorganisms isolated from biostimulated, contaminated and uncontaminated zones at the site of an aviation fuel spill and hydrocarbon-degrading microorganisms isolated from sites contaminated with unleaded gasoline were examined for their abilities to emulsify petroleum hydrocarbons. Emulsifying ability was quantified by a method involving agitation and visual inspection. Biostimulated-zone microbes and hydrocarbon-degrading microorganisms were the best emulsifiers as compared to contaminated and uncontaminated zone microbes. Biostimulation (nutrient and oxygen addition) may have been the dominant factor which selected for and encouraged growth of emulsifiers; exposure to hydrocarbon was also important. Biostimulated microorganisms were better emulsifiers of aviation fuel (the contaminant hydrocarbon) than of heavier hydrocarbon to which they were not previously exposed. By measuring surface tension changes of culture broths, 11 out of 41 emulsifiers tested were identified as possible biosurfactant producers and two isolates produced large surface tension reductions indicating the high probability of biosurfactant production.Biosurfactants have potential for use in enhancement of in situ biorestoration by increasing the bioavailability of contaminants. Microorganisms isolated from biostimulated, contaminated and uncontaminated zones at the site of an aviation fuel spill and hydrocarbon-degrading microorganisms isolated from sites contaminated with unleaded gasoline were examined for their abilities to emulsify petroleum hydrocarbons. Emulsifying ability was quantified by a method involving agitation and visual inspection. Biostimulated-zone microbes and hydrocarbon-degrading microorganisms were the best emulsifiers as compared to contaminated and uncontaminated zone microbes. Biostimulation (nutrient and oxygen addition) may have been the dominant factor which selected for and encouraged growth of emulsifiers; exposure to hydrocarbon was also important. Biostimulated microorganisms were better emulsifiers of aviation fuel (the contaminant hydrocarbon) than of heavier hydrocarbon to which they were not previously exposed. By measuring surface tension changes of culture broths, 11 out of 41 emulsifiers tested were identified as possible biosurfactant producers and two isolates produced large surface tension reductions, indicating a high probability of biosurfactant production.

In situ high-pressure measurement of crystal solubility by using neutron diffraction

NASA Astrophysics Data System (ADS)

Chen, Ji; Hu, Qiwei; Fang, Leiming; He, Duanwei; Chen, Xiping; Xie, Lei; Chen, Bo; Li, Xin; Ni, Xiaolin; Fan, Cong; Liang, Akun

2018-05-01

Crystal solubility is one of the most important thermo-physical properties and plays a key role in industrial applications, fundamental science, and geoscientific research. However, high-pressure in situ measurements of crystal solubility remain very challenging. Here, we present a method involving high-pressure neutron diffraction for making high-precision in situ measurements of crystal solubility as a function of pressure over a wide range of pressures. For these experiments, we designed a piston-cylinder cell with a large chamber volume for high-pressure neutron diffraction. The solution pressures are continuously monitored in situ based on the equation of state of the sample crystal. The solubility at a high pressure can be obtained by applying a Rietveld quantitative multiphase analysis. To evaluate the proposed method, we measured the high-pressure solubility of NaCl in water up to 610 MPa. At a low pressure, the results are consistent with the previous results measured ex situ. At a higher pressure, more reliable data could be provided by using an in situ high-pressure neutron diffraction method.

The Validation of Vapor Phase Hydrogen Peroxide Microbial Reduction for Planetary Protection and a Proposed Vacuum Process Specification

NASA Technical Reports Server (NTRS)

Chung, Shirley; Barengoltz, Jack; Kern, Roger; Koukol, Robert; Cash, Howard

2006-01-01

The Jet Propulsion Laboratory, in conjunction with the NASA Planetary Protection Officer, has selected the vapor phase hydrogen peroxide sterilization process for continued development as a NASA approved sterilization technique for spacecraft subsystems and systems. The goal is to include this technique, with an appropriate specification, in NPR 8020.12C as a low temperature complementary technique to the dry heat sterilization process.To meet microbial reduction requirements for all Mars in-situ life detection and sample return missions, various planetary spacecraft subsystems will have to be exposed to a qualified sterilization process. This process could be the elevated temperature dry heat sterilization process (115 C for 40 hours) which was used to sterilize the Viking lander spacecraft. However, with utilization of such elements as highly sophisticated electronics and sensors in modern spacecraft, this process presents significant materials challenges and is thus an undesirable bioburden reduction method to design engineers. The objective of this work is to introduce vapor hydrogen peroxide (VHP) as an alternative to dry heat microbial reduction to meet planetary protection requirements.The VHP process is widely used by the medical industry to sterilize surgical instruments and biomedical devices, but high doses of VHP may degrade the performance of flight hardware, or compromise material properties. Our goal for this study was to determine the minimum VHP process conditions to achieve microbial reduction levels acceptable for planetary protection.

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: structure-activity relationship

NASA Astrophysics Data System (ADS)

Guo, Yu; Gu, Dong; Jin, Zhao; Du, Pei-Pei; Si, Rui; Tao, Jing; Xu, Wen-Qian; Huang, Yu-Ying; Senanayake, Sanjaya; Song, Qi-Sheng; Jia, Chun-Jiang; Schüth, Ferdi

2015-03-01

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H2-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation.

PubMed

Zhao, Xiao; Liu, Wen; Cai, Zhengqing; Han, Bing; Qian, Tianwei; Zhao, Dongye

2016-09-01

Nano-scale zero-valent iron (nZVI) is one of the most intensively studied materials for environmental cleanup uses over the past 20 years or so. Freshly prepared nZVI is highly reactive due to its high specific surface area and strong reducing power. Over years, the classic borohydride reduction method for preparing nZVI has been modified by use of various stabilizers or surface modifiers to acquire more stable and soil deliverable nZVI for treatment of different organic and inorganic contaminants in water and soil. While most studies have been focused on testing nZVI for water treatment, the greater potential or advantage of nZVI appears to be for in situ remediation of contaminated soil and groundwater by directly delivering stabilized nZVI into the contaminated subsurface as it was proposed from the beginning. Compared to conventional remediation practices, the in situ remediation technique using stabilized nZVI offers some unique advantages. This work provides an update on the latest development of stabilized nZVI for various environmental cleanup uses, and overviews the evolution and environmental applications of stabilized nZVI. Commonly used stabilizers are compared and the stabilizing mechanisms are discussed. The effectiveness and constraints of the nZVI-based in situ remediation technology are summarized. This review also reveals some critical knowledge gaps and research needs, such as interactions between delivered nZVI and the local biogeochemical conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Assessment of in situ and ex situ phytorestoration with grass mixtures in soils polluted with nickel, copper, and arsenic

NASA Astrophysics Data System (ADS)

Zacarías Salinas, Montserrat; Beltrán Villavicencio, Margarita; Bustillos, Luis Gilberto Torres; González Aragón, Abelardo

This work shows a study of in situ and ex situ phytoextraction as a polishing step in the treatment of an industrial urban soil polluted with nickel, arsenic and copper. The soil was previously washed, and phytoextraction was performed by application of a mixture of grass (Festuca rubra, Cynodon dactylon, Lolium multiforum, Pennisetum). The soil had initial heavy metals concentrations of 131 ppm for Ni, 717 for As and 2734 for Cu (mg of metal/kg of dry soil). After seeding and emerging of grass, vegetal and soil samples were taken monthly during 4 months. Biomass generation, and concentration of Ni, As and Cu in vegetal tissue and soil were determined for every sample. Plants biomass growth in ex situ process was inhibited by 37% when compared with blank soil. Grass showed remarkable phytoextraction capability in situ, it produced 38 g of biomass every 15 days (wet weight) during a period of 3 months, but then declined in the fourth month. Concentrations of metals in grass biomass were up to 83 mg Ni/kg, 649 mg As/kg and 305 mg Cu/kg dry weight. Metal reduction of 49% for Ni, and 35% for Cu and As was observed at rhizospheric soil.

A fabrication strategy for nanosized zero valent iron (nZVI)-polymeric anion exchanger composites with tunable structure for nitrate reduction.

PubMed

Jiang, Zhenmao; Zhang, Shujuan; Pan, Bingcai; Wang, Wenfeng; Wang, Xiaoshu; Lv, Lu; Zhang, Weiming; Zhang, Quanxing

2012-09-30

To reveal how the distribution of nanoscale zero-valent iron (nZVI) affect their reduction efficiency of its polymer-based composites and to further develop a simple strategy to tune the structure of the composites, we prepared four nZVI-polymerstyrene anion exchanger composites with similar nZVI loadings (13.5-14.4 Fe % in mass) but different distributions just through varying the concentration of NaBH(4) (0.9, 1.8, 3.6, and 7.2% in mass) solution during reduction of nZVI precursor (FeCl(4)(-) anions). As observed by SEM-EDX images, increasing the NaBH(4) concentration resulted in a more uniform nZVI distribution within the polymer, and thereto higher NH(4)(+)N production, faster reaction rate and more gaseous products during its reduction of nitrate and nitrite. nZVI distribution of the composites was suggested to greatly depend upon two processes, the hydrolyzation of anionic FeCl(4)(-) into cationic Fe(3+) and the reduction of both Fe(III) species by NaBH(4). Higher NaBH(4) concentration favored its faster diffusion into the inside polymer and in situ reduction of Fe(III) species into nZVI, causing a more uniform nZVI distribution. The results reported herein suggest that adjusting the NaBH(4) concentration was a simple and effective method to control the nZVI distribution in the supporting polymers, and indirectly tune the reactivity of the resultant nZVI hybrids. Copyright © 2012 Elsevier B.V. All rights reserved.

Continuous flow reduction of artemisinic acid utilizing multi-injection strategies-closing the gap towards a fully continuous synthesis of antimalarial drugs.

PubMed

Pieber, Bartholomäus; Glasnov, Toma; Kappe, C Oliver

2015-03-09

One of the rare alternative reagents for the reduction of carbon-carbon double bonds is diimide (HN=NH), which can be generated in situ from hydrazine hydrate (N2H4⋅H2O) and O2. Although this selective method is extremely clean and powerful, it is rarely used, as the rate-determining oxidation of hydrazine in the absence of a catalyst is relatively slow using conventional batch protocols. A continuous high-temperature/high-pressure methodology dramatically enhances the initial oxidation step, at the same time allowing for a safe and scalable processing of the hazardous reaction mixture. Simple alkenes can be selectively reduced within 10-20 min at 100-120 °C and 20 bar O2 pressure. The development of a multi-injection reactor platform for the periodic addition of N2H4⋅H2O enables the reduction of less reactive olefins even at lower reaction temperatures. This concept was utilized for the highly selective reduction of artemisinic acid to dihydroartemisinic acid, the precursor molecule for the semisynthesis of the antimalarial drug artemisinin. The industrially relevant reduction was achieved by using four consecutive liquid feeds (of N2H4⋅H2O) and residence time units resulting in a highly selective reduction within approximately 40 min at 60 °C and 20 bar O2 pressure, providing dihydroartemisinic acid in ≥93% yield and ≥95% selectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The remediation of heavy metals contaminated sediment.

