Medical Applications of Synchrotron Radiation

DOE R&D Accomplishments Database

Thomlinson, W.

1991-10-01

Ever since the first diagnostic x-ray was done in the United States on February 3, 1896, the application of ionizing radiation to the field of medicine has become increasingly important. Both in clinical medicine and basic research the use of x-rays for diagnostic imaging and radiotherapy is now widespread. Radiography, angiography, CAT and PETT scanning, mammography, and nuclear medicine are all examples of technologies developed to image the human anatomy. In therapeutic applications, both external and internal sources of radiation are applied to the battle against cancer. The development of dedicated synchrotron radiation sources has allowed exciting advances to take place in many of these applications. The new sources provide tunable, high-intensity monochromatic beams over a wide range of energies which can be tailored to specific programmatic needs. This paper surveys those areas of medical research in which synchrotron radiation facilities are actively involved.

Reverse transcriptase inhibitors as microbicides.

PubMed

Lewi, Paul; Heeres, Jan; Ariën, Kevin; Venkatraj, Muthusamy; Joossens, Jurgen; Van der Veken, Pieter; Augustyns, Koen; Vanham, Guido

2012-01-01

The CAPRISA 004 study in South Africa has accelerated the development of vaginal and rectal microbicides containing antiretrovirals that target specific enzymes in the reproduction cycle of HIV, especially reverse transcriptase inhibitors (RTI). In this review we discuss the potential relevance of HIV-1 RTIs as microbicides, focusing in the nucleotide RTI tenofovir and six classes of nonnucleoside RTIs (including dapivirine, UC781, urea and thiourea PETTs, DABOs and a pyrimidinedione). Although tenofovir and dapivirine appear to be most advanced in clinical trials as potential microbicides, several issues remain unresolved, e.g., the importance of nonhuman primates as a "gatekeeper" for clinical trials, the emergence and spread of drug-resistant mutants, the combination of microbicides that target different phases of viral reproduction and the accessibility to microbicides in low-income countries. Thus, here we discuss the latest research on RTI as microbicides in the light of the continuing spread of the HIV pandemic from the point of view of medicinal chemistry, virological, and pharmaceutical studies.

Measurement in vivo of dopamine receptor density II: Effect of d-amphetamine on spiroperidol binding

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

Friedman, A.M.; De Jesus, O.T.; Woolverton, W.

1984-01-01

In the authors continuing studies to measure dopamine (DA) receptors in vivo using the DA antagonist bromospiroperidol (BrSP) and positron emission tomography (PET). The authors have examined the effect of d-amphetamine (d-AMP) on BrSP distribution in primate brain. Using the University of Chicago PETT VI scanner, /sup 76/Br-BrSP was found to localize in the caudate and putamen of anesthetized rhesus monkeys. The maximum level of this drug in these regions was reached at 100 minutes post-injection and remained constant for the next 200 minutes. Levels in the cerebellum, on the other hand, decline steadily after an hour post-injection. This ismore » consistent with the presence of high level of DA receptors in the basal ganglia and low levels in the cerebellum. Preliminary studies showed that the administration of d-AMP (0.5 mg/kg i.v.) resulted in a small but statistically significant decrease in caudate /sup 76/Br-BrSP levels. Since d-AMP is known to release DA in the caudate, these findings are consistent with the competition of released DA for BrSP binding at caudate DA binding sites.« less

The emerging profile of cross-resistance among the nonnucleoside HIV-1 reverse transcriptase inhibitors.

PubMed

Sluis-Cremer, Nicolas

2014-07-31

Nonnucleoside reverse transcriptase inhibitors (NNRTIs) are widely used to treat HIV-1-infected individuals; indeed most first-line antiretroviral therapies typically include one NNRTI in combination with two nucleoside analogs. In 2008, the next-generation NNRTI etravirine was approved for the treatment of HIV-infected antiretroviral therapy-experienced individuals, including those with prior NNRTI exposure. NNRTIs are also increasingly being included in strategies to prevent HIV-1 infection. For example: (1) nevirapine is used to prevent mother-to-child transmission; (2) the ASPIRE (MTN 020) study will test whether a vaginal ring containing dapivirine can prevent HIV-1 infection in women; (3) a microbicide gel formulation containing the urea-PETT derivative MIV-150 is in a phase I study to evaluate safety, pharmacokinetics, pharmacodynamics and acceptability; and (4) a long acting rilpivirine formulation is under-development for pre-exposure prophylaxis. Given their widespread use, particularly in resource-limited settings, as well as their low genetic barriers to resistance, there are concerns about overlapping resistance between the different NNRTIs. Consequently, a better understanding of the resistance and cross-resistance profiles among the NNRTI class is important for predicting response to treatment, and surveillance of transmitted drug-resistance.

