ALTERATION OF SOIL METAL CHEMISTRY AND PHYTOAVAILABILITY ASSOCIATED WITH BIOSOLIDS APPLICATION (ABSTRACT)

EPA Science Inventory

Biosolids are a complex mixture which contain both inorganic and organic adsorbents. Thus, addition of biosolids to soil not only increases the environmental loading of toxic metals (Cd, Zn, Cu, Ni, Pb, etc.) it alters the phytoavailability of these metals. This reduction in ph...

Control of Chemical Equilibrium by Solvent: A Basis for Teaching Physical Chemistry of Solutions

ERIC Educational Resources Information Center

Prezhdo, Oleg V.; Craig, Colleen F.; Fialkov, Yuriy; Prezhdo, Victor V.

2007-01-01

The study demonstrates that the solvent present in a system can highly alter and control the chemical equilibrium of a system. The results show that the dipole moment and polarizibility of a system can be highly altered by using different mixed solvents.

Management intensity alters decomposition via biological pathways

USGS Publications Warehouse

Wickings, Kyle; Grandy, A. Stuart; Reed, Sasha; Cleveland, Cory

2011-01-01

Current conceptual models predict that changes in plant litter chemistry during decomposition are primarily regulated by both initial litter chemistry and the stage-or extent-of mass loss. Far less is known about how variations in decomposer community structure (e.g., resulting from different ecosystem management types) could influence litter chemistry during decomposition. Given the recent agricultural intensification occurring globally and the importance of litter chemistry in regulating soil organic matter storage, our objectives were to determine the potential effects of agricultural management on plant litter chemistry and decomposition rates, and to investigate possible links between ecosystem management, litter chemistry and decomposition, and decomposer community composition and activity. We measured decomposition rates, changes in litter chemistry, extracellular enzyme activity, microarthropod communities, and bacterial versus fungal relative abundance in replicated conventional-till, no-till, and old field agricultural sites for both corn and grass litter. After one growing season, litter decomposition under conventional-till was 20% greater than in old field communities. However, decomposition rates in no-till were not significantly different from those in old field or conventional-till sites. After decomposition, grass residue in both conventional- and no-till systems was enriched in total polysaccharides relative to initial litter, while grass litter decomposed in old fields was enriched in nitrogen-bearing compounds and lipids. These differences corresponded with differences in decomposer communities, which also exhibited strong responses to both litter and management type. Overall, our results indicate that agricultural intensification can increase litter decomposition rates, alter decomposer communities, and influence litter chemistry in ways that could have important and long-term effects on soil organic matter dynamics. We suggest that future efforts to more accurately predict soil carbon dynamics under different management regimes may need to explicitly consider how changes in litter chemistry during decomposition are influenced by the specific metabolic capabilities of the extant decomposer communities.

Slow-cycle effects of foliar herbivory alter the nitrogen acquisition and population size of Collembola

Treesearch

Mark A. Bradford; Tara Gancos; Christopher J. Frost

2008-01-01

In terrestrial systems there is a close relationship between litter quality and the activity and abundance of decomposers. Therefore, the potential exists for aboveground, herbivore-induced changes in foliar chemistry to affect soil decomposer fauna. These herbivore-induced changes in chemistry may persist across growing seasons. While the impacts of such slow-cycle...

Mountain pine beetle attack alters the chemistry and flammability of lodgepole pine foliage

Treesearch

Wesley G. Page; Michael J. Jenkins; Justin B. Runyon

2012-01-01

During periods with epidemic mountain pine beetle (Dendroctonus ponderosae Hopkins) populations in lodgepole pine (Pinus contorta Dougl. ex Loud. var. latifolia Engelm.) forests, large amounts of tree foliage are thought to undergo changes in moisture content and chemistry brought about by tree decline and death. However, many of the presumed changes have yet to be...

Crystal-chemistry of alteration products of vitrified wastes: Implications on the retention of polluting elements

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

Sterpenich, Jerome

2008-07-01

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO{sub 4} . nH{sub 2}O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes themore » altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.« less

Snohomish RARE project update for Tulalip Tribes | Science ...

EPA Pesticide Factsheets

Rising atmospheric CO2 due to anthropogenic emissions alters local atmospheric gas exchange rates in estuaries, causing alterations of the seawater carbonate system and reductions in pH broadly described as coastal acidification. These changes in marine chemistry have been demonstrated to negatively affect a variety of coastal and estuarine organisms. The naturally dynamic carbonate chemistry of estuaries driven by biological activity, hydrodynamic processes, and intensive biogeochemical cycling has led to uncertainty regarding the role of rising atmospheric CO2 as a driver in these systems, and the suggestion that altered atmospheric exchange may be relatively unimportant to estuarine biogeochemistry. In this presentation, we illustrate how rising atmospheric CO2 from 1765 through 2100 interacts with the observed local carbonate chemistry dynamics of a seagrass bed, and calculated how pHT, pCO2, and Ωaragonite respond. This presentation is part of an informal meeting with the Tulalip Tribes of Tulalip, WA to update them on the progress of the ORD/Region 10 RARE project in the Snohomish estuary to study drivers of coastal acidification. Multiple processes, including primary production and respiration, river runoff, cultural eutrophication, oceanic upwelling, and atmospheric exchange contribute to the characteristically dynamic carbonate conditions in these habitats, with potential interactions amongst these processes leading to coastal acidification. As a

Evidence for organic synthesis in high temperature aqueous media - facts and prognosis

NASA Technical Reports Server (NTRS)

Simoneit, Bernd R. T.

1995-01-01

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to greater than 400 C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. The reactivity of organic compounds in hot water (200-350 C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to greater than 400 C.

Modeling of Nitrogen Oxides Emissions from CFB Combustion

NASA Astrophysics Data System (ADS)

Kallio, S.; Keinonen, M.

In this work, a simplified description of combustion and nitrogen oxides chemistry was implemented in a 1.5D model framework with the aim to compare the results with ones earlier obtained with a detailed reaction scheme. The simplified chemistry was written using 12 chemical components. Heterogeneous chemistry is given by the same models as in the earlier work but the homogeneous and catalytic reactions have been altered. The models have been taken from the literature. The paper describes the numerical model with emphasis on the chemistry submodels. A simulation of combustion of bituminous coal in the Chalmers 12 MW boiler is conducted and the results are compared with the results obtained earlier with the detailed chemistry description. The results are also compared with measured O2, CO, NO and N2O profiles. The simplified reaction scheme produces equally good results as earlier obtained with the more elaborate chemistry description.

Magmatic and fragmentation controls on volcanic ash surface chemistry

NASA Astrophysics Data System (ADS)

Ayris, Paul M.; Diplas, Spyros; Damby, David E.; Hornby, Adrian J.; Cimarelli, Corrado; Delmelle, Pierre; Scheu, Bettina; Dingwell, Donald B.

2016-04-01

The chemical effects of silicate ash ejected by explosive volcanic eruptions on environmental systems are fundamentally mediated by ash particle surfaces. Ash surfaces are a composite product of magmatic properties and fragmentation mechanisms, as well as in-plume and atmospheric alteration processes acting upon those surfaces during and after the eruption. Recent attention has focused on the capacity of alteration processes to shape ash surfaces; most notably, several studies have utilised X-ray photoelectron spectroscopy (XPS), a technique probing the elemental composition and coordination state of atoms within the top 10 nm of ash surfaces, to identify patterns of elemental depletions and enrichments relative to bulk ash chemical composition. Under the presumption of surface and bulk equivalence, any disparities have been previously attributed to surface alteration processes, but the ubiquity of some depletions (e.g., Ca, Fe) across multiple ash studies, irrespective of eruptive origin, could suggest these to be features of the surface produced at the instant of magma fragmentation. To investigate this possibility further, we conducted rapid decompression experiments at different pressure conditions and at ambient and magmatic temperature on porous andesitic rocks. These experiments produced fragmented ash material untouched by secondary alteration, which were compared to particles produced by crushing of large clasts from the same experiments. We investigated a restricted size fraction (63-90 μm) from both fragmented and crushed materials, determining bulk chemistry and mineralogy via XRF, SEM-BSE and EPMA, and investigated the chemical composition of the ash surface by XPS. Analyses suggest that fragmentation under experimental conditions partitioned a greater fraction of plagioclase-rich particles into the selected size fraction, relative to particles produced by crushing. Trends in surface chemical composition in fragmented and crushed particles mirror that partitioning effect, but crucially, disparities between surface and bulk chemistry remain evident. Simple glass-plagioclase mixing calculations suggest that this feature may indicate differences in bulk and surface mineral distributions; future QEMSCAN analysis will investigate this possibility further. Additionally, surface iron enrichments observed in our high temperature experiments suggest that hot oxidation effects can have a near-instantaneous, measurable effect on ash surface chemistry at the nanometre scale. Our preliminary results suggest that the chemical and mineral properties of the source magma, coupled with high temperature fragmentation processes, may have a significant influence on ash surface chemistry and mineralogy, and subsequently, on the post-eruptive alteration of ash particles and their reactivity within biotic and abiotic systems.