PubMed

Peng, Jian-Feng; Song, Yong-Hui; Yuan, Peng; Cui, Xiao-Yu; Qiu, Guang-Lei

2009-01-30

Heavy metal contamination has become a worldwide problem through disturbing the normal functions of rivers and lakes. Sediment, as the largest storage and resources of heavy metal, plays a rather important role in metal transformations. This paper provides a review on the geochemical forms, affecting factors and remediation technologies of heavy metal in sediment. The in situ remediation of sediment aims at increasing the stabilization of some metals such as the mobile and the exchangeable fractions; whereas, the ex situ remediation mainly aims at removing those potentially mobile metals, such as the Mn-oxides and the organic matter (OM) fraction. The pH and OM can directly change metals distribution in sediment; however oxidation-reduction potential (ORP), mainly through changing the pH values, indirectly alters metals distribution. Mainly ascribed to their simple operation mode, low costs and fast remediation effects, in situ remediation technologies, especially being fit for slight pollution sediment, are applied widely. However, for avoiding metal secondary pollution from sediment release, ex situ remediation should be the hot point in future research.

Effect of In-Situ Titanium Boride Particle Addition and Friction Stir Processing on Wear Behavior of Aluminum Alloy 2219

NASA Astrophysics Data System (ADS)

Sampath, V.; Rajasekaran, N. R.

There is paucity of data on the effect of in-situ TiB2 particles on the different behavior of 2219 Al alloy. In the present work, therefore, composites with 2219 Al alloy matrix reinforced with in-situ TiB2 particles were produced by flux-assisted synthesis. Different amounts (5 and 10 wt.%) of TiB2 were incorporated. The base alloy and the composites were subjected to friction stir processing to reduce particle clustering. The wear behavior of the materials was studied. The base alloy showed considerable improvement in the wear behavior due to the in-situ particle addition which is attributed to the presence of finer particles with good interfacial bonding and high hardness. Uniform distribution of TiB2 particles and good interface between the matrix and the particles led to reduction in the wear of friction stir processed composites by 30%. The results are analyzed and discussed in detail in the paper.

Roles of strain and domain boundaries on the phase transition stability of VO2 thin films

NASA Astrophysics Data System (ADS)

Jian, Jie; Chen, Aiping; Chen, Youxing; Zhang, Xinghang; Wang, Haiyan

2017-10-01

The fundamental phase transition mechanism and the stability of the semiconductor-to-metal phase transition properties during multiple thermal cycles have been investigated on epitaxial vanadium dioxide (VO2) thin films via both ex situ heating and in situ heating by transmission electron microscopy (TEM). VO2 thin films were deposited on c-cut sapphire substrates by pulsed laser deposition. Ex situ studies show the broadening of transition sharpness (ΔT) and the width of thermal hysteresis (ΔH) after 60 cycles. In situ TEM heating studies reveal that during thermal cycles, large strain was accumulated around the domain boundaries, which was correlated with the phase transition induced lattice constant change and the thermal expansion. It suggests that the degradation of domain boundary structures in the VO2 films not only caused the transition property reduction (e.g., the decrease in ΔT and ΔH) but also played an important role in preventing the film from fracture during thermal cycles.

Protecting-group-free synthesis of amines: synthesis of primary amines from aldehydes via reductive amination.

PubMed

Dangerfield, Emma M; Plunkett, Catherine H; Win-Mason, Anna L; Stocker, Bridget L; Timmer, Mattie S M

2010-08-20

New methodology for the protecting-group-free synthesis of primary amines is presented. By optimizing the metal hydride/ammonia mediated reductive amination of aldehydes and hemiacetals, primary amines were selectively prepared with no or minimal formation of the usual secondary and tertiary amine byproduct. The methodology was performed on a range of functionalized aldehyde substrates, including in situ formed aldehydes from a Vasella reaction. These reductive amination conditions provide a valuable synthetic tool for the selective production of primary amines in fewer steps, in good yields, and without the use of protecting groups.

Rapid in situ assessment of physiological activities in bacterial biofilms using fluorescent probes

NASA Technical Reports Server (NTRS)

Yu, F. P.; McFeters, G. A.

1994-01-01

Two rapid in situ enumeration methods using fluorescent probes were used to assess the physiological activities of Klebsiella pneumoniae biofilms on stainless steel. Fluorescent dyes, 5-cyano-2,3-ditolyl tetrazolium chloride (CTC) and rhodamine 123 (Rh 123), were chosen to perform this study. CTC is a soluble redox indicator which can be reduced by respiring bacteria to fluorescent CTC-formazan crystals. Rh 123 is incorporated into bacteria with respect to cellular proton motive force. The intracellular accumulation of these fluorescent dyes can be determined using epifluorescence microscopy. The results obtained with these two fluorescent probes in situ were compared to the plate count (PC) and in situ direct viable count (DVC) methods. Viable cell densities within biofilms determined by the three in situ methods were comparable and always showed approximately 2-fold higher values than those obtained with the PC method. As an additional advantage, the results were observed after 2 h, which was shorter than the 4 h incubation time required for the DVC method and 24 h for colony formation. The results indicate that staining with CTC and Rh 123 provides rapid information regarding cell numbers and physiological activities of bacteria within biofilms.

In Situ Integration of Ultrathin PtCu Nanowires with Reduced Graphene Oxide Nanosheets for Efficient Electrocatalytic Oxygen Reduction.

PubMed

Yan, Xiaoxiao; Chen, Yifan; Deng, Sihui; Yang, Yifan; Huang, Zhenna; Ge, Cunwang; Xu, Lin; Sun, Dongmei; Fu, Gengtao; Tang, Yawen

2017-11-27

Ultrathin Pt-based nanowires are considered as promising electrocatalysts owing to their high atomic utilization efficiency and structural robustness. Moreover, integration of Pt-based nanowires with graphene oxide (GO) could further increase the electrocatalytic performance, yet remains challenging to date. Herein, for the first time we demonstrate the in situ synthesis of ultrathin PtCu nanowires grown over reduced GO (PtCu-NWs/rGO) by a one-pot hydrothermal approach with the aid of amine-terminated poly(N-isopropyl acrylamide) (PNIPAM-NH 2 ). The judicious selection of PNIPAM-NH 2 facilitates the in situ nucleation and anisotropic growth of nanowires on the rGO surface and oriented attachment mechanism accounts for the formation of PtCu ultrathin nanowires. Owing to the synergy between PtCu NWs and rGO support, the PtCu-NWs/rGO outperforms the rGO supported PtCu nanoparticles (PtCu-NPs/rGO), PtCu-NWs, and commercial Pt/C toward the oxygen reduction reaction (ORR) with higher activity and better stability, making it a promising cathodic electrocatalyst for both fuel cells and metal-air cells. Moreover, the present synthetic strategy could inspire the future design of other metal alloy nanowires/carbon hybrid catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Model test study on propagation law of plane stress wave in jointed rock mass under different in-situ stresses

NASA Astrophysics Data System (ADS)

Dong, Qian

2017-12-01

The study of propagation law of plane stress wave in jointed rock mass under in-situ stress has important significance for safety excavation of underground rock mass engineering. A model test of the blasting stress waves propagating in the intact rock and jointed rock mass under different in-situ stresses was carried out, and the influencing factors on the propagation law, such as the scale of static loads and the number of joints were studied respectively. The results show that the transmission coefficient of intact rock is larger than that of jointed rock mass under the same loading condition. With the increase of confining pressure, the transmission coefficients of intact rock and jointed rock mass both show an trend of increasing first and then decreasing, and the variation of transmission coefficients in intact rock is smaller than that of jointed rock mass. Transmission coefficient of jointed rock mass decreases with the increase of the number of joints under the same loading condition, when the confining pressure is relatively small, the reduction of transmission coefficients decreases with the increasing of the number of joints, and the variation law of the reduction of transmission coefficients is contrary when the confining pressure is large.

Relating induced in situ conditions of raw chicken breast meat to pinking.

PubMed

Holownia, K; Chinnan, M S; Reynolds, A E; Davis, J W

2004-01-01

Our objective was to simulate the pink color defect in cooked chicken breast meat with treatment combinations that would induce measurable changes in the conditions of raw meat. In addition, the feasibility of using induced raw meat conditions to develop a logistic regression model for prediction of pinking was studied. Approximately 960 breast fillets from 2 plants with 2 replications were used for inducing in situ conditions with 16 combinations of sodium chloride, sodium tripolyphosphate, sodium erythorbate, and sodium nitrite (present and not present). Muscles in all treatments were subjected to individual injections, followed by tumbling, cooking, and chilling. Raw samples were analyzed for pH, oxidation-reduction potential, and pigment evaluation. Results indicated a significant role of induced in situ conditions of raw meat in the occurrence of pinking. Presence of 1 ppm or more of sodium nitrite in raw meat produced significant pinking of cooked meat. The light muscle color group was least affected and the dark group was most affected by induced pH, oxidation-reduction potential conditions, and metmyoglobin and nitrosopigment content. The predictive ability of the logistic model was more than 90% with nitrosopigment, pH, and reducing conditions being the most important factors. Moreover, validation of the model was confirmed by close association between observed pink samples and those predicted as pink.

In-situ determination of residual specific activity in activated concrete walls of a PET-cyclotron room

NASA Astrophysics Data System (ADS)

Matsumura, H.; Toyoda, A.; Masumoto, K.; Yoshida, G.; Yagishita, T.; Nakabayashi, T.; Sasaki, H.; Matsumura, K.; Yamaya, Y.; Miyazaki, Y.