The Emerging Profile of Cross-Resistance among the Nonnucleoside HIV-1 Reverse Transcriptase Inhibitors

PubMed Central

Sluis-Cremer, Nicolas

2014-01-01

Nonnucleoside reverse transcriptase inhibitors (NNRTIs) are widely used to treat HIV-1-infected individuals; indeed most first-line antiretroviral therapies typically include one NNRTI in combination with two nucleoside analogs. In 2008, the next-generation NNRTI etravirine was approved for the treatment of HIV-infected antiretroviral therapy-experienced individuals, including those with prior NNRTI exposure. NNRTIs are also increasingly being included in strategies to prevent HIV-1 infection. For example: (1) nevirapine is used to prevent mother-to-child transmission; (2) the ASPIRE (MTN 020) study will test whether a vaginal ring containing dapivirine can prevent HIV-1 infection in women; (3) a microbicide gel formulation containing the urea-PETT derivative MIV-150 is in a phase I study to evaluate safety, pharmacokinetics, pharmacodynamics and acceptability; and (4) a long acting rilpivirine formulation is under-development for pre-exposure prophylaxis. Given their widespread use, particularly in resource-limited settings, as well as their low genetic barriers to resistance, there are concerns about overlapping resistance between the different NNRTIs. Consequently, a better understanding of the resistance and cross-resistance profiles among the NNRTI class is important for predicting response to treatment, and surveillance of transmitted drug-resistance. PMID:25089538

Influence of cardiac and respiratory motion on tomographic reconstructions of the heart: implications for quantitative nuclear cardiology

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

Ter-Pogossian, M.M.; Bergmann, S.R.; Sobel, B.E.

1982-12-01

The potential influence of physiological, periodic motions of the heart due to the cardiac cycle, the respiratory cycle, or both on quantitative image reconstruction by positron emission tomography (PET) has been largely neglected. To define their quantitative impact, cardiac PET was performed in 6 dogs after injection of /sup 11/C-palmitate under disparate conditions including: normal cardiac and respiration cycles and cardiac arrest with and without respiration. Although in vitro assay of myocardial samples demonstrated that palmitate uptake was homogeneous (coefficient of variation . 10.1%), analysis of the reconstructed images demonstrated significant heterogeneity of apparent cardiac distribution of radioactivity due tomore » both intrinsic cardiac and respiratory motion. Image degradation due to respiratory motion was demonstrated in a healthy human volunteer as well, in whom cardiac tomography was performed with Super PETT I during breath-holding and during normal breathing. The results indicate that quantitatively significant degradation of reconstructions of true tracer distribution occurs in cardiac PET due to both intrinsic cardiac and respiratory induced motion of the heart. They suggest that avoidance of or minimization of these influences can be accomplished by gating with respect to both the cardiac cycle and respiration or by employing brief scan times during breath-holding.« less

[The use of complex interval models for predicting activity of non-nucleoside reverse transcriptase activity].

PubMed

Burliaeva, E V; Tarkhov, A E; Burliaev, V V; Iurkevich, A M; Shvets, V I

2002-01-01

Searching of new anti-HIV agents is still crucial now. In general, researches are looking for inhibitors of certain HIV's vital enzymes, especially for reverse transcriptase (RT) inhibitors. Modern generation of anti-HIV agents represents non-nucleoside reverse transcriptase inhibitors (NNRTIs). They are much less toxic than nucleoside analogues and more chemically stable, thus being slower metabolized and emitted from the human body. Thus, search of new NNRTIs is actual today. Synthesis and study of new anti-HIV drugs is very expensive. So employment of the activity prediction techniques for such a search is very beneficial. This technique allows predicting the activities for newly proposed structures. It is based on the property model built by investigation of a series of known compounds with measured activity. This paper presents an approach of activity prediction based on "structure-activity" models designed to form a hypothesis about probably activity interval estimate. This hypothesis formed is based on structure descriptor domains, calculated for all energetically allowed conformers for each compound in the studied sef. Tetrahydroimidazobenzodiazipenone (TIBO) derivatives and phenylethyltiazolyltiourea (PETT) derivatives illustrated the predictive power of this method. The results are consistent with experimental data and allow to predict inhibitory activity of compounds, which were not included into the training set.