Conifer expansion reduces the competitive ability and herbivore defense of aspen by modifying light environment and soil chemistry.

PubMed

Calder, W John; Horn, Kevin J; St Clair, Samuel B

2011-06-01

Disturbance patterns strongly influence plant community structure. What remains less clear, particularly at a mechanistic level, is how changes in disturbance cycles alter successional outcomes in plant communities. There is evidence that fire suppression is resulting in longer fire return intervals in subalpine forests and that these lengthened intervals increase competitive interactions between aspen and conifer species. We conducted a field and greenhouse study to compare photosynthesis, growth and defense responses of quaking aspen and subalpine fir regeneration under light reductions and shifts in soil chemistry that occur as conifers increase in dominance. The studies demonstrated that aspen regeneration was substantially more sensitive to light and soil resource limitations than that of subalpine fir. For aspen, light reductions and/or shifts in soil chemistry limited height growth, biomass gain, photosynthesis and the production of defense compounds (phenolic glycosides and condensed tannins). Biomass gain and phenolic glycoside concentrations were co-limited by light reduction and changes in soil chemistry. In contrast, subalpine fir seedlings tended to be more tolerant of low light conditions and showed no sensitivity to changes in soil chemistry. Unlike aspen, subalpine fir increased its root to shoot ratio on conifer soils, which may partially explain its maintenance of growth and defense. The results suggest that increasing dominance of conifers in subalpine forests alters light conditions and soil chemistry in a way that places greater physiological and growth constraints on aspen than subalpine fir, with a likely outcome being more successful recruitment of conifers and losses in aspen cover.

Relationships between moisture, chemistry, and ignition of Pinus contorta needles during the early stages of mountain pine beetle attack

Treesearch

W. Matt Jolly; Russell A. Parsons; Ann M. Hadlow; Greg M. Cohn; Sara S. McAllister; John B. Popp; Robert M. Hubbard; Jose F. Negron

2012-01-01

Very little is known about how foliar moisture and chemistry change after a mountain pine beetle attack and even less is known about how these intrinsic foliar characteristics alter foliage ignitability. Here, we examine the fuel characteristics and ignition potential of Pinus contorta (lodgepole pine) foliage during the early stages of a mountain pine beetle attack....

Enhanced litter input rather than changes in litter chemistry drive soil carbon and nitrogen cycles under elevated CO2: a microcosm study

Treesearch

Lingli Lui; John S. King; Fitzgerald L. Booker; Christian P. Giardina; H. Lee Allen; Shuijin Hu

2009-01-01

Elevated CO2 has been shown to stimulate plant productivity and change litter chemistry. These changes in substrate availability may then alter soil microbial processes and possibly lead to feedback effects on N availability. However, the strength of this feedback, and even its direction, remains unknown. Further, uncertainty remains whether...

Serpentinization and alteration in an olivine cumulate from the Stillwater Complex, Southwestern Montana

USGS Publications Warehouse

Page, N.J.

1976-01-01

Some of the olivine cumulates of the Ultramafic zone of the Stillwater Complex, Montana, are progressively altered to serpentine minerals and thompsonite. Lizardite and chrysotile developed in the cumulus olivine and postcumulus pyroxenes; thompsonite developed in postcumulus plagioclase. The detailed mineralogy, petrology, and chemistry indicate that olivine and plagioclase react to form the alteration products, except for H2O, without changes in the bulk composition of the rocks. ?? 1976 Springer-Verlag.

Invasive plants found in Louisiana’s forests, 2009 forest inventory and analysis factsheet

Treesearch

Sonja N. Oswalt; Christopher M. Oswalt

2012-01-01

Foresters and ecologists have noted the spread of nonnative invasive species onto U.S. forest land for decades. Despite soaring costs related to the management of and removal of invasive plants, and inestimable environmental impacts (e.g., altered soil chemistry, competition with native species, altered light environment; Pimentel and others 2005), nonnative invasive...

Improving Ionic Conductivity and Lithium-Ion Transference Number in Lithium-Ion Battery Separators.

PubMed

Zahn, Raphael; Lagadec, Marie Francine; Hess, Michael; Wood, Vanessa

2016-12-07

The microstructure of lithium-ion battery separators plays an important role in separator performance; however, here we show that a geometrical analysis falls short in predicting the lithium-ion transport in the electrolyte-filled pore space. By systematically modifying the surface chemistry of a commercial polyethylene separator while keeping its microstructure unchanged, we demonstrate that surface chemistry, which alters separator-electrolyte interactions, influences ionic conductivity and lithium-ion transference number. Changes in separator surface chemistry, particularly those that increase lithium-ion transference numbers can reduce voltage drops across the separator and improve C-rate capability.

Progress in the medicinal chemistry of silicon: C/Si exchange and beyond.

PubMed

Fujii, Shinya; Hashimoto, Yuichi

2017-04-01

Application of silyl functionalities is one of the most promising strategies among various 'elements chemistry' approaches for the development of novel and distinctive drug candidates. Replacement of one or more carbon atoms of various biologically active compounds with silicon (so-called sila-substitution) has been intensively studied for decades, and is often effective for alteration of activity profile and improvement of metabolic profile. In addition to simple C/Si exchange, several novel approaches for utilizing silicon in medicinal chemistry have been suggested in recent years, focusing on the intrinsic differences between silicon and carbon. Sila-substitution offers great potential for enlarging the chemical space of medicinal chemistry, and provides many options for structural development of drug candidates.

Indoor Chemistry: Materials, Ventilation Systems, and Occupant Activities

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

Morrison, G.C.; Corsi, R.L.; Destaillats, H.

2006-05-01

Chemical processes taking place in indoor environments can significantly alter the nature and concentrations of pollutants. Exposure to secondary contaminants generated in these reactions needs to be evaluated in association with many aspects of buildings to minimize their impact on occupant health and well-being. Focusing on indoor ozone chemistry, we describe alternatives for improving indoor air quality by controlling chemical changes related to building materials, ventilation systems, and occupant activities.

Meteor wake in high frame-rate images--implications for the chemistry of ablated organic compounds

NASA Technical Reports Server (NTRS)

Jenniskens, Peter; Stenbaek-Nielsen, Hans C.

2004-01-01

Extraterrestrial organic matter may have been chemically altered into forms more ameanable for prebiotic chemistry in the wake of a meteor after ablation. We measured the rate of cooling of the plasma in the meteor wake from the intensity decay just behind a meteoroid by freezing its motion in high frame-rate 1000 frames/s video images, with an intensified camera that has a short phosphor decay time. Though the resulting cooling rate was found to be lower than theoretically predicted, our calculations indicated that there would have been insufficient collisions to break apart large organic compounds before most reactive radicals and electrons were lost from the air plasma. Organic molecules delivered from space to the early Earth via meteors might therefore have survived in a chemically altered form. In addition, we discovered that relatively small meteoroids generated far-ultraviolet emission that is absorbed in the immediate environment of the meteoroid, which may chemically alter the atmosphere over a much larger region than previously recognized.

Effects of acid deposition on calcium nutrition and health of Southern Appalachian spruce fir forests

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

McLaughlin, S.B.; Wullschleger, S.; Stone, A.

The role of acid deposition in the health of spruce fir forests in the Southern Appalachian Mountains has been investigated by a wide variety of experimental approaches during the past 10 years. These studies have proceeded from initial dendroecological documentation of altered growth patterns of mature trees to increasingly more focused ecophysiological research on the causes and characteristics of changes in system function associated with increased acidic deposition. Field studies across gradients in deposition and soil chemistry have been located on four mountains spanning 85 km of latitude within the Southern Appalachians. The conclusion that calcium nutrition is an importantmore » component regulating health of red spruce in the Southern Appalachians and that acid deposition significantly reduces calcium availability in several ways has emerged as a consistent result from multiple lines or research. These have included analysis of trends in wood chemistry, soil solution chemistry, foliar nutrition, gas exchange physiology, root histochemistry, and controlled laboratory and field studies in which acid deposition and/or calcium nutrition has been manipulated and growth and nutritional status of saplings or mature red spruce trees measured. This earlier research has led us to investigate the broader implications and consequences of calcium deficiency for changing resistance of spruce-fir forests to natural stresses. Current research is exploring possible relationships between altered calcium nutrition and shifts in response of Fraser fir to insect attack by the balsam wooly adelgid. In addition, changes in wood ultrastructural properties in relation to altered wood chemistry is being examined to evaluate its possible role in canopy deterioration, under wind and ice stresses typical of high elevation forests.« less

Microbiologically Influenced Corrosion: Causative Organisms and Mechanisms

DTIC Science & Technology

2012-01-31

corrosion is both predictable and complex. In aquatic environments and under some atmospheric conditions . microorganisms settle on surfaces and alter the...some atmospheric conditions , microorganisms settle on sin laces and alter the surface chemistry controlling the rates of corrosion or shifting the...pitting corrosion of some allO) S continues under deposits of iron-oxidizing bacteria independent of bacterial activity. Similarly, microbiologicall

Impact of wildfire on stream nutrient chemistry and ecosystem metabolism in boreal forest catchments of interior Alaska

Treesearch

Emma F. Betts; Jeremy B. Jones

2009-01-01

With climatic warming, wildfire occurrence is increasing in the boreal forest of interior Alaska. Loss of catchment vegetation during fire can impact streams directly through altered solute and debris inputs and changed light and temperature regimes. Over longer time scales, fire can accelerate permafrost degradation, altering catchment hydrology and stream nutrient...