2018-06-01

In the decommissioning work for concrete walls of PET-cyclotron rooms, an in-situ measurement is expected to be useful for obtaining a contour map of the specific activity on the walls without destroying the structure. In this study, specific activities of γ-ray-emitting radionuclides in concrete walls were determined by using an in-situ measurement method employing a portable Ge semiconductor detector, and compared with the specific activity obtained using the sampling measurement method, at the Medical and Pharmacological Research Center Foundation in Hakui, Ishikawa, Japan. Accordingly, the specific activity could be determined by the in-situ determination method. Since there is a clear correlation between the total specific activity of γ-ray-emitting radionuclides and contact dose rate, the specific activity can be determined approximately by contact dose-rate measurement using a NaI scintillation survey meter. The specific activity of each γ-ray-emitting radionuclide can also be estimated from the contact dose rate using a NaI scintillation survey meter. The in-situ measurement method is a powerful tool for the decommissioning of the PET cyclotron room.

Assessing coral health and disease from digital photographs and in situ surveys.

PubMed

Page, C A; Field, S N; Pollock, F J; Lamb, J B; Shedrawi, G; Wilson, S K

2017-01-01

Methods for monitoring the status of marine communities are increasingly adopting the use of images captured in the field. However, it is not always clear how data collected from photographic images relate to historic data collected using traditional underwater visual census methods. Here, we compare coral health and disease data collected in situ by scuba divers with photographic images collected simultaneously at 12 coral reef sites. Five globally relevant coral diseases were detected on 194 colonies from in situ surveys and 79 colonies from photos, whilst 698 colonies from in situ surveys and 535 colonies from photos exhibited signs of compromised health other than disease. Comparisons of in situ surveys with photographic analyses indicated that the number of disease cases occurring in the examined coral populations (prevalence) was six times higher (4.5 vs. 0.8% of colonies), whilst compromised health was three times higher (14 vs. 4% of colonies) from in situ surveys. Skeletal eroding band disease, sponge overgrowth and presence of Waminoa flatworms were not detected in photographs, though they were identified in situ. Estimates of black band disease and abnormally pigmented coral tissues were similar between the two methods. Estimates of the bleached and healthy colonies were also similar between methods and photographic analyses were a strong predictor of bleached (r 2  = 0.8) and healthy (r 2  = 0.5) colony prevalence from in situ surveys. Moreover, when data on disease and compromised health states resulting in white or pale coral colony appearance were pooled, the prevalence of 'white' colonies from in situ (14%) and photographic analyses (11%) were statistically similar. Our results indicate that information on coral disease and health collected by in situ surveys and photographic analyses are not directly comparable, with in situ surveys generally providing higher estimates of prevalence and greater ability to identify some diseases and compromised states. Careful sampling of photographs can however identify signs of coral stress, including some coral diseases, which may be used to trigger early-warning management interventions.

In situ Bioreduction of Uranium (VI) in Groundwater and Sediments with Edible Oil as the Electron Donor

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Mehlhorn, T.; Zhang, G.; Earles, J.; Lowe, K.; Phillips, J.; Boyanov, M.; Kemner, K. M.; Schadt, C. W.; Brooks, S. C.; Criddle, C.; Jardine, P.

2009-12-01

In situ bioremediation of a uranium-contaminated aquifer was conducted at the US DOE Environmental Remediation Sciences Program (ERSP) Integrated Field Research Challenge (IFRC) site, in Oak Ridge, TN. Edible oil was tested as a slow-release electron donor for microbially mediated U (VI) reduction. Uranium contaminated sediments from the site were used in laboratory microcosm tests to study the feasibility of using this electron donor under anaerobic, ambient temperature conditions. Parallel microcosms were established using ethanol as electron donor for comparison. The tests also examined the impact of sulfate concentrations on U (VI) reduction. The oil was degraded by indigenous microorganisms with acetate as a major product but at a much slower rate than ethanol. The rapid removal of U (VI) from the aqueous phase occurred concurrently with acetate production and sulfate reduction. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 vs. 5 mM), likely due to U(VI) desorption from the solid phase, but more U(VI) was reduced with higher initial sulfate level. Finally, the bioreaction in microcosms progressed to methanogenesis. Subsequently, a field test with the edible oil was conducted in a highly permeable gravelly layer (hydraulic conductivity 0.076 cm/sec). Groundwater at the site contained 5-6 μM U; 1.0-1.2 mM sulfate; 3-4 mM Ca; pH 6.8. Diluted emulsified oil (20% solution) was injected into three injection wells within 2 hrs. Geochemical analysis of site groundwater demonstrated the sequential reduction of nitrate, Mn, Fe(III) and sulfate. Transient accumulation of acetate was observed as an intermediate in the oil degradation. Reduction and removal of uranium from groundwater was observed in all wells connected to the injection wells after 2-4 weeks. Uranium concentrations in groundwater were reduced to below 0.126 μM (EPA drinking water standard), at some well locations. Rebound of U in groundwater was observed together with the rebound of sulfate concentrations as the oil was consumed. Uranium (VI) reduction to U (IV) in the microcosm and in situ field tests was confirmed by X-ray near-edge absorption spectroscopy analysis. Bacterial populations in microcosms and field samples were analyzed using 16S rRNA gene libraries and Geochip analysis.

Comparison of four extraction/methylation analytical methods to measure fatty acid composition by gas chromatography in meat.

PubMed

Juárez, M; Polvillo, O; Contò, M; Ficco, A; Ballico, S; Failla, S

2008-05-09

Four different extraction-derivatization methods commonly used for fatty acid analysis in meat (in situ or one-step method, saponification method, classic method and a combination of classic extraction and saponification derivatization) were tested. The in situ method had low recovery and variation. The saponification method showed the best balance between recovery, precision, repeatability and reproducibility. The classic method had high recovery and acceptable variation values, except for the polyunsaturated fatty acids, showing higher variation than the former methods. The combination of extraction and methylation steps had great recovery values, but the precision, repeatability and reproducibility were not acceptable. Therefore the saponification method would be more convenient for polyunsaturated fatty acid analysis, whereas the in situ method would be an alternative for fast analysis. However the classic method would be the method of choice for the determination of the different lipid classes.

Unlocking the Potential of Phenacyl Protecting Groups: CO2-Based Formation and Photocatalytic Release of Caged Amines.

PubMed

Speckmeier, Elisabeth; Klimkait, Michael; Zeitler, Kirsten

2018-04-06

Orthogonal protection and deprotection of amines remain important tools in synthetic design as well as in chemical biology and material research applications. A robust, highly efficient, and sustainable method for the formation of phenacyl-based carbamate esters was developed using CO 2 for the in situ preparation of the intermediate carbamates. Our mild and broadly applicable protocol allows for the formation of phenacyl urethanes of anilines, primary amines, including amino acids, and secondary amines in high to excellent yields. Moreover, we demonstrate the utility by a mild and convenient photocatalytic deprotection protocol using visible light. A key feature of the [Ru(bpy) 3 ](PF 6 ) 2 -catalyzed method is the use of ascorbic acid as reductive quencher in a neutral, buffered, two-phase acetonitrile/water mixture, granting fast and highly selective deprotection for all presented examples.

Vanadium Respiration by Geobacter metallireducens: Novel Strategy for In Situ Removal of Vanadium from Groundwater

PubMed Central

Ortiz-Bernad, Irene; Anderson, Robert T.; Vrionis, Helen A.; Lovley, Derek R.

2004-01-01

Vanadium can be an important contaminant in groundwaters impacted by mining activities. In order to determine if microorganisms of the Geobacteraceae, the predominant dissimilatory metal reducers in many subsurface environments, were capable of reducing vanadium(V), Geobacter metallireducens was inoculated into a medium in which acetate was the electron donor and vanadium(V) was the sole electron acceptor. Reduction of vanadium(V) resulted in the production of vanadium(IV), which subsequently precipitated. Reduction of vanadium(V) was associated with cell growth with a generation time of 15 h. No vanadium(V) was reduced and no precipitate was formed in heat-killed or abiotic controls. Acetate was the most effective of all the electron donors evaluated. When acetate was injected into the subsurface to enhance the growth and activity of Geobacteraceae in an aquifer contaminated with uranium and vanadium, vanadium was removed from the groundwater even more effectively than uranium. These studies demonstrate that G. metallireducens can grow via vanadium(V) respiration and that stimulating the activity of Geobacteraceae, and hence vanadium(V) reduction, can be an effective strategy for in situ immobilization of vanadium in contaminated subsurface environments. PMID:15128571

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

USGS Publications Warehouse

Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

2001-01-01

The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

Simultaneous AuIII Extraction and In Situ Formation of Polymeric Membrane-Supported Au Nanoparticles: A Sustainable Process with Application in Catalysis.

PubMed

Mora-Tamez, Lucía; Esquivel-Peña, Vicente; Ocampo, Ana L; Rodríguez de San Miguel, Eduardo; Grande, Daniel; de Gyves, Josefina

2017-04-10

A polymeric membrane-supported catalyst with immobilized gold nanoparticles (AuNPs) was prepared through the extraction and in situ reduction of Au III salts in a one-step strategy. Polymeric inclusion membranes (PIMs) and polymeric nanoporous membranes (PNMs) were tested as different membrane-support systems. Transport experiments indicated that PIMs composed of cellulose triacetate, 2-nitrophenyloctyl ether, and an aliphatic tertiary amine (Adogen 364 or Alamine 336) were the most efficient supports for Au III extraction. The simultaneous extraction and reduction processes were proven to be the result of a synergic phenomenon in which all the membrane components were involved. Scanning electron microscopy characterization of cross-sectional samples suggested a distribution of AuNPs throughout the membrane. Transmission electron microscopy characterization of the AuNPs indicated average particle sizes of 36.7 and 2.9 nm for the PIMs and PNMs, respectively. AuNPs supported on PIMs allowed for >95.4 % reduction of a 0.05 mmol L -1 4-nitrophenol aqueous solution with 10 mmol L -1 NaBH 4 solution within 25 min. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous and rapid determination of multiple component concentrations in a Kraft liquor process stream

DOEpatents

Li, Jian [Marietta, GA; Chai, Xin Sheng [Atlanta, GA; Zhu, Junyoung [Marietta, GA

2008-06-24

The present invention is a rapid method of determining the concentration of the major components in a chemical stream. The present invention is also a simple, low cost, device of determining the in-situ concentration of the major components in a chemical stream. In particular, the present invention provides a useful method for simultaneously determining the concentrations of sodium hydroxide, sodium sulfide and sodium carbonate in aqueous kraft pulping liquors through use of an attenuated total reflectance (ATR) tunnel flow cell or optical probe capable of producing a ultraviolet absorbency spectrum over a wavelength of 190 to 300 nm. In addition, the present invention eliminates the need for manual sampling and dilution previously required to generate analyzable samples. The inventive method can be used in Kraft pulping operations to control white liquor causticizing efficiency, sulfate reduction efficiency in green liquor, oxidation efficiency for oxidized white liquor and the active and effective alkali charge to kraft pulping operations.