PET - radiopharmaceutical facilities at Washington University Medical School - an overview

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

Dence, C.S.; Welch, M.J.

1994-12-31

The PET program at Washington University has evolved over more than three decades of research and development in the use of positron-emitting isotopes in medicine and biology. In 1962 the installation of the first hospital cyclotron in the USA was accomplished. This first machine was an Allis Chalmers (AC) cyclotron and it was operated until July, 1990. Simultaneously with this cyclotron the authors also ran a Cyclotron Corporation (TCC) CS-15 cyclotron that was purchased in 1977. Both of these cyclotrons were maintained in-house and operated with a relatively small downtime (approximately 3.5%). After the dismantling of the AC machine inmore » 1990, a Japanese Steel Works 16/8 (JSW-16/8) cyclotron was installed in the vault. Whereas the AC cyclotron could only accelerate deuterons (6.2 MeV), the JSW - 16/8 machine can accelerate both protons and deuterons, so all of the radiopharmaceuticals can be produced on either of the two presently owned accelerators. At the end of May 1993, the medical school installed the first clinical Tandem Cascade Accelerator (TCA) a collaboration with Science Research Laboratories (SRL) of Somerville, MA. Preliminary target testing, design and development are presently under way. In 1973, the University installed the first operational PETT device in the country, and at present there is a large basic science and clinical research program involving more than a hundred staff in nuclear medicine, radiation sciences, neurology, neurosurgery, psychiatry, cardiology, pulmonary medicine, oncology, and surgery.« less

Metabolic activity of uncultivated magnetotactic bacteria revealed by NanoSIMS

NASA Astrophysics Data System (ADS)

He, M.; Zhang, W.; Gu, L.; Pan, Y.; Lin, W.

2017-12-01

Microorganisms that exhibit magnetotaxis behavior, collectively known as the magnetotactic bacteria (MTB), are those whose motility is influenced by the Earth's magnetic field. MTB are a physiologically diverse group of bacteria with a unique feature of intracellular biomineralization of magnetosomes (Fe3O4 and/or Fe3S4) (Bazylinski et al., 2013). However, the ecophysiology of uncultivated MTB, especially those within the Nitrospirae phylum forming hundreds of bullet-shaped magnetite magnetosomes per cell, is still not well characterized (Lin et al., 2014). Nanoscale secondary ion mass spectrometry (NanoSIMS) is a powerful tool for revealing element distribution in nanometer-scale resolution, which opens exciting possibilities for the study of interactions between microorganisms and environments (Gao et al., 2016; Musat et al., 2016). Here we applied NanoSIMS to investigate the dynamics of carbon and nitrogen assimilations in two magnetotactic Nitrospirae populations at single cell level. Our NanoSIMS results confirmed the metabolic potential of Nitrospirae MTB proposed by genomic and metagenomic analysis and provided additional insights into the ecophysiology of uncultivated MTB. This study suggests that NanoSIMS-based analyses are powerful approaches for investigating and characterizing the ecological function of environmental microorganisms. References: Bazylinski D A., Lefèvre, C T., Schüler D., 2013. Magnetotactic Bacteria. 453-494.Lin W, Bazylinski DA, Xiao T, Wu L- F, Pan Y., 2014. Life with compass: diversity and biogeography of magnetotactic bacteria. Environ Microbiol, 16: 1462-2920.Gao D., Huang X., Tao Y., 2016. A critical review of NanoSIMS in analysis of microbial metabolic activities at single-cell level. Crit Rev Biotechnol, 36: 884-890.Musat N., Musat F., Weber PK., Pett-Ridge J., 2016. Tracking microbial interactions with NanoSIMS. Curr Opin Biotechnol, 41: 114-121.