Vernal freeze damage and genetic variation alter tree growth, chemistry, and insect interactions.

PubMed

Rubert-Nason, Kennedy F; Couture, John J; Gryzmala, Elizabeth A; Townsend, Philip A; Lindroth, Richard L

2017-11-01

Anticipated consequences of climate change in temperate regions include early spring warmup punctuated by intermittent hard freezes. Warm weather accelerates leaf flush in perennial woody species, potentially exposing vulnerable young tissues to damaging frosts. We employed a 2 × 6 randomized factorial design to examine how the interplay of vernal (springtime) freeze damage and genetic variation in a hardwood species (Populus tremuloides) influences tree growth, phytochemistry, and interactions with an insect herbivore (Chaitophorus stevensis). Acute effects of freezing included defoliation and mortality. Surviving trees exhibited reduced growth and altered biomass distribution. Reflushed leaves on these trees had lower mass per area, lower lignin concentrations, and higher nitrogen concentrations, altered chemical defence profiles, and supported faster aphid population growth. Many effects varied among plant genotypes and were related with herbivore performance. This study suggests that a single damaging vernal freeze event can alter tree-insect interactions through effects on plant growth and chemistry. Differential responses of various genotypes to freeze damage suggest that more frequent vernal freeze events could also influence natural selection, favouring trees with greater freeze hardiness, and more resistance or tolerance to herbivores following damage. © 2017 John Wiley & Sons Ltd.

Covalent Surface Modifications of Carbon Nanotubes.

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

Pavia Sanders, Adriana; O'Bryan, Greg

A report meant to document the chemistries investigated by the author for covalent surface modification of CNTs. Oxidation, cycloaddition, and radical reactions were explored to determine their success at covalently altering the CNT surface. Characterization through infrared spectroscopy, Raman spectroscopy, and thermo gravimetric analysis was performed in order to determine the success of the chemistries employed. This report is not exhaustive and was performed for CNT surface modification exploration as it pertains to the "Next Gen" project.

Particulate matter in cigarette smoke increases ciliary axoneme beating through mechanical stimulation.

PubMed

Navarrette, Chelsea R; Sisson, Joseph H; Nance, Elizabeth; Allen-Gipson, Diane; Hanes, Justin; Wyatt, Todd A

2012-06-01

The lung's ability to trap and clear foreign particles via the mucociliary elevator is an important mechanism for protecting the lung against respirable irritants and microorganisms. Although cigarette smoke (CS) exposure and particulate inhalation are known to alter mucociliary clearance, little is known about how CS and nanoparticles (NPs) modify cilia beating at the cytoskeletal infrastructure, or axonemal, level. We used a cell-free model to introduce cigarette smoke extract (CSE) and NPs with variant size and surface chemistry to isolated axonemes and measured changes in ciliary motility. We hypothesized that CSE would alter cilia beating and that alterations in ciliary beat frequency (CBF) due to particulate matter would be size- and surface chemistry-dependent. Demembranated axonemes were isolated from ciliated bovine tracheas and exposed to adenosine triphosphate (ATP) to initiate motility. CBF was measured in response to 5% CSE, CSE filtrate, and carboxyl-modified (COOH), sulphate (SO(4))-modified (sulfonated), or PEG-coated polystyrene (PS) latex NPs ranging in size from 40 nm to 500 nm. CSE concentrations as low as 5% resulted in rapid, significant stimulation of CBF (p<0.05 vs. baseline control). Filtering CSE through a 0.2-μm filter attenuated this effect. Introduction of sulphate-modified PS beads ~300 nm in diameter resulted in a similar increase in CBF above baseline ATP levels. Uncharged, PEG-coated beads had no effect on CBF regardless of size. Similarly, COOH-coated particles less than 200 nm in diameter did not alter ciliary motility. However, COOH-coated PS particles larger than 300 nm increased CBF significantly and increased the number of motile points. These data show that NPs, including those found in CSE, mechanically stimulate axonemes in a size- and surface chemistry-dependent manner. Alterations in ciliary motility due to physicochemical properties of NPs may be important for inhalational lung injury and efficient drug delivery of respirable particles.

RIS4E at Kilauea's December 1974 Flow: Chemical, mineralogical and spectral characteristics of Hawaiian basaltic alteration products measured with portable instruments

NASA Astrophysics Data System (ADS)

Young, K. E.; Rogers, D.; Dyar, M. D.; Ito, G.; Yant, M.; McAdam, A.; Bleacher, J. E.; Glotch, T. D.

2015-12-01

A major objective of the SSERVI RIS4E (Remote, In-situ, and Synchrotron Studies for Science and Exploration) investigation is to evaluate the performance of portable chemical and mineralogical instruments in a variety of planetary volcanic analog settings. To that end, we used a suite of true/proxy portable instruments (XRF, LIBS, XRD, near-IR and mid-IR spectrometers), to measure the chemical and spectral characteristics of young basaltic flows (erupted December 1974, or D1974) within the southwest rift zone of Kilauea, Hawaii. The D1974 lavas exhibit multiple flow morphologies and textures, and have undergone alteration by a variety of processes, including acid weathering, oxidation and devitrification. The mineralogy, chemistry and infrared spectral properties of select samples from these altered surfaces have been well characterized by previous groups using high resolution (e.g. SEM, TEM) and/or laboratory measurements (XRD, Mossbauer, infrared). Typical alteration products include coatings of Fe-Ti-oxide +/- an overlying silica-rich coating. Coatings are commonly discontinuous and vary in color. Oxidation fronts are also present, most visible as reddish brown discoloration along the edges of broken and uplifted flow crusts. The previous detailed characterizations provide the basis for evaluating instrument performance and also allow us to assess areas where portable instruments can contribute new information to current understanding. These areas include characterizing the spatial variability in alteration chemistry/mineralogy, relating chemical/mineralogical properties to texture and context, and comparing chemical/mineralogical variations with infrared spectral properties. Because infrared spectra are commonly used to assess compositional variations of a site remotely, either from the ground or from orbit, relating changes in chemistry and mineralogy to spectral variations is particularly important. Last, the D1974 site provides an excellent location to test the performance of portable chemical instruments on coated surfaces of variable texture. Results from this multi-technique approach will be presented at the meeting.

The potential for retreating alpine glaciers to alter alpine ecosystems in the Colorado Front Range

NASA Astrophysics Data System (ADS)

Hall, E.; Baron, J.

2013-12-01

Glaciers are retreating at an unprecedented rate. In mid-latitude alpine ecosystems the presence of glaciers and rock glaciers govern rates and ecology of alpine and sub-alpine ecosystems. Changes in the thermal environment due to the loss of isothermal habitat and inputs from glacier melt chemistry are altering alpine ecosystems in unpredictable ways. In particular, glacier may be a source of nitrogen that is altering alpine ecosystem dynamics. Loch Vale Watershed (LVWS) located within Rocky Mountain National Park. LVWS contains a surface glacier (Andrew's glacier) and a rock glacier (Taylor's glacier) at the headwater of each of the two drainages within the watershed. We collected precipitation from a National Atmospheric Deposition Site and surface water from multiple alpine lakes and streams during a particularly high and low snow year in the Colorado Front Range. We also sampled stream and lake sediments at each site to analyze the associated microbial community. Concentrations of nitrate and ammonium, relative abundance of amoA (the gene responsible for a key step in the microbial nitrification pathway), and the dual isotope signal to nitrate all point to snow melt as a key deliverer of nitrogen to ecosystems along the Colorado Front Range. However, late summer surface water chemistry is isotopically similar to the chemistry of glacial ice. This suggests that retreating glacier may be an additional source of N to alpine ecosystems and have the potential to alter microbial community composition, biogeochemical rate processes, and ecosystem function. These dynamics are most likely not unique to the Colorado Front Range and should be globally distributed as glaciers continue to retreat in high altitude ecosystems around the world.

Mineral and whole-rock compositions of seawater-dominated hydrothermal alteration at the Arctic volcanogenic massive sulfide prospect, Alaska

USGS Publications Warehouse

Schmidt, J.M.

1988-01-01

The Arctic volcanogenic massive sulfide prospect, located in the Ambler mineral district of northwestern Alaska, includes three types of hydrothermally altered rocks overlying, underlying, and interlayered with semimassive sulfide mineralization. Hydrothermal alteration of wall rocks and deposition of sulfide and gangue minerals were contemporaneous with Late Devonian of Early Mississippian basalt-rhyolite volcanism. Alteration developed asymmetrically around a linear fissure, suggesting fracture control of ore fluids rather than a point source. Microprobe analyses of phyllosilicates from the Arctic area indicate two discrete mineral populations. These differences in mineral chemistry are the result of differences in protolith composition caused by hydrothermal alteration-metasomatism. -from Author

Alteration heterogeneities in peridotites tectonically exhumed along slow-spreading ridges

NASA Astrophysics Data System (ADS)

Rouméjon, S.; Frueh-Green, G. L.; Williams, M. J.