Quantitative comparison of in situ soil CO2 flux measurement methods

Treesearch

Jennifer D. Knoepp; James M. Vose

2002-01-01

Development of reliable regional or global carbon budgets requires accurate measurement of soil CO2 flux. We conducted laboratory and field studies to determine the accuracy and comparability of methods commonly used to measure in situ soil CO2 fluxes. Methods compared included CO2...

Synthesis of Strained 1,3-Diene Macrocycles via Copper-Mediated Castro-Stephens Coupling/Alkyne Reduction Tandem Reactions.

PubMed

Li, Wei; Schneider, Christopher M; Georg, Gunda I

2015-08-07

A copper-mediated macrocyclization involving the reaction of a vinyl iodide and a terminal alkyne followed by an in situ reduction of the enyne intermediate is reported. The reaction generates a conjugated Z-double bond within a strained medium-size lactone, lactam, or ether macrocycle. A variety of macrocyclic compounds bearing different ring sizes and functionalities were synthesized. A complementary stepwise procedure was also developed for less strained ring systems.

High strength-high conductivity Cu-Fe composites produced by powder compaction/mechanical reduction

DOEpatents

Verhoeven, J.D.; Spitzig, W.A.; Gibson, E.D.; Anderson, I.E.

1991-08-27

A particulate mixture of Cu and Fe is compacted and mechanically reduced to form an ''in-situ'' Cu-Fe composite having high strength and high conductivity. Compaction and mechanical reduction of the particulate mixture are carried out at a temperature and time at temperature selected to avoid dissolution of Fe into the Cu matrix particulates to a harmful extent that substantially degrades the conductivity of the Cu-Fe composite. 5 figures.

3D-Hydrogel Based Polymeric Nanoreactors for Silver Nano-Antimicrobial Composites Generation

PubMed Central

Soto-Quintero, Albanelly; Romo-Uribe, Ángel; Bermúdez-Morales, Víctor H.; Quijada-Garrido, Isabel

2017-01-01

This study underscores the development of Ag hydrogel nanocomposites, as smart substrates for antibacterial uses, via innovative in situ reactive and reduction pathways. To this end, two different synthetic strategies were used. Firstly thiol-acrylate (PSA) based hydrogels were attained via thiol-ene and radical polymerization of polyethylene glycol (PEG) and polycaprolactone (PCL). As a second approach, polyurethane (PU) based hydrogels were achieved by condensation polymerization from diisocyanates and PCL and PEG diols. In fact, these syntheses rendered active three-dimensional (3D) hydrogel matrices which were used as nanoreactors for in situ reduction of AgNO3 to silver nanoparticles. A redox chemistry of stannous catalyst in PU hydrogel yielded spherical AgNPs formation, even at 4 °C in the absence of external reductant; and an appropriate thiol-functionalized polymeric network promoted spherical AgNPs well dispersed through PSA hydrogel network, after heating up the swollen hydrogel at 103 °C in the presence of citrate-reductant. Optical and swelling behaviors of both series of hydrogel nanocomposites were investigated as key factors involved in their antimicrobial efficacy over time. Lastly, in vitro antibacterial activity of Ag loaded hydrogels exposed to Pseudomona aeruginosa and Escherichia coli strains indicated a noticeable sustained inhibitory effect, especially for Ag–PU hydrogel nanocomposites with bacterial inhibition growth capabilities up to 120 h cultivation. PMID:28763050

In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ross, Philip N.; ...

2015-12-11

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). In this paper, we have studied a common electrolyte, 1.0 M LiPF 6/ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials wheremore » electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC 2H 5) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. Finally, these findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.« less

Evaluation of carbon isotope fractionation during anaerobic reductive dehalogenation of chlorinated and brominated benzenes.

PubMed

Sohn, Seo Yean; Kuntze, Kevin; Nijenhuis, Ivonne; Häggblom, Max M

2018-02-01

Compound specific stable isotope analysis (CSIA) has been established as a useful tool to evaluate in situ biodegradation. Here, CSIA was used to determine microbial dehalogenation of chloro- and bromobenzenes in microcosms derived from Hackensack River sediments. Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) was used to measure carbon isotope fractionation during reductive dehalogenation of hexachlorobenzene (HCB), pentachlorobenzene (PeCB), 1,2,3,5-tetrachlorobenzene (TeCB), 1,2,3,5-tetrabromobenzene (TeBB), and 1,3,5-tribromobenzene (TriBB). Strong evidence of isotope fractionation coupled to dehalogenation was not observed in the substrate, possibly due to the low solubilities of the highly halogenated benzene substrates and a dilution of the isotope signal. Nonetheless, we could measure a depletion of the δ 13 C value in the dichlorobenzene product during dechlorination of HCB, the sequential depletion and enrichment of δ 13 C value for trichlorobenzene in TeCB dechlorinating cultures, and the enrichment of δ 13 C during debromination of TriBB. This indicates that a measurable isotope fractionation occurred during reductive dehalogenation of highly halogenated chloro- and bromobenzenes in aquatic sediments. Thus, although more quantitative measurements will be needed, the data suggests that CSIA may have application for monitoring in situ microbial reductive dehalogenation of highly halogenated benzenes. Copyright © 2017. Published by Elsevier Ltd.

Methods for characterizing subsurface volatile contaminants using in-situ sensors

DOEpatents

Ho, Clifford K [Albuquerque, NM

2006-02-21

An inverse analysis method for characterizing diffusion of vapor from an underground source of volatile contaminant using data taken by an in-situ sensor. The method uses one-dimensional solutions to the diffusion equation in Cartesian, cylindrical, or spherical coordinates for isotropic and homogenous media. If the effective vapor diffusion coefficient is known, then the distance from the source to the in-situ sensor can be estimated by comparing the shape of the predicted time-dependent vapor concentration response curve to the measured response curve. Alternatively, if the source distance is known, then the effective vapor diffusion coefficient can be estimated using the same inverse analysis method. A triangulation technique can be used with multiple sensors to locate the source in two or three dimensions. The in-situ sensor can contain one or more chemiresistor elements housed in a waterproof enclosure with a gas permeable membrane.

Hierarchical porous silver metal using Pluronic F-127 and graphene oxide as reinforcing agents for the reduction of o-nitroaniline to 1, 2-benzenediamine

NASA Astrophysics Data System (ADS)

Bano, Mustri; Ahirwar, Devendra; Thomas, Molly; Sheikh, Mehraj Ud Din; Khan, Farid

2017-04-01

An elegant method is used to prepare silver monoliths with Pluronic F-127(F-127) as sacrificial template by modified sol-gel method. Si nanoparticles (SiNPs) and graphene oxide (GO) are added in situ to Ag/F-127 hydrogel for the reduction of ο-nitroaniline (ο-NA) to 1, 2-benzenediamine. Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermogravimetric analysis (TGA), Raman Spectroscopy, Powder X-Ray Diffraction (PXRD) analysis and Brunauer-Emmett-Teller (BET) Nitrogen adsorption techniques were used for characterization of monoliths. An epoch-making catalytic activity of Ag/F-127/GO monoliths is observed in the reduction of ο-NA to 1, 2-benzenediamine in presence of NaBH4 in aqueous media. The catalyst Ag/F-127/GO took only 2 min which is the minimum time reported so far with significant rate constant claimed itself a leading catalyst for the reduction of ο-NA to 1,2-benzenediamine. Pseudo first order rate constant (k) and Turn over frequency (TOF) values are 0.231 min-1 and 30.053×1019 molecules min-1 respectively suggest that the catalyst has industrial importance. Recyclability and stability of Ag/F-127/GO catalyst are studied successfully up to 10 cycles. Energy of activation (Ea), and thermodynamic parameters viz. activation enthalpy (ΔH≠), activation Gibbs free energy (ΔG≠), and entropy of activation (ΔS≠) were also ascertained. Catalytic activities of Ag/F-127, Ag/F-127/Dextran, Ag/F-127/Trimethylbenzene (TMB), Ag/F-127/SiNPs, and Ag/F-127/Si/GO monoliths were also studied.

An ultrasonically powered implantable micro-oxygen generator (IMOG).

PubMed

Maleki, Teimour; Cao, Ning; Song, Seung Hyun; Kao, Chinghai; Ko, Song-Chu Arthur; Ziaie, Babak

2011-11-01

In this paper, we present an ultrasonically powered implantable micro-oxygen generator (IMOG) that is capable of in situ tumor oxygenation through water electrolysis. Such active mode of oxygen generation is not affected by increased interstitial pressure or abnormal blood vessels that typically limit the systemic delivery of oxygen to hypoxic regions of solid tumors. Wireless ultrasonic powering (2.15 MHz) was employed to increase the penetration depth and eliminate the directional sensitivity associated with magnetic methods. In addition, ultrasonic powering allowed for further reduction in the total size of the implant by eliminating the need for a large area inductor. IMOG has an overall dimension of 1.2 mm × 1.3 mm × 8 mm, small enough to be implanted using a hypodermic needle or a trocar. In vitro and ex vivo experiments showed that IMOG is capable of generating more than 150 μA which, in turn, can create 0.525 μL/min of oxygen through electrolytic disassociation. In vivo experiments in a well-known hypoxic pancreatic tumor models (1 cm (3) in size) also verified adequate in situ tumor oxygenation in less than 10 min.

A novel thermoresponsive hydrogel based on chitosan.

PubMed

Schuetz, Yannic B; Gurny, Robert; Jordan, Olivier

2008-01-01

Injectable thermosetting chitosan hydrogels are attractive systems for drug delivery and tissue engineering that combine biodegradability, biocompatibility and the ability to form in situ gel-like implants. Thermally-induced gelation relies advantageously on biopolymer secondary interactions, avoiding potentially toxic polymerization reactions that may occur with in situ polymerizing formulations. In view of a biomedical use, such formulations have to be sterilizable and storable on extended periods without losing their thermosetting properties. These two key features have been studied in the present paper. Chitosans from two different sources were added with several phosphate-free polyols or polyoses as gelling agents. Despite a reduction in chitosan molecular weight following autoclaving, the hydrogels prepared with autoclaved chitosan showed the desired thermosetting properties. Hence, chitosan steam sterilization combined with aseptic preparation of the hydrogel allows a sterile formulation to be obtained. Whereas thermosetting hydrogels were shown to be unstable when refrigerated, freezing was shown to be conceivable as a storage method. When trehalose or mannitol was used as stabilizing agent, the formulation reconstituted from a lyophilizate displayed thermosetting properties and was still injectable, paving the way to the development of a clinically utilizable, novel chitosan thermosetting hydrogel.