GROWTH AND METABOLISM OF INDIVIDUAL BACTERIAL CELLS UTILIZING NANOSIMS

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

NEALSON, H. K.

This work involved the use of the Nano-SIMS Instrument at Lawrence Livermore Laboratory, in an effort to utilize this unique tool for experiments in Biology. The work consisted primarily of experiments to measure in real time, C and N fixation in cyanobacteria. The work revealed a number of the difficulties in using the nano-SIMS approach with biological material, but with collaboration from a number of individuals at USC and LLNL, major progress was made. The collaborators from LLNL were from the Chemistry Group (Dr. Peter Weber), and the Biology Group (Dr. Jennifer Pett-Ridge). In addition, there were a number ofmore » other scientists involved from LLNL. The USC group consisted of Dr. K.H. Nealson, the PI on the grant, Dr. R. Popa, a postdoctoral fellow and research associate at USC, Professor Douglas Capone, and Juliet Finze, a graduate student in biology. Two major experiments were done, both of which yielded new and exciting data. (1) We studied nitrogen and carbon fixation in Anabaena, demonstrating that fixation ofN occurred rapidly in the heterocysts, and that the fixed N was transported rapidly and completely to the vegetative cells. C fixation occurred in the vegetative cells, with labeled C remaining in these cells in support of their growth and metabolism. This work was accepted in the ISME Journal (Nature Publication), and published last month. (2) We studied nitrogen and carbon fixation in Trichodesmium, a non-heterocystous cyanobacterium that also fixes nitrogen. Interestingly, the nitrogen fixation was confined to regions within the filaments that seem to be identical to the so-called cyanophycaen granules. The fixed N is then transported to other parts of the cyanobacterium, as judged by movement of the heavy N throughout the filaments. On the basis of these very exciting results, we have applied for funding from the NSF to continue the collaboration with LLNL. The results of both studies were presented in the summer of 2007 at the Gordon Research Conference (Applied Environmental Microbiol.).« less

Competing for phosphors under changing redox conditions: biological versus geochemical sinks

NASA Astrophysics Data System (ADS)

Gross, A.; Pett-Ridge, J.; Silver, W. L.

2016-12-01

Competing for phosphorus under changing redox conditions: biological versus geochemical sinksAvner Gross1, Jennifer Pett-Ridge2 and Whendee L Silver1 University of California Berkeley, Department of Environmental Science, Policy, & Management, Berkeley, CA, USA. Lawrence Livermore National Laboratory, Physical and Life Science Directorate, Livermore, CA, USA. The cycling of phosphorous (P) in highly weathered, humid tropical forest soils is tightly regulated by P sorption dynamics to the surfaces of Fe(III) (hydr)oxides and root and microbial demands for P. Periods of anoxic soil conditions, which are common in humid environments, induce the reduction of Fe (III) to Fe (II) and may release sorbed P into the soil solution. The microbial demand for P is influenced by the C and nutrient composition of their available substrates. Therefore, we hypothesize that soil redox conditions and substrate quality and availability will control the partitioning of P between microbial biomass and the soil mineral phase. The aim of this study was to examine how fluctuations in soil redox conditions and changes in microbial P demand affect the fate of new P that enters the soil solution. To achieve this aim we conducted a series of soil incubation experiments using a wet tropical soil from Puerto Rico (where redox conditions and P availability naturally oscillate) with a single pulse of phosphate (PO4), altering both the microbial activity and redox conditions. To follow the fate the added P, the added phosphate was labeled with 18O. As the exchange of oxygen between phosphate and water only occurs during biological processes, P-18O labeling can be used as an indicator of microbial use. To quantify sizes of the microbial and mineral P pools we used traditional chemical extractions in the bulk scale. We used NanoSIMS isotopic imaging to map the distribution of P-16O and P-18O and co-localization with Fe minerals at the nano scale. Our results show that the amount of the added P fixed by the mineral phase was inversely correlated to the amount of P assimilated by the microbial biomass. In addition, we discovered the iron redox state did not affect the microbial or mineral P pool sizes. Overall, our results indicate the partition of the added P between the biological and mineral pools is regulated by the microbial biomass demands for P.