2017-12-01

Serpentinized peridotites associated with mafic lithologies commonly outcrop along slow-spreading ridges. They are exhumed along large offset normal faults, called detachment faults, that uplift fresh peridotites and gabbros from the base of the brittle lithosphere to shallower levels where they are hydrothermally altered. Numerous petrological studies in these environments reveal that peridotites are variably altered depending on factors such as the temperature, redox state, intensity of hydrothermal fluid input and the chemistry of these fluids. It follows that the detachment footwalls are heterogeneous at scales less than a kilometer, reflecting initial distribution of primary lithologies and later variable alteration. Here we investigate the nature, distribution and typical length scales of alteration heterogeneities. We primarily focus on samples drilled at five sites across the Atlantis Massif (Mid-Atlantic Ridge, 30°N) during IODP Exp. 357 (Nov. 2015, RRS James Cook) and on samples dredged along the easternmost Southwest Indian Ridge (Smoothseafloor cruise, Oct. 2010, N/O Marion Dufresne). Multiple petrological observations are combined: hand sample description, sequences of textures and the associated mineralogical assemblages identifiable in thin section, in situ major and trace elements data as well as bulk rock and in situ oxygen isotopes ratios in serpentine textures. We show that all serpentinized peridotites develop serpentine mesh textures. However, some domains of the footwall are overprinted by further serpentine recrystallization and veins (mostly chrysotile- or antigorite-bearing) as a result of localized fluid-rock interaction and evolving fluids. Other domains are impacted by the alteration of the surrounding mafic bodies that influences both the mineralogy and chemistry of the altered peridotites. Using these results, we propose a conceptual model for the development of alteration heterogeneities during exhumation at slow-spreading ridges.

9 CFR 439.53 - Revocation of accreditation.

Code of Federal Regulations, 2014 CFR

2014-01-01

... ACCREDITATION OF NON-FEDERAL CHEMISTRY LABORATORIES § 439.53 Revocation of accreditation. The accreditation of a... has: (1) Altered any official sample or analytical finding; or (2) Substituted any analytical result...

9 CFR 439.53 - Revocation of accreditation.

Code of Federal Regulations, 2012 CFR

2012-01-01

... ACCREDITATION OF NON-FEDERAL CHEMISTRY LABORATORIES § 439.53 Revocation of accreditation. The accreditation of a... has: (1) Altered any official sample or analytical finding; or (2) Substituted any analytical result...

9 CFR 439.53 - Revocation of accreditation.

Code of Federal Regulations, 2013 CFR

2013-01-01

... ACCREDITATION OF NON-FEDERAL CHEMISTRY LABORATORIES § 439.53 Revocation of accreditation. The accreditation of a... has: (1) Altered any official sample or analytical finding; or (2) Substituted any analytical result...

9 CFR 439.53 - Revocation of accreditation.

Code of Federal Regulations, 2011 CFR

2011-01-01

... ACCREDITATION OF NON-FEDERAL CHEMISTRY LABORATORIES § 439.53 Revocation of accreditation. The accreditation of a... has: (1) Altered any official sample or analytical finding; or (2) Substituted any analytical result...

Multiple stages of aqueous alteration along fractures in mudstone and sandstone strata in Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Yen, A. S.; Ming, D. W.; Vaniman, D. T.; Gellert, R.; Blake, D. F.; Morris, R. V.; Morrison, S. M.; Bristow, T. F.; Chipera, S. J.; Edgett, K. S.; Treiman, A. H.; Clark, B. C.; Downs, R. T.; Farmer, J. D.; Grotzinger, J. P.; Rampe, E. B.; Schmidt, M. E.; Sutter, B.; Thompson, L. M.; MSL Science Team

2017-08-01

The Mars rover Curiosity in Gale crater conducted the first-ever direct chemical and mineralogical comparisons of samples that have clear parent (unaltered) and daughter (altered) relationships. The mineralogy and chemistry of samples within and adjacent to alteration halos in a sandstone formation were established by the Chemistry and Mineralogy (CheMin) X-ray diffraction (XRD) instrument and the Alpha Particle X-ray Spectrometer (APXS), respectively. The Stimson formation sandstones unconformably overlie the Murray mudstone formation and represent the youngest stratigraphic unit explored by Curiosity to date. Aqueous alteration of the parent sandstone resulted in a loss of half of the original crystalline mineral phases and a three-fold increase in X-ray amorphous material. Aqueous fluids extensively leached Mg, Al, Mn, Fe, Ni, Zn and other elements from the parent material, decreased the pyroxene to feldspar ratio by a factor of two, introduced Ca and mixed-cation sulfates, and both passively and actively enriched the silica content. Leaching of Mg, Al, Mn, Fe, Ni and Zn and enrichment of Si and S are also observed in alteration halos in the underlying mudstone. These observations are consistent with infiltration of subsurface fluids, initially acidic and then alkaline, propagating along fractures crosscutting the Stimson sandstone and Murray mudstone. The geochemistry and mineralogy suggest a complicated diagenetic history with multiple stages of aqueous alteration under a variety of environmental conditions (e.g. both low and moderate pH). The formation of these alteration halos post-dates lithification of the sandstones and mudstones and represents one of the youngest hydrogeologic events presently known to have occurred in Gale crater.

Chemistry of diagenetically altered tuffs at a potential nuclear waste repository, Yucca Mountain, Nye County, Nevada

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

Broxton, D.E.; Warren, R.G.; Hagan, R.C.

1986-10-01

The chemistry of diagenetically altered tuffs at a potential nuclear waste repository, Yucca Mountain, Nevada is described. These tuffs contain substantial amounts of zeolites that are highly sorptive of certain radionuclides. Because of their widespread distribution, the zeolitic tuffs could provide important barriers to radionuclide migration. Physical properties of these tuffs and of their constituent zeolites are influenced by their chemical compositions. This study defines the amount of chemical variability within diagenetically altered tuffs and within diagenetic minerals at Yucca Mountain. Zeolitic tuffs at Yucca Mountain formed by diagenetic alteration of rhyolitic vitric tuffs. Despite their similar starting compositions, thesemore » tuffs developed compositions that vary both vertically and laterally. Widespread chemical variations were the result of open-system chemical diagenesis in which chemical components of the tuffs were mobilized and redistributed by groundwaters. Alkalies, alkaline earths, and silica were the most mobile elements during diagenesis. The zeolitic tuffs can be divided into three compositional groups: (1) calcium- and magnesium-rich tuffs associated with relatively thin zones of alteration in the unsaturated zone; (2) tuffs in thick zones of alteration at and below the water table that grade laterally from sodic compositions on the western side of Yucca Mountain to calcic compositions on the eastern side; and (3) potassic tuffs at the north end of Yucca Mountain. Physical properties of tuffs and their consistuent zeolites at Yucca Mountain may be affected by variations in compositions. Properties important for assessment of repository performance include behavior and ion exchange.« less

Mineralogical, geochemical and isotopic characteristics of hydrothermal alteration processes in the active, submarine, felsic-hosted PACMANUS field, Manus Basin, Papua New Guinea

NASA Astrophysics Data System (ADS)

Lackschewitz, K. S.; Devey, C. W.; Stoffers, P.; Botz, R.; Eisenhauer, A.; Kummetz, M.; Schmidt, M.; Singer, A.

2004-11-01

During ODP Leg 193, 4 sites were drilled in the active PACMANUS hydrothermal field on the crest of the felsic Pual Ridge to examine the vertical and lateral variations in mineralization and alteration patterns. We present new data on clay mineral assemblages, clay and whole rock chemistry and clay mineral strontium and oxygen isotopic compositions of altered rocks from a site of diffuse low-temperature venting (Snowcap, Site 1188) and a site of high-temperature venting (Roman Ruins, Site 1189) in order to investigate the water-rock reactions and associated elemental exchanges. The volcanic succession at Snowcap has been hydrothermally altered, producing five alteration zones: (1) chlorite ± illite-cristobalite-plagioclase alteration apparently overprinted locally by pyrophyllite bleaching at temperatures of 260-310°C; (2) chlorite ± mixed-layer clay alteration at temperatures of 230°C; (3) chlorite and illite alteration; (4) illite and chlorite ± illite mixed-layer alteration at temperatures of 250-260°C; and (5) illite ± chlorite alteration at 290-300°C. Felsic rocks recovered from two holes (1189A and 1189B) at Roman Ruins, although very close together, show differing alteration features. Hole 1189A is characterized by a uniform chlorite-illite alteration formed at ˜250°C, overprinted by quartz veining at 350°C. In contrast, four alteration zones occur in Hole 1189B: (1) illite ± chlorite alteration formed at ˜300°C; (2) chlorite ± illite alteration at 235°C; (3) chlorite ± illite and mixed layer clay alteration; and (4) chlorite ± illite alteration at 220°C. Mass balance calculations indicate that the chloritization, illitization and bleaching (silica-pyrophyllite assemblages) alteration stages are accompanied by different chemical changes relative to a calculated pristine precursor lava. The element Cr appears to have a general enrichment in the altered samples from PACMANUS. The clay concentrate data show that Cr and Cu are predominantly present in the pyrophyllites. Illite shows a significant enrichment for Cs and Cu relative to the bulk altered samples. Considerations of mineral stability allow us to place some constraints on fluid chemistry. Hydrothermal fluid pH for the chloritization and illitization was neutral to slightly acidic and relatively acidic for the pyrophyllite alteration. In general the fluids, especially from Roman Ruins and at intermediate depths below Snowcap, show only a small proportion of seawater mixing (<10%). Fluids in shallow and deep parts of the Snowcap holes, in contrast, show stronger seawater influence.