A novel (ex situ) method to quantify oxygen diffusion coefficient of polymer fuel cells backing and catalyst layers

NASA Astrophysics Data System (ADS)

Baricci, Andrea; Casalegno, Andrea

2016-09-01

Limiting current density of oxygen reduction reaction in polymer electrolyte fuel cells is determined by several mass transport resistances that lower the concentration of oxygen on the catalyst active site. Among them, diffusion across porous media plays a significant role. Despite the extensive experimental activity documented in PEMFC literature, only few efforts have been dedicated to the measurement of the effective transport properties in porous layers. In the present work, a methodology for ex situ measurement of the effective diffusion coefficient and Knudsen radius of porous layers for polymer electrolyte fuel cells (gas diffusion layer, micro porous layer and catalyst layer) is described and applied to high temperature polymer fuel cells State of Art materials. Regression of the measured quantities by means of a quasi 2D physical model is performed to quantify the Knudsen effect, which is reported to account, respectively, for 30% and 50% of the mass transport resistance in micro porous layer and catalyst layer. On the other side, the model reveals that pressure gradient consequent to permeation in porous layers of high temperature polymer fuel cells has a negligible effect on oxygen concentration in relevant operating conditions.

In situ electrochemical assessment of cytotoxicity of chlorophenols in MCF-7 and HeLa cells.

PubMed

Qin, Hongwei; Liu, Jiguang; Zhang, Zeshi; Li, Jinlian; Gao, Guanggang; Yang, Yuxin; Yuan, Xing; Wu, Dongmei

2014-10-01

An in situ electrochemical method was used to assess the cytotoxicity of chlorophenols using human breast cancer (MCF-7) and cervical carcinoma (HeLa) cells as models. On treatment with different chlorophenols, the electrochemical responses of the selected cells, resulting from the oxidation of guanine and xanthine in the cytoplasm, indicated the cell viability. In addition, the in situ in vitro electrochemical method was further compared with the traditional MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays. Although similar cytotoxicity data were obtained from both methods, the effective concentrations of chlorophenols that inhibited 50% cell growth (EC50 values) from the electrochemical method were only slightly lower than those from the MTT assay. These results indicate that the in situ in vitro electrochemical method paves a simple, rapid, strongly responsive, and label-free way to the cytotoxicity assessment of different chlorophenol pollutants. Copyright © 2014 Elsevier Inc. All rights reserved.

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

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

Iisa, Kristiina; French, Richard J.; Orton, Kellene A.

In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h -1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun.more » The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO 2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.« less

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

DOE PAGES

Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; ...

2016-02-03

In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h -1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun.more » The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO 2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.« less

In Situ Splitting of a Rib Bone Graft for Reconstruction of Orbital Floor and Medial Wall.

PubMed

Uemura, Tetsuji; Yanai, Tetsu; Yasuta, Masato; Harada, Yoshimi; Morikawa, Aya; Watanabe, Hidetaka; Kurokawa, Masato

2017-06-01

In situ splitting of rib bone graft was conducted in 22 patients for the repair of orbital fracture with no other complicating fractures. A bone graft was harvested from the sixth or seventh rib in the right side. The repair of the orbital floor and medial wall was successful in all the cases. Ten patients had bone grafting to the orbital floor, eight had it done onto medial wall, and 4 onto both floor and wall after reduction. The mean length of in situ rib bone graft was 40.9 mm (range, 20-70 mm), the mean width of these was 14.9 mm (range, 8-20 mm). The bone grafting was done by one leaf for 15 cases and two leafs for 7 cases in size of defects. The technique of in situ splitting of a rib bone graft for the repair of the orbital floor and medial wall is a simple and safe procedure, easily taking out the in situ splitting of a rib, and less pain in donor site. It has proved to be an optimal choice in craniofacial reconstruction, especially the defects of orbital floor and medial wall.

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

PubMed

Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

2008-09-01

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

Convenient, inexpensive quantification of elemental sulfur by simultaneous in situ reduction and colorimetric detection.

PubMed

Kwasniewski, Misha T; Allison, Rachel B; Wilcox, Wayne F; Sacks, Gavin L

2011-10-03

Rapid, inexpensive, and convenient methods for quantifying elemental sulfur (S(0)) with low or sub-μgg(-1) limits of detection would be useful for a range of applications where S(0) can act as a precursor for noxious off-aromas, e.g., S(0) in pesticide residues on winegrapes or as a contaminant in drywall. However, existing quantification methods rely on toxic reagents, expensive and cumbersome equipment, or demonstrate poor selectivity. We have developed and optimized an inexpensive, rapid method (∼15 min per sample) for quantifying S(0) in complex matrices. Following dispersion of the sample in PEG-400 and buffering, S(0) is quantitatively reduced to H(2)S in situ by dithiothreitol and simultaneously quantified by commercially available colorimetric H(2)S detection tubes. By employing multiple tubes, the method demonstrated linearity from 0.03 to 100 μg S(0) g(-1) for a 5 g sample (R(2)=0.994, mean CV=6.4%), and the methodological detection limit was 0.01 μg S(0) g(-1). Interferences from sulfite or sulfate were not observed. Mean recovery of an S(0) containing sulfur fungicide in grape macerate was 84.7% with a mean CV of 10.4%. Mean recovery of S(0) in a colloidal sulfur preparation from a drywall matrix was 106.6% with a mean CV of 6.9%. Comparable methodological detection limits, sensitivity, and recoveries were achieved in grape juice, grape macerate and with 1g drywall samples, indicating that the methodology should be robust across a range of complex matrices. Copyright © 2011 Elsevier B.V. All rights reserved.

Enhanced deodorization and sludge reduction in situ by a humus soil cooperated anaerobic/anoxic/oxic (A2O) wastewater treatment system.

PubMed

Yan, Xing; Li, Biqing; Lei, Fang; Feng, Xin; Pang, Bo

2016-08-01

Simultaneous sludge reduction and malodor abatement in humus soil cooperated an anaerobic/anoxic/oxic (A2O) wastewater treatment were investigated in this study. The HSR-A2O was composed of a humus soil reactor (HSR) and a conventional A2O (designated as C-A2O).The results showed that adding HSR did not deteriorate the chemical oxygen demand (COD) removal, while total phosphorus (TP) removal efficiency in HSR-A2O was improved by 18 % in comparison with that in the C-A2O. Both processes had good performance on total nitrogen (TN) removal, and there was no significant difference between them (76.8 and 77.1 %, respectively). However, NH4 (+)-N and NO3 (-)-N were reduced to 0.3 and 6.7 mg/L in HSR-A2O compared to 1.5 and 4.5 mg/L. Moreover, adding HSR induced the sludge reduction, and the sludge production rate was lower than that in the C-A2O. The observed sludge yield was estimated to be 0.32 kg MLSS/day in HSR-A2O, which represent a 33.5 % reduction compared to a C-A2O process. Activated sludge underwent humification and produced more humic acid in HSR-A2O, which is beneficial to sludge reduction. Odor abatement was achieved in HSR-A2O, ammonium (NH3), and sulfuretted hydrogen (H2S) emission decreased from 1.34 and 1.33 to 0.06 mg/m(3), 0.025 mg/m(3) in anaerobic area, with the corresponding reduction efficiency of 95.5 and 98.1 %. Microbial community analysis revealed that the relevant microorganism enrichment explained the reduction effect of humus soil on NH3 and H2S emission. The whole study demonstrated that humus soil enhanced odor abatement and sludge reduction in situ.

In situ electronic probing of semiconducting nanowires in an electron microscope.

PubMed

Fauske, V T; Erlbeck, M B; Huh, J; Kim, D C; Munshi, A M; Dheeraj, D L; Weman, H; Fimland, B O; Van Helvoort, A T J

2016-05-01

For the development of electronic nanoscale structures, feedback on its electronic properties is crucial, but challenging. Here, we present a comparison of various in situ methods for electronically probing single, p-doped GaAs nanowires inside a scanning electron microscope. The methods used include (i) directly probing individual as-grown nanowires with a sharp nano-manipulator, (ii) contacting dispersed nanowires with two metal contacts and (iii) contacting dispersed nanowires with four metal contacts. For the last two cases, we compare the results obtained using conventional ex situ litho-graphy contacting techniques and by in situ, direct-write electron beam induced deposition of a metal (Pt). The comparison shows that 2-probe measurements gives consistent results also with contacts made by electron beam induced deposition, but that for 4-probe, stray deposition can be a problem for shorter nanowires. This comparative study demonstrates that the preferred in situ method depends on the required throughput and reliability. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

Ex situ and in situ characterization of patterned photoreactive thin organic surface layers using friction force microscopy

PubMed Central

Shen, Quan; Edler, Matthias; Griesser, Thomas; Knall, Astrid-Caroline; Trimmel, Gregor; Kern, Wolfgang; Teichert, Christian

2014-01-01

Photolithographic methods allow an easy lateral top-down patterning and tuning of surface properties with photoreactive molecules and polymers. Employing friction force microscopy (FFM), we present here different FFM-based methods that enable the characterization of several photoreactive thin organic surface layers. First, three ex situ methods have been evaluated for the identification of irradiated and non-irradiated zones on the same organosilane sample by irradiation through different types of masks. These approaches are further extended to a time dependent ex situ FFM measurement, which allows to study the irradiation time dependent evolution of the resulting friction forces by sequential irradiation through differently sized masks in crossed geometry. Finally, a newly designed in situ FFM measurement, which uses a commercial bar-shaped cantilever itself as a noncontact shadow mask, enables the determination of time dependent effects on the surface modification during the photoreaction. SCANNING 36:590–598, 2014. PMID:25183629

Cadmium sulfide quantum dots/poly(acrylic acid-co-acrylic amide) composite hydrogel synthesized by gamma irradiation

NASA Astrophysics Data System (ADS)

Yang, Tao; Li, Qing; Wen, Wanxin; Hu, Liang; He, Weiwei; Liu, Hanzhou

2018-04-01

To improve the durability and stability of quantum dots (QDs) in the composite hydrogel, an irradiation induced reduction and polymerization-crosslinking method was reported herein where CdS QDs could be synthesized in situ and fastened to polymer chains due to the coordination forces between amino groups and CdS nanoparticles. The morphology and photoluminescence (PL) property of the composite hydrogel were studied. The result indicated that the CdS QDs with uniform size were dispersed evenly in the composite hydrogel, and the introduced CdS QDs had no obvious effect on the hydrogel structure. With the increases of reagent concentrations, PL intensity of the composite hydrogel was enhanced; however, the emission wavelength had no change.