Toward a new system approach of complexity in geomorphology

NASA Astrophysics Data System (ADS)

Masson, E.

2012-04-01

Since three decades the conceptual vision of catchment and fluvial geomorphology is strongly based on the "fluvial system" (S. A. Schumm, 1977) and the "river continuum system" (R. L. Vannote et al., 1980) concepts that can be embedded in a classical physical "four dimensions system" (C. Amoros and G.-E. Petts, 1993). Catchment and network properties, sediment and water budgets and their time-space variations are playing a major role in this geomorpho-ecological approach of hydro-geomorphosystems in which human impacts are often considered as negative externalities. The European Water Framework Directive (i.e. WFD, Directive 2000/60/EC) and its objective of good environmental status is addressing the question of fluvial/catchment/landscape geomorphology and its integration into IWRM in such a sustainable way that deeply brings back society and social sciences into the water system analysis. The DPSIR methodology can be seen as an attempt to cope with the analysis of unsustainable consequences of society's water-sediment-landscape uses, environmental pressures and their consequences on complex fluvial dynamics. Although more and more scientific fields are engaged in this WFD objective there's still a lack of a global theory that could integrate geomorphology into the multi-disciplinary brainstorming discussion about sustainable use of water resources. Our proposition is to promote and discuss a trans-disciplinary approach of catchments and fluvial networks in which concepts can be broadly shared across scientific communities. The objective is to define a framework for thinking and analyzing geomorphological issues within a whole "Environmental and Social System" (i.e. ESS, E. Masson 2010) with a common set of concepts and "meta-concepts" that could be declined and adapted in any scientific field for any purpose connected with geomorphology. We assume that geomorphological research can benefit from a six dynamic dimensions system approach based on structures, functions, connections, phases, topologies and adaptations. By combining these six dimensions one can easily understand that geomorphological features and dynamics are then considered as very complex systems in which hierarchies, information, discontinuities, openness, resilience and self-organized responses are fundamental properties emerging among many others (E. Masson 2010). This conceptual approach is consistent with many other scientific concepts used in ecological sciences (S-E. Jorgensen et al. 2007, C-S. Holling and al. 2002, I. Prigogine 1997, W-M. Elsasser 1987…) but also in human sciences (A. Dauphiné 2003, Ch.P.Péguy 2001, P. Bourdieu 1987, U. Beck 1986, J. Tricart 1968, C. Levy-Strauss 1958…), in physics (P. Bak, 1996, K-R. Popper 1982, I. Prigogine 1955…) and obviously into systemic science (E. Morin 1977, J-L. Moigne 1977, L. Von Bertalanffy 1968). Our contribution is then an encouraging attempt to expand the frontier of geomorphological theory with a new trans-disciplinary approach that deals with the huge complexity of hydrosystems considered as a whole Environmental and Social System.

Life's Impact on the Soil Production Function

NASA Astrophysics Data System (ADS)