Direct and indirect effects of invasive plants on soil chemistry and ecosystem function.

PubMed

Weidenhamer, Jeffrey D; Callaway, Ragan M

2010-01-01

Invasive plants have a multitude of impacts on plant communities through their direct and indirect effects on soil chemistry and ecosystem function. For example, plants modify the soil environment through root exudates that affect soil structure, and mobilize and/or chelate nutrients. The long-term impact of litter and root exudates can modify soil nutrient pools, and there is evidence that invasive plant species may alter nutrient cycles differently from native species. The effects of plants on ecosystem biogeochemistry may be caused by differences in leaf tissue nutrient stoichiometry or secondary metabolites, although evidence for the importance of allelochemicals in driving these processes is lacking. Some invasive species may gain a competitive advantage through the release of compounds or combinations of compounds that are unique to the invaded community—the “novel weapons hypothesis.” Invasive plants also can exert profound impact on plant communities indirectly through the herbicides used to control them. Glyphosate, the most widely used herbicide in the world, often is used to help control invasive weeds, and generally is considered to have minimal environmental impacts. Most studies show little to no effect of glyphosate and other herbicides on soil microbial communities. However, herbicide applications can reduce or promote rhizobium nodulation and mycorrhiza formation. Herbicide drift can affect the growth of non-target plants, and glyphosate and other herbicides can impact significantly the secondary chemistry of plants at sublethal doses. In summary, the literature indicates that invasive species can alter the biogeochemistry of ecosystems, that secondary metabolites released by invasive species may play important roles in soil chemistry as well as plant-plant and plant-microbe interactions, and that the herbicides used to control invasive species can impact plant chemistry and ecosystems in ways that have yet to be fully explored.

Matrices of carbonaceous chondrite meteorites

NASA Technical Reports Server (NTRS)

Buseck, Peter R.; Hua, Xin

1993-01-01

The morphology, classification, and chemistry of the matrices of carbonaceous chondrite (CC) meteorites is reviewed based on recent research results. The various kinds of CCs are examined in terms of their matrix mineralogy. Alteration processes in CCs are discussed.

Fixation of Bovine Pericardium-Based Tissue Biomaterial with Irreversible Chemistry Improves Biochemical and Biomechanical Properties

PubMed Central

Tam, H.; Zhang, W.; Infante, D.; Parchment, N.; Sacks, M.

2018-01-01

Bioprosthetic heart valves (BHVs), derived from glutaraldehyde crosslinked (GLUT) porcine aortic valve leaflets or bovine pericardium (BP), are used to replace defective heart valves. However, valve failure can occur within 12–15 years due to calcification and/or progressive structural degeneration. We present a novel fabrication method that utilizes carbodiimide, neomycin trisulfate, and pentagalloyl glucose crosslinking chemistry (TRI) to better stabilize the extracellular matrix of BP. We demonstrate that TRI-treated BP is more compliant than GLUT-treated BP. GLUT-treated BP exhibited permanent geometric deformation and complete alteration of apparent mechanical properties when subjected to induced static strain. TRI BP, on the other hand, did not exhibit such permanent geometric deformations or significant alterations of apparent mechanical properties. TRI BP also exhibited better resistance to enzymatic degradation in vitro and calcification in vivo when implanted subcutaneously in juvenile rats for up to 30 days. PMID:28213846

Experimental Alteration of Basalt to Support Interpretation of Remote Sensing and In Situ Meausrements from Mars

NASA Technical Reports Server (NTRS)

Bell, M. S.

2014-01-01

Major occurrences of hydrous alteration minerals on Mars have been found in Noachian impact craters formed in basaltic targets and detected using visible/near infrared (VNIR) spectroscopy. Until recently phyllosilicates were detected only in craters in the southern hemisphere [1, 2]. However, it has been reported that at least nine craters in the northern plains apparently excavated thick layers of lava and sediment to expose phyllosilicates [3] as well. The MER (Mars Exploration Rovers) rovers previously reported results of in situ measurement indicating the presence of alteration minerals on Mars [4,5] and it was recently reported that the Mars Curiosity rover has detected alteration phases in situ at Yellowknife Bay in Gale crater as well [6,7]. An important discovery for Mars geochronology is that the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument on Curiosity detected phyllosilicates indicating that phyllosilicate formation on Mars extended beyond the Noachian Epoch [8]. These discoveries indicate that Mars was globally altered by water in the past but does not constrain formation conditions for alteration phase occurrences, which have important implications for the evolution of the surface and the biological potential on Mars. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures as well as in situ measurements and to decipher the environment and evolution of early Mars. The martian surface has been intensely altered by meteorite impacts whose effects include brecciation and melting of target materials as well as the initiation of hydrothermal circulation in a hydrous target [9,10,11,12]. Impact effects may facilitate aqueous alteration of a basaltic target because the rate of silicate dissolution is a function of the degree of crystallinity, surface area, and temperature. The resultant alteration mineralogies from shocked basaltic target material are a function of the original mineral assemblage in the parent rocks, the chemistry of fluids that interacted with the rocks, and physico-chemical conditions (pH, temperatures, and pressure) during the time of mineral formation. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures and to decipher the environment and evolution of early Mars, and especially for identifying habitable niches in which life could be initiated and sustained. No experimentally controlled and well characterized analog materials that simulate martian shock metamorphism and alteration conditions currently exist for calibrating either remote sensing or in situ measurements of Mars. A series of experiments was initiated to assess the effects of systematic changes in the physico-chemical conditions on Mars analog materials thereby providing samples to ground-truth Mars remote sensing observations from CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) and in situ measurements from Opportunity's Mössbauer and Curiosity's CHEMIN (Chemistry and Mineralogy X-Ray Diffraction/XRay Fluorescence) instruments. Results of initial experimental runs as analysed by SEM-EDS (Secondary Electron Microscopy -Energy Dispersive Spectroscopy) and X-ray Diffraction (XRD) analysis are reported here and lay the foundation for comparison with shocked and altered samples that will be characterized in the next phase of this work.

Safety assessment of high fructose corn syrup (HFCS) as an ingredient added to cigarette tobacco.

PubMed

Stavanja, Mari S; Ayres, Paul H; Meckley, Daniel R; Bombick, Elizabeth R; Borgerding, Michael F; Morton, Michael J; Garner, Charles D; Pence, Deborah H; Swauger, James E

2006-03-01

A tiered testing strategy has been developed to evaluate the potential for new ingredients, tobacco processes, and technological developments to alter the biological activity that results from burning tobacco. A series of studies was initially conducted with cigarettes containing 3% high fructose corn syrup (HFCS) as an alternate tobacco casing material to corn syrup/invert sugar, including determination of selected mainstream cigarette smoke (MS) constituent yields, Ames assay, sister chromatid exchange (SCE) assay in Chinese hamster ovary (CHO) cells, a 30-week dermal tumor-promotion evaluation of cigarette smoke condensate (CSC) in SENCAR mice, and a 13-week subchronic inhalation study of MS in Sprague-Dawley rats. A second series of studies was conducted with cigarettes containing 3%, 4% and 5% HFCS including MS chemistry, Ames assay, SCE assay in CHO cells, and a neutral red cytotoxicity assays. Collectively, mainstream smoke chemistry, genotoxicity, dermal tumor-promotion, and inhalation toxicity studies demonstrated no differences between cigarettes with 3% HFCS and cigarettes with 3% corn syrup/invert sugar. Also, mainstream smoke chemistry and genotoxicity of cigarettes with 4% and 5% HFCS were not different from cigarettes with 3% HFCS. In conclusion, the addition of up to 5% HFCS to cigarette does not alter the mainstream smoke chemistry or biological activity of mainstream smoke or mainstream smoke condensate as compared to cigarettes with 3% corn syrup/invert sugar with regard to the parameters investigated and presented.

Soil microbial communities alter leaf chemistry and influence allelopathic potential among coexisting plant species.