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

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

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE PAGES

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2017-04-24

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

VAPOR PHASE TREATMENT OF PCE IN A SOIL COLUMN BY LAB-SCALE ANAEROBIC BIOVENTING

EPA Science Inventory

Microbial destruction of highly chlorinated organic compounds must be initiated by anaerobic followed by aerobic dechlorination. In-situ dechlorination of vadose zone soil contaminated with these compounds requires, among other factors, the establishment of highly reductive anaer...

DESIGN AND COST REDUCTION OF REMEDIATION TECHNOLOGY PILOT TESTING

EPA Science Inventory

In order to effectively address the inherent variability of MTBE concentrations at a small fuel contamination site chosen for an in-situ remedial technology test demonstration, curtain walls for metering mixtures of conservative and non-conservative tracers into an aquifer were u...

Electrochemical behavior of platinum nanoparticles on a carbon xerogel support modified with a [(trifluoromethyl)-benzenesulfonyl]imide electrolyte.

PubMed

Liu, Bing; Mei, Hua; DesMarteau, Darryl; Creager, Stephen E

2014-12-11

A monoprotic [(trifluoromethyl)benzenesulfonyl]imide (SI) superacid electrolyte was used to covalently modify a mesoporous carbon xerogel (CX) support via reaction of the corresponding trifluoromethyl aryl sulfonimide diazonium zwitterion with the carbon surface. Electrolyte attachment was demonstrated by elemental analysis, acid-base titration, and thermogravimetric analysis. The ion-exchange capacity of the fluoroalkyl-aryl-sulfonimide-grafted carbon xerogel (SI-CX) was ∼0.18 mequiv g(-1), as indicated by acid-base titration. Platinum nanoparticles were deposited onto the SI-grafted carbon xerogel samples by the impregnation and reduction method, and these materials were employed to fabricate polyelectrolyte membrane fuel-cell (PEMFC) electrodes by the decal transfer method. The SI-grafted carbon-xerogel-supported platinum (Pt/SI-CX) was characterized by X-ray diffraction and transmission electron microscopy to determine platinum nanoparticle size and distribution, and the findings are compared with CX-supported platinum catalyst without the grafted SI electrolyte (Pt/CX). Platinum nanoparticle sizes are consistently larger on Pt/SI-CX than on Pt/CX. The electrochemically active surface area (ESA) of platinum catalyst on the Pt/SI-CX and Pt/CX samples was measured with ex situ cyclic voltammetry (CV) using both hydrogen adsorption/desorption and carbon monoxide stripping methods and by in situ CV within membrane electrode assemblies (MEAs). The ESA values for Pt/SI-CX are consistently lower than those for Pt/CX. Some possible reasons for the behavior of samples with and without grafted SI layers and implications for the possible use of SI-grafted carbon layers in PEMFC devices are discussed.

CLT and AE methods of in-situ load testing : comparison and development of evaluation criteria : in-situ evaluation of post-tensioned parking garage, Kansas City, Missouri

DOT National Transportation Integrated Search

2008-02-01

The objective of the proposed research project is to compare the results of two recently introduced nondestructive load test methods to the existing 24-hour load test method described in Chapter 20 of ACI 318-05. The two new methods of nondestructive...

In situ XAS of Pt monolayer model fuel cell catalysts: balance of na-nostructure and bimetallic interactions

NASA Astrophysics Data System (ADS)

Friebel, Daniel; Viswanathan, Venkat; Larsen, Ask; Miller, Daniel J.; Ogasawara, Hirohito; Anniyev, Toyli; O'Grady, Christopher P.; Nørskov, Jens; Nilsson, Anders

2012-02-01

The mechanism of the electrochemical oxygen reduction reaction (ORR) has been well understood based on DFT calculations, but there has been a lack of supporting experimental data, due to the difficulties of probing the electrocatalyst surface in situ. Our new approach using Pt monolayer model catalysts provides true surface sensitivity for - originally bulk sensitive - x-ray absorption spectroscopy (XAS) and, owing to the high resolution of the Bragg analyzer at SSRL beamline 6-2, allows for in situ detection of chemisorbed O and OH, whose stability can be used as a descriptor in predicting the activity of new ORR catalyst materials. Our ability to control the growth mode in the Pt/Rh(111) model system allows us to generate Pt nanostructures with highly different O affinities from identical starting materials.

Gemini primary mirror in situ wash

NASA Astrophysics Data System (ADS)

Vucina, Tomislav; Boccas, Maxime; Araya, Claudio; Ah Hee, Clayton; Cavedoni, Chas

2008-07-01

The Gemini twins were the first large modern telescopes to receive protected silver coatings on their mirrors in 2004. The low emissivity requirement is fundamental for the IR optimization. In the mid-IR a factor of two reduction in telescope emissivity is equivalent to increasing the collecting area by the same factor. Our emissivity maintenance requirement is very stringent: 0.5% maximum degradation during operations, at any single wavelength beyond 2.2 μm. We developed a very rigorous standard to wash the primary mirrors in the telescope without science down time. The in-situ washes are made regularly, and the reflectivity and emissivity gains are significant. The coating lifetime has been extended far more than our original expectations. In this report we describe the in-situ process and hardware, explain our maintenance plan, and show results of the coating performance over time.

Recent trends in breast cancer incidence in US white women by county-level urban/rural and poverty status.

PubMed

Hausauer, Amelia K; Keegan, Theresa H M; Chang, Ellen T; Glaser, Sally L; Howe, Holly; Clarke, Christina A

2009-06-26

Unprecedented declines in invasive breast cancer rates occurred in the United States between 2001 and 2004, particularly for estrogen receptor-positive tumors among non-Hispanic white women over 50 years. To understand the broader public health import of these reductions among previously unstudied populations, we utilized the largest available US cancer registry resource to describe age-adjusted invasive and in situ breast cancer incidence trends for non-Hispanic white women aged 50 to 74 years overall and by county-level rural/urban and poverty status. We obtained invasive and in situ breast cancer incidence data for the years 1997 to 2004 from 29 population-based cancer registries participating in the North American Association of Central Cancer Registries resource. Annual age-adjusted rates were examined overall and by rural/urban and poverty of patients' counties of residence at diagnosis. Joinpoint regression was used to assess trends by annual quarter of diagnosis. Between 2001 and 2004, overall invasive breast cancer incidence fell 13.2%, with greater reductions among women living in urban (-13.8%) versus rural (-7.5%) and low- (-13.0%) or middle- (-13.8%) versus high- (-9.6%) poverty counties. Most incidence rates peaked around 1999 then declined after second quarter 2002, although in rural counties, rates decreased monotonically after 1999. Similar but more attenuated patterns were seen for in situ cancers. Breast cancer rates fell more substantially in urban and low-poverty, affluent counties than in rural or high-poverty counties. These patterns likely reflect a major influence of reductions in hormone therapy use after July 2002 but cannot exclude possible effects due to screening patterns, particularly among rural populations where hormone therapy use was probably less prevalent.

Application of landfill treatment approaches for stabilization of municipal solid waste.

PubMed

Bolyard, Stephanie C; Reinhart, Debra R

2016-09-01

This research sought to compare the effectiveness of three landfill enhanced treatment approaches aimed at removing releasable carbon and nitrogen after anaerobic landfilling including flushing with clean water (FB 1), leachate recirculation with ex-situ treatment (FB 2), and leachate recirculation with ex-situ treatment and in-situ aeration (FB 3). After extensive treatment of the waste in the FB scenarios, the overall solids and biodegradable fraction were reduced relative to the mature anaerobically treated waste. In terms of the overall degradation, aeration did not provide any advantage over flushing and anaerobic treatment. Flushing was the most effective approach at removing biodegradable components (i.e. cellulose and hemicellulose). Leachate quality improved for all FBs but through different mechanisms. A significant reduction in ammonia-nitrogen occurred in FB 1 and 3 due to flushing and aeration, respectively. The reduction of chemical oxygen demand (COD) in FB 1 was primarily due to flushing. Conversely, the reduction in COD in FBs 2 and 3 was due to oxidation and precipitation during Fenton's Reagent treatment. A mass balance on carbon and nitrogen revealed that a significant fraction still remained in the waste despite the additional treatment provided. Carbon was primarily converted biologically to CH4 and CO2 in the FBs or removed during treatment using Fenton's Reagent. The nitrogen removal occurred through leaching or biological conversion. These results show that under extensive treatment the waste and leachate characteristics did meet published stability values. The minimum stability values achieved were through flushing although FB 2 and 3 were able to improve leachate quality and solid waste characteristics but not to the same extent as FB 1. Copyright © 2016 Elsevier Ltd. All rights reserved.

In situ transmission electron microscopic observations of redox cycling of a Ni-ScSZ cermet fuel cell anode.

PubMed

Matsuda, Junko; Kawasaki, Tatsuya; Futamura, Shotaro; Kawabata, Tsutomu; Taniguchi, Shunsuke; Sasaki, Kazunari

2018-05-19

In situ transmission electron microscopy (TEM) observations of a Ni(O)-Sc2O3-stabilized ZrO2 (ScSZ; 10 mol% Sc2O3, 1 mol% CeO2, 89 mol% ZrO2) anode in a solid oxide fuel cell (SOFC) have been performed at high temperatures under a hydrogen/oxygen gas atmosphere using an environmental transmission electron microscope (ETEM); the specimens were removed from cross-sections of the real SOFC by focused ion beam milling and lifting. When heating the NiO-ScSZ anode under a hydrogen atmosphere of 3 mbar in ETEM, nano-pores were formed at the grain boundaries and on the surface of NiO particles at around 400°C due to the volume shrinkage accompanying the reduction of NiO to Ni. Moreover, densification of Ni occurred when increasing the temperature from 600 to 700°C. High-magnification TEM images obtained in the early stages of NiO reduction revealed that the (111) planes of Ni grew almost parallel to the (111) planes of NiO. In the case of heating Ni-ScSZ under an oxygen atmosphere of 3 mbar in ETEM, oxidation of Ni starting from the surface of the particles occurred above 300°C. All Ni particles became polycrystalline NiO after the temperature was increased to 800°C. Volume expansion/contraction by mass transfer to the outside/inside of the Ni particles in the anode during repeated oxidation/reduction seems to result in the agglomeration of Ni catalysts during long-term SOFC operation. We emphasize that our in situ TEM observations will be applied to observe electrochemical reactions in SOFCs under applied electric fields.