Harrison, Emma; Willenbring, Jane; Brocard, Gilles

2016-04-01

Soil melds life and lithology, but the top-down production of soil by the incorporation of organic matter has typically been viewed through a lens of soil biogeochemistry and the bottom-up weathering of bedrock viewed from a geomorphologic perspective. We merge these perspectives by developing a variation on the classic geomorphological soil production function [1] that accounts for the influence of top-down soil production by additions of organic material. In the classic view [1], production rate of soil from bedrock weathering is a function of the thickness of the soil horizon. Under steady state conditions, this thickness is controlled by a constant coefficient of diffusion and by the hillslope curvature. Across the globe, equilibrium landscapes can be hard to find. We explore the many ways that biota influence the upper soil horizons and move the soil-hillslope system out of steady state using measurements of in situ 10Be at depth in soil profiles. Our empirical case study is in the Luquillo Critical Zone Observatory of northeastern Puerto Rico, where long term ecological monitoring suggests an average of 375 m My-1 of litter fall [2] and as much as 17.5 m My-1 of dust [3] is contributed to the forest floor. This substantial volume of material forms an active surficial layer, functionally increasing the residence time of grains deeper in the soil profile. Litter recycling influences the cosmogenic dose rate to be higher by increasing the residence time of grains and to be lower by increasing environmental shielding. In unconstrained systems, probabilistic modeling can determine a range of solutions for the ages of grains determined with 10Be depth profiles[4]. We compare the probabilistic outcomes to actual measurements of the in situ 10Be at depth in soil profiles from the Luquillo Mountains. Life living in the soil, rather than on it, is of equal importance in the Luquillo Mountains. On average, the soil is occupied by 200 individual earthworms per m2 [5]. The depth of soil mixing in the soil profiles we collect is shown by the homogenization of 10Be concentrations in grains. Mixing changes the residence time of grains in soil. The length of this residence time is a critical component in the rate of weathering reactions, the mechanism by which material is lost to chemical dissolution and leaching. Additionally, mixing may drive the value of the diffusion coefficient, which determines the flux of sediment out of the soil mantle in the geomorphic soil production function. Life actively impacts the soil-hillslope system, and quantifying these effects is an essential modification of a fundamental paradigm in the geomorphology of soil-mantled landscapes. [1] Heimsath et al. 1997. Nature 388:358-361 [2] Zou et al., 1995. Forest Ecol. and Management 78:147-157 [3] Pett-Ridge et al., 2009. Geochim. Cosmochim. Acta 73:25-43 [4] Hidy et al. 2010. Geochem. Geophys., Geosys. 11 [5] González et al. 2007. Eur. J. Soil Biol. 43:S24-S32

Carbon transfer from plant roots to soil - NanoSIMS analyses of undisturbed rhizosphere samples

NASA Astrophysics Data System (ADS)

Vidal, Alix; Hirte, Juliane; Bender, S. Franz; Mayer, Jochen; Gattinger, Andreas; Mueller, Carsten W.

2017-04-01

Soils are composed of a wide diversity of organic and mineral compounds, interacting to form complex mosaics of microenvironments. Roots and microorganisms are both key sources of organic carbon (OC). The volume of soil around living roots, i.e. the rhizosphere, is a privileged area for soil microbial activity and diversity. The microscopic observation of embedded soil sections has been applied since the 1950´s and has enabled observation of the rhizosphere at the smallest scale of organism interaction, i.e. at the level of root cells and bacteria (Alexander and Jackson, 1954). However, the observation of microorganisms in their intact environment, especially in soil, remains challenging. Existing microscopic images do not provide clear evidence of the chemical composition of compounds observed in the rhizosphere. Nano-scale secondary ion mass spectrometry (NanoSIMS) is a high spatial resolution method providing elemental and isotopic maps of organic and mineral materials. This technic has been increasingly used in soil science during the last decade (Hermann et al., 2007; Vogel et al., 2014) and more specifically for undisturbed soil sample observations (Vidal et al., 2016). In the present study, NanoSIMS was used to illustrate the biological, physical and chemical processes occurring in the rhizosphere at the microscale. To meet this objective, undisturbed rhizosphere samples were collected from a field experiment in Switzerland where wheat plants were pulse-labelled with 99% 13C-CO2 in weekly intervals throughout the growing season and sampled at flowering. Samples were embedded, sectioned, polished and analyzed with NanoSIMS, obtaining secondary ion images of 12C, 13C, 12C14N, 16O, 31P16O2, and 32S. The δ13C maps were obtained thanks to 12C and 13C images. 13C labelled root cells were clearly distinguished on images and presented highly variable δ13C values. Labelled spots (< 1 µm), identified as bacteria, were located at the root cell surroundings. These microorganisms were intimately associated with soil particles, forming microaggregates tightly bound to root cells. Finally, some images revealed the presence of larger labelled spots (> 4 µm) potentially assignable to arbuscular fungal hyphae. These results illustrate the transfer of carbon from the root tissues towards the microbial communities and the direct fate as organo-mineral associated OC at mineral soil particles. Alexander, F., Jackson, R., 1954. Examination of soil micro-organisms in their natural environment. Nature. 174, 750-751. Herrmann, A.M., Ritz, K., Nunan, N., Clode, P.L., Pett-Ridge, J., Kilburn, M.R., Murphy, D.V., O'Donnell, A.G., Stockdale, E.A., 2007. Nano-scale secondary ion mass spectrometry — A new analytical tool in biogeochemistry and soil ecology: A review article. Soil Biology and Biochemistry. 39, 1835-1850. Vidal, A., Remusat, L., Watteau, F., Derenne, S., Quenea K., 2016. Incorporation of 13C labelled shoot residues in Lumbricus terrestris casts: A combination of Transmission Electron Microscopy and Nanoscale Secondary Ion Mass Spectrometry. Soil Biology and Biochemistry. 93, 8-16. Vogel, C., Mueller, C.W., Höschen, C., Buegger, F., Heister, K., Schulz, S., Schloter, M., Kögel-Knabner, I., 2014. Submicron structures provide preferential spots for carbon and nitrogen sequestration in soils. Nature Communications 5.