PubMed

Meiners, Scott J; Phipps, Kelsey K; Pendergast, Thomas H; Canam, Thomas; Carson, Walter P

2017-04-01

While both plant-soil feedbacks and allelochemical interactions are key drivers of plant community dynamics, the potential for these two drivers to interact with each other remains largely unexplored. If soil microbes influence allelochemical production, this would represent a novel dimension of heterogeneity in plant-soil feedbacks. To explore the linkage between soil microbial communities and plant chemistry, we experimentally generated soil microbial communities and evaluated their impact on leaf chemical composition and allelopathic potential. Four native perennial old-field species (two each of Aster and Solidago) were grown in pairwise combination with each species' soil microbial community as well as a sterilized inoculum. We demonstrated unequivocally that variation in soil microbial communities altered leaf chemical fingerprints for all focal plant species and also changed their allelopathic potential. Soil microbes reduced allelopathic potential in bioassays by increasing germination 25-54% relative to sterile control soils in all four species. Plants grown with their own microbial communities had the lowest allelopathic potential, suggesting that allelochemical production may be lessened when growing with microbes from conspecifics. The allelopathic potential of plants grown in congener and confamilial soils was indistinguishable from each other, indicating an equivalent response to all non-conspecific microbial communities within these closely related genera. Our results clearly demonstrated that soil microbial communities cause changes in leaf tissue chemistry that altered their allelopathic properties. These findings represent a new mechanism of plant-soil feedbacks that may structure perennial plant communities over very small spatial scales that must be explored in much more detail.

Warming and increased precipitation frequency on the Colorado Plateau: Implications for biological soil crusts and soil processes

USGS Publications Warehouse

Zelikova, Tamara J.; Housman, David C.; Grote, Ed E.; Neher, Deborah A.; Belnap, Jayne

2012-01-01

Taken together, our results highlight the limited effects of warming alone on biological soil crust communities and soil chemistry, but demonstrate the substantially larger effects of altered summertime precipitation.

EXPOSURE TO CONCENTRATED AMBIENT AIR PARTICLES ALTERS HEMATOLOGIC INDICES IN HUMANS

EPA Science Inventory

Descriptions of changes in hematological indices have contested the premise that the biological effects of suspended particulate matter (PM) are restricted to the lung. Employing approximately 40 hematologic parameters reflecting blood cells, chemistries, mediators, and coagulati...

LOW DOSE PESTICIDE EXPOSURE AND ALTERED REPRODUCTIVE SYSTEM DEVELOPMENT IN REPTILES

EPA Science Inventory

In: Environmental Sciences in the 21st Century: Paradigms, Opportunities, and Challenges: Abstract Book: SETAC 21st Annual Meeting, 12-16 November 2000, Nashville, TN. Society of Environmental Toxicology and Chemistry, Pensacola, FL. Pp. 99.

Observations of Inland Snowpack-driven Bromine Chemistry near the Brooks Range, Alaska

NASA Astrophysics Data System (ADS)

Peterson, P.; Pöhler, D.; Sihler, H.; Zielcke, J.; S., General; Friess, U.; Platt, U.; Simpson, W. R.; Nghiem, S. V.; Shepson, P. B.; Stirm, B. H.; Pratt, K.

2017-12-01

The snowpack produces high amounts of reactive bromine in the polar regions during spring. The resulting atmospheric bromine chemistry depletes boundary layer ozone to near-zero levels and alters oxidation of atmospheric pollutants, particularly elemental mercury. To improve our understanding of the spatial extent of this bromine chemistry in Arctic coastal regions, the Purdue Airborne Laboratory for Atmospheric Research (ALAR), equipped with the Heidelberg Imaging differential optical absorption spectroscopy (DOAS) instrument, measured the spatial distribution of BrO, an indicator of active bromine chemistry, over northern Alaska during the March 2012 BRomine Ozone Mercury Experiment (BROMEX). Here we show that this bromine chemistry, commonly associated with snow-covered sea ice regions in the Arctic Ocean, is active 200 km inland in the foothills of the Brooks Range. Profiles retrieved from limb-viewing measurements show this event was located near the snowpack surface, with measured BrO mole ratios of 20 pmol mol-1 in a 500 m thick layer. This observed bromine chemistry is likely enabled by deposition of transported sea salt aerosol or gas phase bromine species from prior activation events to the snowpack. These observations of halogen activation hundreds of km from the coast suggest the impacts of this springtime bromine chemistry are not restricted to sea ice regions and directly adjacent coastal regions.

Laser Rewelding of 304L Stainless Steel.

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

Maguire, Michael Christopher; Rodelas, Jeffrey

Laser welding of 304L stainless steel during component fabrication has been found to alter the chemical composition of the steel due to material evaporation. During repair or rework, or during potential reuse/ rewelding of certain components, the potential exists to alter the composition to the extent that the material becomes prone to solidification cracking. This work aims to characterize the extent of this susceptibility in order to make informed decisions regarding rewelding practice and base metal chemistry allowances.

Hyperspectral mapping of alteration assemblages within a hydrothermal vug at the Haughton impact structure, Canada

NASA Astrophysics Data System (ADS)

Greenberger, Rebecca N.; Mustard, John F.; Osinski, Gordon R.; Tornabene, Livio L.; Pontefract, Alexandra J.; Marion, Cassandra L.; Flemming, Roberta L.; Wilson, Janette H.; Cloutis, Edward A.

2016-12-01

Meteorite impacts on Earth and Mars can generate hydrothermal systems that alter the primary mineralogies of rocks and provide suitable environments for microbial colonization. We investigate a calcite-marcasite-bearing vug at the 23 km diameter Haughton impact structure, Devon Island, Nunavut, Canada, using imaging spectroscopy of the outcrop in the field (0.65-1.1 μm) and samples in the laboratory (0.4-2.5 μm), point spectroscopy (0.35-2.5 μm), major element chemistry, and X-ray diffraction analyses. The mineral assemblages mapped at the outcrop include marcasite; marcasite with minor gypsum and jarosite; fibroferrite and copiapite with minor gypsum and melanterite; gypsum, Fe3+ oxides, and jarosite; and calcite, gypsum, clay, microcline, and quartz. Hyperspectral mapping of alteration phases shows spatial patterns that illuminate changes in alteration conditions and formation of specific mineral phases. Marcasite formed from the postimpact hydrothermal system under reducing conditions, while subsequent weathering oxidized the marcasite at low temperatures and water/rock ratios. The acidic fluids resulting from the oxidation collected on flat-lying portions of the outcrop, precipitating fibroferrite + copiapite. That assemblage then likely dissolved, and the changing chemistry and pH resulting from interaction with the calcite-rich host rock formed gypsum-bearing red coatings. These results have implications for understanding water-rock interactions and habitabilities at this site and on Mars.

Diagenesis and clay mineral formation at Gale Crater, Mars

PubMed Central

Bridges, J C; Schwenzer, S P; Leveille, R; Westall, F; Wiens, R C; Mangold, N; Bristow, T; Edwards, P; Berger, G

2015-01-01

The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO2-poor and oxidizing, dilute aqueous solution (Gale Portage Water) in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ∽7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component. PMID:26213668

Diagenesis and clay mineral formation at Gale Crater, Mars

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

Bridges, J. C.; Schwenzer, S. P.; Leveille, R.

The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO₂-poor and oxidizing, dilute aqueous solution (Gale Portage Water)more » in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ~7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component.« less

Diagenesis and clay mineral formation at Gale Crater, Mars

DOE PAGES

Bridges, J. C.; Schwenzer, S. P.; Leveille, R.; ...

2015-01-18

The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO₂-poor and oxidizing, dilute aqueous solution (Gale Portage Water)more » in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ~7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component.« less

Enabling Technologies for the Future of Chemical Synthesis.

PubMed

Fitzpatrick, Daniel E; Battilocchio, Claudio; Ley, Steven V

2016-03-23

Technology is evolving at breakneck pace, changing the way we communicate, travel, find out information, and live our lives. Yet chemistry as a science has been slower to adapt to this rapidly shifting world. In this Outlook we use highlights from recent literature reports to describe how progresses in enabling technologies are altering this trend, permitting chemists to incorporate new advances into their work at all levels of the chemistry development cycle. We discuss the benefits and challenges that have arisen, impacts on academic-industry relationships, and future trends in the area of chemical synthesis.

Cannabis sativa (Marijuana) alters blood chemistry and the cytoarchitecture of some organs in Sprague Dawley rat models.

PubMed

Abey, Nosarieme Omoregie

2018-06-01

There is evidence that Cannabis whose active ingredient is tetrahydrocannabinol (THC) is the most commonly abused neuroactive substance, among young adults. This work investigated the effects of Cannabis sativa on the cytoarchitecture of some key organs and the blood chemistry of rat models. Twenty-one (21) male Sprague Dawley rats were fed different percentage of cannabis chow (0%, 5% and 10%) for a period of seven (7) weeks. Rats were subjected to intermittent cognitive function test and sacrificed after the seventh week, collecting the blood, brain and other important tissues for analysis which include; brain total protein and nitric oxide concentration, blood chemistry and histopathology. Results revealed a dose-dependent decline in the cognitive function, statistically significant decrease in the brain total protein and nitric oxide. Histopathology revealed significant hypertrophy in the heart, hypercellularity in neuronal cells, prominent sinusoids cytoarchitecture of the hepatocytes and vascular congestion in the seminiferous tubules of testes. There was a statistically significant difference in the plasma ALP, ALT, AST level between controls and the cannabis test groups. Cannabis use caused cellular damage through mediation of imbalance and altered cytoarchitecture which may affects the overall health of dependent user. Copyright © 2018 Elsevier Ltd. All rights reserved.