A Critical Assessment of Microbiological Biogas to Biomethane Upgrading Systems.

PubMed

Rittmann, Simon K-M R

2015-01-01

Microbiological biogas upgrading could become a promising technology for production of methane (CH(4)). This is, storage of irregular generated electricity results in a need to store electricity generated at peak times for use at non-peak times, which could be achieved in an intermediate step by electrolysis of water to molecular hydrogen (H(2)). Microbiological biogas upgrading can be performed by contacting carbon dioxide (CO(2)), H(2) and hydrogenotrophic methanogenic Archaea either in situ in an anaerobic digester, or ex situ in a separate bioreactor. In situ microbiological biogas upgrading is indicated to require thorough bioprocess development, because only low volumetric CH(4) production rates and low CH(4) fermentation offgas content have been achieved. Higher volumetric production rates are shown for the ex situ microbiological biogas upgrading compared to in situ microbiological biogas upgrading. However, the ex situ microbiological biogas upgrading currently suffers from H(2) gas liquid mass transfer limitation, which results in low volumetric CH(4) productivity compared to pure H(2)/CO(2) conversion to CH(4). If waste gas utilization from biological and industrial sources can be shown without reduction in volumetric CH(4) productivity, as well as if the aim of a single stage conversion to a CH(4) fermentation offgas content exceeding 95 vol% can be demonstrated, ex situ microbiological biogas upgrading with pure or enrichment cultures of methanogens could become a promising future technology for almost CO(2)-neutral biomethane production.

Comparison of some aspects of the in situ and in vitro methods in evaluation of neutral detergent fiber digestion.

PubMed

Krizsan, S J; Jančík, F; Ramin, M; Huhtanen, P

2013-02-01

The objective of the present study was to compare digestion rates (kd) of NDF for different feeds estimated with the in situ method or derived from an automated gas in vitro system. A meta-analysis was conducted to evaluate how in situ derived kd of NDF related to in vivo digestibility of NDF. Furthermore, in vitro true digestibility of the feed samples incubated within filter bags or dispersed in the medium was compared, and kd for insoluble and soluble components of those feeds were estimated. Four different concentrates and 4 forages were used in this study. Two lactating Swedish Red cows fed a diet of 60% grass silage and 40% concentrate on DM basis were used for in situ incubations and for collection of rumen fluid. The feed samples were ground through a 2.0-mm screen before the in situ incubations and a 1.0-mm screen before the in vitro gas incubations. In situ nylon bags were introduced into the rumen for determination of kd of NDF. Additional kinetic data were produced from isolated NDF and intact samples subjected to in vitro incubations in which gas production was recorded for 72 h. Samples were weighed in the bottles or within filter bags (for fiber and in vitro studies) that were placed in the bottles. The interaction between feed and method was significant (P < 0.01); kd of NDF for grass hay tended (P = 0.06) to be less whereas kd of NDF for alfalfa, barley grain, canola meal, and dried sugar beet pulp were greater (P < 0.01) when estimated with the in situ method than from gas production recordings. The meta-analysis suggested that in situ derived kd of NDF were biased and underestimated in vivo digestibility of NDF. Digestion rates of the intact samples were lower for all feeds, except for the hay, when incubated within the bags compared with dispersed in the medium (P < 0.01). Less OM and NDF were digested for all feeds when incubated within bags than dispersed in the medium (P < 0.01). It is concluded from the in vitro study that microbial activity within the bags is less than in the medium. Significant interactions between method (in situ vs. in vitro) and feed suggest that one or both methods result in biased estimates of digestion kinetics.

Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry.

PubMed

Durham, Jessica L; Poyraz, Altug S; Takeuchi, Esther S; Marschilok, Amy C; Takeuchi, Kenneth J

2016-09-20

Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multifunctionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cations can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multimechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM'O) or phosphorus oxides (MM'PO) where M = Ag and M' = V or Fe. One discharge process can be described as reduction-displacement where Ag(+) is reduced to Ag(0) and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in situ and ex situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. Full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.

A method to investigate the electron scattering characteristics of ultrathin metallic films by in situ electrical resistance measurements.

PubMed

Trindade, I G; Fermento, R; Leitão, D; Sousa, J B

2009-07-01

In this article, a method to measure the electrical resistivity/conductivity of metallic thin films during layer growth on specific underlayers is described. The in situ monitoring of an underlayer electrical resistance, its change upon the incoming of new material atoms/molecules, and the growth of a new layer are presented. The method is easy to implement and allows obtaining in situ experimental curves of electrical resistivity dependence upon film thickness with a subatomic resolution, providing insight in film growth microstructure characteristics, specular/diffuse electron scattering surfaces, and optimum film thicknesses.

Influence of grinding on the nutritive value of peas for ruminants: comparison between in vitro and in situ approaches

PubMed Central

Giger-Reverdin, Sylvie; Maaroufi, Chiraze; Chapoutot, Patrick; Peyronnet, Corinne; Sauvant, Daniel

2014-01-01

In ruminant nutrition, peas are characterized by high protein solubility and degradability, which impair its protein value estimated by the official in situ method. Grinding can be used as a technological treatment of pea seeds to modify their nutritional value. The aim of this study was to compare the in situ method with an in vitro method on the same pea either in a coarse pea flour form (PCF) or in a ground pea fine flour form (PFF) to understand the effect of grinding. Both forms were also reground (GPCF and GPFF). PCF presented a lower rate of in vitro degradation than PFF, and more stable fermentation parameters (pH, ammonia, soluble carbohydrates) even if gas production was higher for the PCF after 48 h of incubation. In situ dry matter and protein degradation were lower for PCF than those for PFF; these differences were more marked than with the in vitro method. Reground peas were very similar to PFF. The values for pea protein digestible in the intestine (PDI) were higher for PCF than those for PFF. This study points out the high sensitivity of the in situ method to grinding. The study needs to be validated by in vivo measurements. PMID:25473488

Visualizing the Cu/Cu2(O) Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy.

PubMed

LaGrow, Alec P; Ward, Michael R; Lloyd, David C; Gai, Pratibha L; Boyes, Edward D

2017-01-11

Understanding the oxidation and reduction mechanisms of catalytically active transition metal nanoparticles is important to improve their application in a variety of chemical processes. In nanocatalysis the nanoparticles can undergo oxidation or reduction in situ, and thus the redox species are not what are observed before and after reactions. We have used the novel environmental scanning transmission electron microscope (ESTEM) with 0.1 nm resolution in systematic studies of complex dynamic oxidation and reduction mechanisms of copper nanoparticles. The oxidation of copper has previously been reported to be dependent on its crystallography and its interaction with the substrate. By following the dynamic oxidation process in situ in real time with high-angle annular dark-field imaging in the ESTEM, we use conditions ideal to track the oxidation front as it progresses across a copper nanoparticle by following the changes in the atomic number (Z) contrast with time. The oxidation occurs via the nucleation of the oxide phase (Cu 2 O) from one area of the nanoparticle which then progresses unidirectionally across the particle, with the Cu-to-Cu 2 O interface having a relationship of Cu{111}//Cu 2 O{111}. The oxidation kinetics are related to the temperature and oxygen pressure. When the process is reversed in hydrogen, the reduction process is observed to be similar to the oxidation, with the same crystallographic relationship between the two phases. The dynamic observations provide unique insights into redox mechanisms which are important to understanding and controlling the oxidation and reduction of copper-based nanoparticles.

The role of capital realignment versus in situ stabilization for the treatment of slipped capital femoral epiphysis.

PubMed

Souder, Christopher D; Bomar, James D; Wenger, Dennis R

2014-12-01

Slipped capital femoral epiphysis (SCFE) can be treated by a variety of methods with the traditional method of in situ pin fixation being most commonly used. More recently, the Modified Dunn (Mod. Dunn) procedure consisting of capital realignment has been popularized as a treatment method for SCFE, particularly for more severe cases. Over the last 5 years, our institution has selectively used this method for more complex cases. The purpose of this article is to evaluate the differences between these 2 treatment methods in terms of avascular necrosis (AVN) rate, reoperation rate, and complication rate. Eighty-eight hips that were surgically treated for SCFE between July 2004 and June 2012 met our inclusion criteria. The in situ fixation group included 71 hips, whereas 17 hips were anatomically reduced with the Mod. Dunn procedure. Loder classification, severity, acuity, complication rate, and reoperation rate were determined for the 2 cohorts. The χ analysis was performed to evaluate the relationship between the treatment method and outcome. As expected, stable slips did well with in situ pinning with no cases of AVN, even in more severe slips. Ten stable slips were treated with the Mod. Dunn approach and 2 (20%) developed AVN. Unstable slips were more difficult to treat with 3 of the 7 hips stabilized in situ developing AVN (43%). Two of the 7 unstable slips treated by the Mod. Dunn procedure developed AVN (29%). The other outcomes studied (reoperation rate and complication rate) were not significantly related to the surgical treatment method (P = 0.732 and 0.261, respectively). In situ pinning remains a safe and predictable method for treatment of stable SCFE with no AVN noted, even in severe slips. Attempts to anatomically reduce stable slips led to severe AVN in 20% of cases, thus this treatment approach should be considered with caution. Treatment of unstable slips remains problematic with high AVN rates noted whether treated by in situ fixation or capital realignment (Mod. Dunn). Level III retrospective comparative study.

Development and application of a rapid, user-friendly, and inexpensive method to detect Dehalococcoides sp. reductive dehalogenase genes from groundwater.