Spatial and temporal distribution of 13C labelled plant residues in soil aggregates and Lumbricus terrestris surface casts: A combination of Transmission Electron Microscopy and Nanoscale Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Vidal, Alix; Remusat, Laurent; Watteau, Françoise; Derenne, Sylvie; Quenea, Katell

2016-04-01

Earthworms play a central role in litter decomposition, soil structuration and carbon cycling. They ingest both organic and mineral compounds which are mixed, complexed with mucus and dejected in form of casts at the soil surface and along burrows. Bulk isotopic or biochemical technics have often been used to study the incorporation of litter in soil and casts, but they could not reflect the complex interaction between soil, plant and microorganisms at the microscale. However, the heterogeneous distribution of organic carbon in soil structures induces contrasted microbial activity areas. Nano-scale secondary ion mass spectrometry (NanoSIMS), which is a high spatial resolution method providing elemental and isotopic maps of organic and mineral materials, has recently been applied in soil science (Herrmann et al., 2007; Vogel et al., 2014). The combination of Nano-scale secondary ion mass spectrometry (NanoSIMS) and Transmission Electron Microscopy (TEM) has proven its potential to investigate labelled residues incorporation in earthworm casts (Vidal et al., 2016). In line of this work, we studied the spatial and temporal distribution of plant residues in soil aggregates and earthworm surface casts. This study aimed to (1) identify the decomposition states of labelled plant residues incorporated at different time steps, in casts and soil, (2) identify the microorganisms implied in this decomposition (3) relate the organic matter states of decomposition with their 13C signature. A one year mesocosm experiment was set up to follow the incorporation of 13C labelled Ryegrass (Lolium multiflorum) litter in a soil in the presence of anecic earthworms (Lumbricus terrestris). Soil and surface cast samples were collected after 8 and 54 weeks, embedded in epoxy resin and cut into ultra-thin sections. Soil was fractionated and all and analyzed with TEM and NanoSIMS, obtaining secondary ion images of 12C, 16O, 12C14N, 13C14N and 28Si. The δ13C maps were obtained using the 13C14N-/12C14N- ratio. We identified various states of decomposition within a same sample, associated with a high heterogeneity of δ13C values of plant residues. We also recognized various labelled microorganisms, mainly bacteria and fungi, underlining their participation in residues decomposition. δ13C values were higher in casts than soil aggregates and decreased between 8 and 54 weeks for both samples. Herrmann, A.M., Ritz, K., Nunan, N., Clode, P.L., Pett-Ridge, J., Kilburn, M.R., Murphy, D.V., O'Donnell, A.G., Stockdale, E.A., 2007. Nano-scale secondary ion mass spectrometry - A new analytical tool in biogeochemistry and soil ecology: A review article. Soil Biology and Biochemistry. 39, 1835-1850. Vidal, A., Remusat, L., Watteau, F., Derenne, S., Quenea K., 2016. Incorporation of 13C labelled shoot residues in Lumbricus terrestris casts: A combination of Transmission Electron Microscopy and Nanoscale Secondary Ion Mass Spectrometry. Soil Biology and Biochemistry. Vogel, C., Mueller, C.W., Höschen, C., Buegger, F., Heister, K., Schulz, S., Schloter, M., Kögel-Knabner, I., 2014. Submicron structures provide preferential spots for carbon and nitrogen sequestration in soils. Nature Communications 5.