Chemistry, mineralogy and alteration intensity of hydrothermal altered Mt Unzen conduit rocks (Shimabara/Japan)

NASA Astrophysics Data System (ADS)

Hess, Kai-Uwe; Yilmaz, Tim; Gilg, H. Albert; Janots, Emilie; Mayer, Klaus; Nakada, Setsuya; Dingwell, Donald

2017-04-01

Investigations were carried out on hydrothermally altered coherent dacitic dykes samples from (USDP-4) drill core at Mt Unzen stratovolcano (Shimabara/Japan). XRF, XRD, EMPA, C-O-isotope, hot-cathode CL and SEM analysis led to insights concerning chemistry, mineralogy, and intensity and type of alteration as well as the origin of carbonate-precipitating fluids. Additionally a textural characterization of the occurring replacement features in the volcanic conduit rocks was performed. The occurrence of the main secondary phases such as chlorite, pyrite, carbonates, and R1 (Reichweite parameter) illite-smectite and kaolinite group minerals indicate a weak to moderate propylitic to phyllic hydrothermal alteration. The dacitic samples of the dykes show different hydrothermal alteration features: (i) carbonate and chlorite pseudomorphs after hornblende as well as core and zonal textures due to replacement of plagioclase by R1 illite-smectite as well as kaolinite group minerals, (ii) colloform banded fracture fillings and fillings in dissolution vugs, and (iii) chlorite, R1 illite-smectite as well as kaolinite group minerals in the groundmass. Late chlorite veins crosscut precipitates of R1 illite-smectite as well as kaolinite group minerals. Carbonates in fractures and in pseudomorphs after hornblende comprise iron-rich dolomite solid solutions ("ankerite") and calcite. Isotopic values indicate a hydrothermal-magmatic origin for the carbonate formation. The chlorite-carbonate-pyrite index (CCPI) and the Ishikawa alteration index (AI), applied to the investigated samples show significant differences (CCPI=52.7-57.8; AI=36.1-40.6) indicating their different degree of alteration. According to Nakada et al., 2005, the C13 to C16 dykes represent the feeder dyke from the latest eruption (1991-1995) whereas C8 represents an earlier dyke feeder dyke from an older eruption. Weakest alteration, which was obtained in samples C16-1-5 and C13-2-5, correlates with the alteration degree of the pristine dome rocks. The highest CCPI value was determined for sample C14-1-5 and the highest AI value was determined for sample C15-2-6. The degrees of alteration do not indicate highest alteration of the samples C8-1-2 and C8-2-1 from the older dykes.

Enhancing Aluminum Reactivity by Exploiting Surface Chemistry and Mechanical Properties

DTIC Science & Technology

2015-06-01

alter its mechanical properties . In bulk material processing , annealing and quenching metals such as Al can relieve residual stress and improve...increasing  Al  reactivity is to alter its mechanical  properties .  In bulk material  processing , annealing and quenching metals such as  Al  can relieve...mechanical properties . On a single particle level, affecting mechanical properties may also affect Al particle reactivity. Aluminum particles underwent

Thermal Studies of Ammonium Cyanide Reactions: A Model for Thermal Alteration of Prebiotic Compounds in Meteorite Parent Bodies

NASA Technical Reports Server (NTRS)

Hammer, P. G.; Locke, D. R.; Burton, A. S.; Callahan, M. P.

2017-01-01

Organic compounds in carbonaceous chondrites were likely transformed by a variety of parent body processes including thermal and aqueous processing. Here, we analyzed ammonium cyanide reactions that were heated at different temperatures and times by multiple analytical techniques. The goal of this study is to better understand the effect of hydrothermal alteration on cyanide chemistry, which is believed to be responsible for the abiotic synthesis of purine nucleobases and their structural analogs detected in carbonaceous chondrites.

The role of surface chemistry in the cytotoxicity profile of graphene.

PubMed

Majeed, Waqar; Bourdo, Shawn; Petibone, Dayton M; Saini, Viney; Vang, Kieng Bao; Nima, Zeid A; Alghazali, Karrer M; Darrigues, Emilie; Ghosh, Anindya; Watanabe, Fumiya; Casciano, Daniel; Ali, Syed F; Biris, Alexandru S

2017-04-01

Graphene and its derivative, because of their unique physical, electrical and chemical properties, are an important class of nanomaterials being proposed as foundational materials in nanomedicine as well as for a variety of industrial applications. A major limitation for graphene, when used in biomedical applications, is its poor solubility due to its rather hydrophobic nature. Therefore, chemical functionalities are commonly introduced to alter both its surface chemistry and biochemical activity. Here, we show that surface chemistry plays a major role in the toxicological profile of the graphene structures. To demonstrate this, we chemically increased the oxidation level of the pristine graphene and compared the corresponding toxicological effects along with those for the graphene oxide. X-ray photoelectron spectroscopy revealed that pristine graphene had the lowest amount of surface oxygen, while graphene oxide had the highest at 2.5% and 31%, respectively. Low and high oxygen functionalized graphene samples were found to have 6.6% and 24% surface oxygen, respectively. Our results showed a dose-dependent trend in the cytotoxicity profile, where pristine graphene was the most cytotoxic, with decreasing toxicity observed with increasing oxygen content. Increased surface oxygen also played a role in nanomaterial dispersion in water or cell culture medium over longer periods. It is likely that higher dispersity might result in graphene entering into cells as individual flakes ~1 nm thick rather than as more cytotoxic aggregates. In conclusion, changes in graphene's surface chemistry resulted in altered solubility and toxicity, suggesting that a generalized toxicity profile would be rather misleading. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Effects of the hippopotamus on the chemistry and ecology of a changing watershed.

PubMed

Stears, Keenan; McCauley, Douglas J; Finlay, Jacques C; Mpemba, James; Warrington, Ian T; Mutayoba, Benezeth M; Power, Mary E; Dawson, Todd E; Brashares, Justin S

2018-05-29

Cross-boundary transfers of nutrients can profoundly shape the ecology of recipient systems. The common hippopotamus, Hippopotamus amphibius , is a significant vector of such subsidies from terrestrial to river ecosystems. We compared river pools with high and low densities of H. amphibius to determine how H. amphibius subsidies shape the chemistry and ecology of aquatic communities. Our study watershed, like many in sub-Saharan Africa, has been severely impacted by anthropogenic water abstraction reducing dry-season flow to zero. We conducted observations for multiple years over wet and dry seasons to identify how hydrological variability influences the impacts of H. amphibius During the wet season, when the river was flowing, we detected no differences in water chemistry and nutrient parameters between pools with high and low densities of H. amphibius Likewise, the diversity and abundance of fish and aquatic insect communities were indistinguishable. During the dry season, however, high-density H. amphibiu s pools differed drastically in almost all measured attributes of water chemistry and exhibited depressed fish and insect diversity and fish abundance compared with low-density H. amphibius pools. Scaled up to the entire watershed, we estimate that H. amphibius in this hydrologically altered watershed reduces dry-season fish abundance and indices of gamma-level diversity by 41% and 16%, respectively, but appears to promote aquatic invertebrate diversity. Widespread human-driven shifts in hydrology appear to redefine the role of H. amphibius , altering their influence on ecosystem diversity and functioning in a fashion that may be more severe than presently appreciated.

Detection of Organics at Mars: How Wet Chemistry Onboard SAM Helps

NASA Technical Reports Server (NTRS)

Buch, A.; Freissinet, Caroline; Szopa, C.; Glavin, D.; Coll, P.; Cabane, M.; Eigenbrode, J.; Navarro-Gonzalez, R.; Coscia, D.; Teinturier, S.;

BOTULISM E IN LAKE ERIE: ECOLOGY AND LOWER FOOD WEB TRANSFER

EPA Science Inventory

This project will determine the environmental conditions that favor botulism Type E bacteria in Lake Erie and explore whether quagga mussels are altering bottom sediment conditions to favor C. botulinum growth. Analysis of environmental parameters, including water chemistry, alg...

Watershed Alteration Impacts to Benthic Diatom Assemblages in Streams

EPA Science Inventory

To examine the use of diatoms as indicators of urban impacts to streams, we identified relationships of diatom assemblages with water chemistry and land use for 160 sites in New England. The first axis of a nonmetric multidimensional scaling ordination showed significant relation...

Correlated Microanalysis of Cometary Organic Grains Returned by Stardust

NASA Technical Reports Server (NTRS)

DeGregorio, B. T.; Stroud, R. M.; Nittler, L. R.; Cody, G. D,; Kilcoyne, A. L. D.