PubMed

Kanitkar, Yogendra H; Stedtfeld, Robert D; Hatzinger, Paul B; Hashsham, Syed A; Cupples, Alison M

2017-06-01

TaqMan probe-based quantitative polymerase chain reaction (qPCR) specific to the biomarker reductive dehalogenase (RDase) genes is a widely accepted molecular biological tool (MBT) for determining the abundance of Dehalococcoides sp. in groundwater samples from chlorinated solvent-contaminated sites. However, there are significant costs associated with this MBT. In this study, we describe an approach that requires only low-cost laboratory equipment (a bench top centrifuge and a water bath) and requires less time and resources compared to qPCR. The method involves the concentration of biomass from groundwater, without DNA extraction, and loop-mediated isothermal amplification (LAMP) of the cell templates. The amplification products are detected by a simple visual color change (orange/green). The detection limits of the assay were determined using groundwater from a contaminated site. In addition, the assay was tested with groundwater from three additional contaminated sites. The final approach to detect RDase genes, without DNA extraction or a thermal cycler, was successful to 1.8 × 10 5  gene copies per L for vcrA and 1.3 × 10 5  gene copies per L for tceA. Both values are below the threshold recommended for effective in situ dechlorination.

Solutions Network Formulation Report. The Potential Contributions of the Global Precipitation Measurement Mission to Phosphorus Reduction Efforts in the Florida Everglades

NASA Technical Reports Server (NTRS)

Anderson, Daniel; Hilbert, Kent; Lewis, David

2009-01-01

This candidate solution suggests the use of GPM precipitation observations to enhance the CERP. Specifically, GPM measurements could augment in situ precipitation data that are used to model agricultural phosphorus discharged into the Everglades. This solution benefits society by aiding water resource managers in identifying effective phosphorus reduction scenarios and thereby returning the Everglades to a more natural state. This solution supports the Water Management, Coastal Management, and Ecological Forecasting National Applications.

CH4 production via CO2 reduction in a temperate bog - A source of (C-13)-depleted CH4

NASA Technical Reports Server (NTRS)

Lansdown, J. M.; Quay, P. D.; King, S. L.

1992-01-01

The paper reports measurements, taken over two annual cycles, of the flux and delta(C-13) of CH4 released from an acidic peat bog located in the foothills of the Cascade Range in Washington state, U.S. Measurements of the rate of aceticlastic methanogenesis and CO2 reduction in peat soil, using (C-14)-labeled acetate and sodium bicarbonate, show that acetate was not an important CH4 precursor and that CO2 reduction could account for all of the CH4 production. The in situ kinetic isotope effect for CO2 reduction, calculated using the delta-(C-13) of soil water CO2 and CH4 flux, was 0.932 +/- 0.007.

In-situ monitoring of H2O2 degradation by live cells using voltammetric detection in a lab-on-valve system.

PubMed

Lähdesmäki, Ilkka; Park, Young K; Carroll, Andrea D; Decuir, Michael; Ruzicka, Jaromir

2007-08-01

This paper describes a method for monitoring the degradation of hydrogen peroxide by cells immobilized on a beaded support. The detection is based on the voltammetric reduction of hydrogen peroxide on a mercury film working electrode, whilst combining the concept of sequential injection (SI) with the lab-on-valve (LOV) manifold allows the measurements to be carried out in real time and automatically, in well-defined conditions. The method is shown to be capable of simultaneously monitoring hydrogen peroxide in the 10-1000 microM range and oxygen in the 160-616 microM range. A correction algorithm has been used to ensure reliable H2O2 results in the presence of varying oxygen levels. The method has been successfully applied to monitoring the degradation of H2O2 by wild-type cells and by catalase-overexpressing mouse embryonic fibroblasts. Since the technique allows the monitoring of the initial response rate, it provides data not accessible by current methods that are end-point-based measurements.

Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

EPA Science Inventory

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

In-situ observation of the growth of individual silicon wires in the zinc reduction reaction of SiCl4

NASA Astrophysics Data System (ADS)

Inasawa, Susumu

2015-02-01

We conducted in-situ monitoring of the formation of silicon wires in the zinc reduction reaction of SiCl4 at 950 °C. Tip growth with a constant growth rate was observed. Some wires showed a sudden change in the growth direction during their growth. We also observed both the lateral faces and cross sections of formed wires using a scanning electron microscope. Although wires with smooth lateral faces had a smooth hexagonal cross section, those with rough lateral faces had a polygonal cross section with a radial pattern. The transition of lateral faces from smooth to rough was found even in a single wire. Because the diameter of the rough part became larger than that of the smooth part, we consider that the wire diameter is a key factor for the lateral faces. Our study revealed that both dynamic and static observations are still necessary to further understand the VLS growth of wires and nanowires.

Renewable Molecular Flasks with NADH Models: Combination of Light-Driven Proton Reduction and Biomimetic Hydrogenation of Benzoxazinones.

PubMed

Zhao, Liang; Wei, Jianwei; Lu, Junhua; He, Cheng; Duan, Chunying

2017-07-17

Using small molecules with defined pockets to catalyze chemical transformations resulted in attractive catalytic syntheses that echo the remarkable properties of enzymes. By modulating the active site of a nicotinamide adenine dinucleotide (NADH) model in a redox-active molecular flask, we combined biomimetic hydrogenation with in situ regeneration of the active site in a one-pot transformation using light as a clean energy source. This molecular flask facilitates the encapsulation of benzoxazinones for biomimetic hydrogenation of the substrates within the inner space of the flask using the active sites of the NADH models. The redox-active metal centers provide an active hydrogen source by light-driven proton reduction outside the pocket, allowing the in situ regeneration of the NADH models under irradiation. This new synthetic platform, which offers control over the location of the redox events, provides a regenerating system that exhibits high selectivity and efficiency and is extendable to benzoxazinone and quinoxalinone systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ assessment of pesticide genotoxicity in an integrated pest management program: II. Maize waxy mutation assay.

PubMed

Rodrigues, G S; Pimentel, D; Weinstein, L H

1998-02-13

The mutagenicity induced by pesticides applied in an integrated pest management (IPM) program was evaluated in situ with the maize forward waxy mutation bioassay. Three pesticide application rates were prescribed as follows: (1) Low--no field pesticide spray; (2) Medium--IPM test rate: banded cyanazine plus metolachlor (2.7 kg a.i. and 2.3 l a.i./ha of herbicides, respectively); and (3) High--a preventative pesticide application program: broadcast cyanazine plus metolachlor (same application rates as above) plus chlorpyrifos (1 kg a.i./ha of insecticide). In general, there was no significant reduction in the genotoxic effects from the high to the medium treatment levels of the IPM program. This suggests that the reduction in pesticide application rates attained with the implementation of the proposed IPM program was not sufficient to abate the genotoxicity of the pesticides. The results indicate that replacing genotoxic compounds may be the only effective remediation measure if concern about environmental mutagenesis were to result in changes in agricultural management.

Investigating different mechanisms for biogenic selenite transformations: Geobacter sulfurreducens, Shewanella oneidensis and Veillonella atypica

USGS Publications Warehouse

Pearce, C.I.; Pattrick, R.A.D.; Law, N.; Charnock, J.M.; Coker, V.S.; Fellowes, J.W.; Oremland, R.S.; Lloyd, J.R.

2009-01-01

The metal-reducing bacteria Geobacter sulfurreducens, Shewanella oneidensis and Veillonella atypica, use different mechanisms to transform toxic, bioavailable sodium selenite to less toxic, non-mobile elemental selenium and then to selenide in anaerobic environments, offering the potential for in situ and ex situ bioremediation of contaminated soils, sediments, industrial effluents, and agricultural drainage waters. The products of these reductive transformations depend on both the organism involved and the reduction conditions employed, in terms of electron donor and exogenous extracellular redox mediator. The intermediary phase involves the precipitation of elemental selenium nanospheres and the potential role of proteins in the formation of these structures is discussed. The bionanomineral phases produced during these transformations, including both elemental selenium nanospheres and metal selenide nanoparticles, have catalytic, semiconducting and light-emitting properties, which may have unique applications in the realm of nanophotonics. This research offers the potential to combine remediation of contaminants with the development of environmentally friendly manufacturing pathways for novel bionanominerals. ?? 2009 Taylor & Francis.

Significant reduction of sperm disomy in six men: effect of traditional Chinese medicine?

PubMed

Tempest, Helen G; Homa, Sheryl T; Zhai, Xiao-Ping; Griffin, Darren K

2005-12-01

To test the hypothesis that levels of sperm disomy fell significantly in six men treated by traditional Chinese medicine (TCM). Fluorescence in situ hybridization (FISH) was done on the sperm heads of six men before and during treatment by TCM. There was a significant reduction in sperm disomy in all six men. This coincided with TCM treatment. This is the first study reporting a significant reduction in sperm disomy in men over a given time course. The fact that this coincided with TCM treatment is intriguing but no conclusions can be drawn from this until placebo-controlled clinical trials are implemented.

Antimicrobial effect of chlorhexidine digluconate in dentin: In vitro and in situ study.

PubMed

Borges, Fátima Maria Cavalcante; de Melo, Mary Anne Sampaio; Lima, Juliana Paiva Marques; Zanin, Iriana Carla Junqueria; Rodrigues, Lidiany Karla Azevedo

2012-01-01

The aim of this study was to evaluate a very short-term in vitro and in situ effect of 2% chlorhexidine-digluconate-based (CHX) cavity cleanser on the disinfection of dentin demineralized by cariogenic bacteria. Human dentin slabs were randomly allocated and used in 2 distinct phases, in vitro and in situ, for obtaining demineralized dentin. In vitro, the slabs (n=15) were immersed for 5 days in BHI broth inoculated with Streptococcus mutans CTT 3440. In situ, a double-blind design was conducted in one phase of 14 days, during which 20 volunteers wore palatal devices containing two human dental dentin slabs. On 5(th) day in vitro and 14(th) day in situ, the slabs were allocated to the two groups: Control group (5 μl of 0.9% NaCl solution) and CHX group (5 μl of 2% chlorhexidine digluconate solution, Cavity Cleanser™ BISCO, Schaumburg, IL, EUA), for 5 minutes. The microbiological analyses were performed immediately before and after the treatments. The log reductions means found for CHX treatment on tested micro organisms were higher when compared to Control group either in vitro or in situ conditions. Our results showed that CHX was effective in reducing the cultivable microbiota in contaminated dentin. Furthermore, although the use of chlorhexidine-digluconate-based cavity disinfectant did not completely eliminate the viable microorganisms, it served as a suitable agent to disinfect tooth preparations.

A Low-Cost, In Situ Resistivity and Temperature Monitoring System

EPA Science Inventory

We present a low-cost, reliable method for long-term in situ autonomous monitoring of subsurface resistivity and temperature in a shallow, moderately heterogeneous subsurface. Probes, to be left in situ, were constructed at relatively low cost with close electrode spacing. Once i...