Low-temperature oxidizing plasma surface modification and composite polymer thin-film fabrication techniques for tailoring the composition and behavior of polymer surfaces

NASA Astrophysics Data System (ADS)

Tompkins, Brendan D.

This dissertation examines methods for modifying the composition and behavior of polymer material surfaces. This is accomplished using (1) low-temperature low-density oxidizing plasmas to etch and implant new functionality on polymers, and (2) plasma enhanced chemical vapor deposition (PECVD) techniques to fabricate composite polymer materials. Emphases are placed on the structure of modified polymer surfaces, the evolution of polymer surfaces after treatment, and the species responsible for modifying polymers during plasma processing. H2O vapor plasma modification of high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), polycarbonate (PC), and 75A polyurethane (PU) was examined to further our understanding of polymer surface reorganization leading to hydrophobic recovery. Water contact angles (wCA) measurements showed that PP and PS were the most susceptible to hydrophobic recovery, while PC and HDPE were the most stable. X-ray photoelectron spectroscopy (XPS) revealed a significant quantity of polar functional groups on the surface of all treated polymer samples. Shifts in the C1s binding energies (BE) with sample age were measured on PP and PS, revealing that surface reorganization was responsible for hydrophobic recovery on these materials. Differential scanning calorimetry (DSC) was used to rule out the intrinsic thermal properties as the cause of reorganization and hydrophobic recovery on HDPE, LDPE, and PP. The different contributions that polymer cross-linking and chain scission mechanisms make to polymer aging effects are considered. The H2O plasma treatment technique was extended to the modification of 0.2 microm and 3.0 microm track-etched polycarbonate (PC-TE) and track-etched polyethylene terephthalate (PET-TE) membranes with the goal of permanently increasing the hydrophilicity of the membrane surfaces. Contact angle measurements on freshly treated and aged samples confirmed the wettability of the membrane surfaces was significantly improved by plasma treatment. XPS and SEM analyses revealed increased oxygen incorporation onto the surface of the membranes, without any damage to the surface or pore structure. Contact angle measurements on a membrane treated in a stacked assembly suggest the plasma effectively modified the entire pore cross section. Plasma treatment also increased water flux through the membranes, with results from plasma modified membranes matching those from commercially available hydrophilic membranes (treated with wetting agent). Mechanisms for the observed modification are discussed in terms of OH and O radicals implanting oxygen functionality into the polymers. Oxidizing plasma systems (O2, CO2, H2O vapor, and formic acid vapor) were used to modify track-etched polycarbonate membranes and explore the mechanisms and species responsible for etching polycarbonate during plasma processing. Etch rates were measured using scanning electron microscopy; modified polycarbonate surfaces were further characterized using x-ray photoelectron spectroscopy and water contact angles. Etch rates and surface characterization results were combined with optical emission spectroscopy data used to identify gas-phase species and their relative densities. Although the oxide functionalities implanted by each plasma system were similar, the H2O vapor and formic acid vapor plasmas yielded the lowest contact angles after treatment. The CO2, H2O vapor, and formic acid vapor plasma-modified surfaces were, however, found to be similarly stable one month after treatment. Overall, etch rate correlated directly to the relative gas-phase density of atomic oxygen and, to a lesser extent, hydroxyl radicals. PECVD of acetic acid vapor (CH3COOH) was used to deposit films on PC-TE and silicon wafer substrates. The CH3COOH films were characterized using XPS, wCA, and SEM. This modification technique resulted in continuous deposition and self-limiting deposition of a-CxO yHz films on Si wafers and PC-TE, respectively. The self-limiting deposition on PC-TE revealed that resulting films have minimal impact on 3D PC structures. This technique would allow for more precise fabrication of patterned or nano-textured PC. PECVD is used to synthesize hydrocarbon/fluorocarbon thin films with compositional gradients by continuously changing the ratio of gases in a C 3F8/H2 plasma. The films are characterized using variable angle spectroscopic ellipsometry (VASE), Fourier transform infrared spectroscopy (FTIR), XPS, wCA, and SEM. These methods revealed that shifting spectroscopic signals can be used to characterize organization in the deposited film. Using these methods, along with gas-phase diagnostics, film chemistry and the underlying deposition mechanisms are elucidated, leading to a model that accurately predicts film thickness.