2011-01-01

Preliminary examination (PE) of samples returned from Comet 81P/Wild 2 by the NASA Stardust mission revealed a wide variety of carbonaceous samples [e.g. 1]. Carbonaceous matter is present as inclusions, rinds, and films in polyminerallic terminal particles [2-4], as carbon-rich particles along track walls [2, 5, 6], and as organic matter in aerogel around tracks [7, 8]. The organic chemistry of these samples ranges from purely aliphatic hydrocarbons to highly-aromatic material, often modified by various organic functional groups [2, 4, 5, 9-11]. Difficulty arises when interpreting the genesis of these carbonaceous samples, since contaminants could be introduced from the spacecraft [12], aerogel [1, 8], or during sample preparation. In addition, hypervelocity capture into aerogel may have heated cometary material in excess of 1000 C, which could have significantly altered the structure and chemistry of carbonaceous matter. Fortunately, much of this contamination or alteration can be identified through correlated microanalysis with transmission electron microscopy (TEM), scanning-transmission X-ray microscopy (STXM), and nanoscale secondary ion mass spectroscopy (SIMS).

Knockdown of a laccase in Populus deltoides confers altered cell wall chemistry and increased sugar release

DOE PAGES

Bryan, Anthony C.; Jawdy, Sara; Gunter, Lee; ...

2016-04-15

Plant laccases are thought to function in the oxidation of monolignols which leads to higher order lignin formation. Only a hand-full of laccases in plants have been functionally evaluated and as such little is known about the breadth of their impact on cell wall chemistry or structure. Here we describe a previously uncharacterized laccase from Populus, encoded by locus Potri.008G06400, whose reduced expression resulted in transgenic Populus trees with changes in syringyl/guaiacyl (S/G) ratios as well as altered sugar release phenotypes. These phenotypes are consistent with plant biomass exhibiting reduced recalcitrance. Interestingly, the transgene effect on recalcitrance is dependent onmore » a mild pretreatment prior to chemical extraction of sugars. Metabolite profiling suggests the transgene modulates phenolics that are associated with the cell wall structure. Finally, we propose a model in which this particular laccase has a range of functions related to oxidation of phenolics that interact with lignin in the cell wall.« less

Knockdown of a laccase in Populus deltoides confers altered cell wall chemistry and increased sugar release

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

Bryan, Anthony C.; Jawdy, Sara; Gunter, Lee

Plant laccases are thought to function in the oxidation of monolignols which leads to higher order lignin formation. Only a hand-full of laccases in plants have been functionally evaluated and as such little is known about the breadth of their impact on cell wall chemistry or structure. Here we describe a previously uncharacterized laccase from Populus, encoded by locus Potri.008G06400, whose reduced expression resulted in transgenic Populus trees with changes in syringyl/guaiacyl (S/G) ratios as well as altered sugar release phenotypes. These phenotypes are consistent with plant biomass exhibiting reduced recalcitrance. Interestingly, the transgene effect on recalcitrance is dependent onmore » a mild pretreatment prior to chemical extraction of sugars. Metabolite profiling suggests the transgene modulates phenolics that are associated with the cell wall structure. Finally, we propose a model in which this particular laccase has a range of functions related to oxidation of phenolics that interact with lignin in the cell wall.« less

Preparing for a Global Scientific Workforce: Lessons Learned by the Chemistry Community

NASA Astrophysics Data System (ADS)

Baranovic, M.; Nameroff, T.

2005-12-01

Globalization has significant implications for science, science education, and the workforce. Flows of capital and knowledge are altering patterns of economic and technological development. Technology is allowing science to be conducted in real time on a global scale. International connections and mobility are increasing worldwide. At the same time science is becoming a truly global endeavor, the convergence of disciplines suggests that scientists from different backgrounds can learn from each other's experiences in addressing these challenges and opportunities. This presentation reviews some of the impacts of globalization on the chemically related sciences, students, and profession. As a result of globalization, today's practitioners of chemistry need an ever-expanding skill set to succeed. In addition to a strong command of the basic principles of chemistry, students and practitioners need to know how to work on multicultural teams, have knowledge of other languages, and be able to communicate effectively. The American Chemical Society (ACS) is coming to terms with and responding to changes in the nature of chemistry and its practice. This presentation will explore some of the innovative efforts of ACS to meet the challenges for chemistry in an era of globalization. The Earth and space sciences community may benefit from the chemistry community's "lessons learned."

Enabling Technologies for the Future of Chemical Synthesis

PubMed Central

2016-01-01

Technology is evolving at breakneck pace, changing the way we communicate, travel, find out information, and live our lives. Yet chemistry as a science has been slower to adapt to this rapidly shifting world. In this Outlook we use highlights from recent literature reports to describe how progresses in enabling technologies are altering this trend, permitting chemists to incorporate new advances into their work at all levels of the chemistry development cycle. We discuss the benefits and challenges that have arisen, impacts on academic–industry relationships, and future trends in the area of chemical synthesis. PMID:27163040

The origin of soil organic matter controls its composition and bioreactivity across a mesic boreal forest latitudinal gradient.

PubMed

Kohl, Lukas; Philben, Michael; Edwards, Kate A; Podrebarac, Frances A; Warren, Jamie; Ziegler, Susan E

2018-02-01

Warmer climates have been associated with reduced bioreactivity of soil organic matter (SOM) typically attributed to increased diagenesis; the combined biological and physiochemical transformation of SOM. In addition, cross-site studies have indicated that ecosystem regime shifts, associated with long-term climate warming, can affect SOM properties through changes in vegetation and plant litter production thereby altering the composition of soil inputs. The relative importance of these two controls, diagenesis and inputs, on SOM properties as ecosystems experience climate warming, however, remains poorly understood. To address this issue we characterized the elemental, chemical (nuclear magnetic resonance spectroscopy and total hydrolysable amino acids analysis), and isotopic composition of plant litter and SOM across a well-constrained mesic boreal forest latitudinal transect in Atlantic Canada. Results across forest sites within each of three climate regions indicated that (1) climate history and diagenesis affect distinct parameters of SOM chemistry, (2) increases in SOM bioreactivity with latitude were associated with elevated proportions of carbohydrates relative to plant waxes and lignin, and (3) despite the common forest type across regions, differences in SOM chemistry by climate region were associated with chemically distinct litter inputs and not different degrees of diagenesis. The observed climate effects on vascular plant litter chemistry, however, explained only part of the regional differences in SOM chemistry, most notably the higher protein content of SOM from warmer regions. Greater proportions of lignin and aliphatic compounds and smaller proportions of carbohydrates in warmer sites' soils were explained by the higher proportion of vascular plant relative to moss litter in the warmer relative to cooler forests. These results indicate that climate change induced decreases in the proportion of moss inputs not only impacts SOM chemistry but also increases the resistance of SOM to decomposition, thus significantly altering SOM cycling in these boreal forest soils. © 2017 John Wiley & Sons Ltd.

Naturally acidic surface and ground waters draining porphyry-related mineralized areas of the Southern Rocky Mountains, Colorado and New Mexico

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Bove, D.J.; Plumlee, G.S.; Runkel, R.L.

2009-01-01

Acidic, metal-rich waters produced by the oxidative weathering and resulting leaching of major and trace elements from pyritic rocks can adversely affect water quality in receiving streams and riparian ecosystems. Five study areas in the southern Rocky Mountains with naturally acidic waters associated with porphyry mineralization were studied to document variations in water chemistry and processes that control the chemical variations. Study areas include the Upper Animas River watershed, East Alpine Gulch, Mount Emmons, and Handcart Gulch in Colorado and the Red River in New Mexico. Although host-rock lithologies in all these areas range from Precambrian gneisses to Cretaceous sedimentary units to Tertiary volcanic complexes, the mineralization is Tertiary in age and associated with intermediate to felsic composition, porphyritic plutons. Pyrite is ubiquitous, ranging from ???1 to >5 vol.%. Springs and headwater streams have pH values as low as 2.6, SO4 up to 3700 mg/L and high dissolved metal concentrations (for example: Fe up to 400 mg/L; Cu up to 3.5 mg/L; and Zn up to 14.4 mg/L). Intensity of hydrothermal alteration and presence of sulfides are the primary controls of water chemistry of these naturally acidic waters. Subbasins underlain by intensely hydrothermally altered lithologies are poorly vegetated and quite susceptible to storm-induced surface runoff. Within the Red River study area, results from a storm runoff study documented downstream changes in river chemistry: pH decreased from 7.80 to 4.83, alkalinity decreased from 49.4 to <1 mg/L, SO4 increased from 162 to 314 mg/L, dissolved Fe increased from to 0.011 to 0.596 mg/L, and dissolved Zn increased from 0.056 to 0.607 mg/L. Compared to mine drainage in the same study areas, the chemistry of naturally acidic waters tends to overlap but not reach the extreme concentrations of metals and acidity as some mine waters. The chemistry of waters draining these mineralized but unmined areas can be used to estimate premining conditions at sites with similar geologic and hydrologic conditions. For example, the US Geological Survey was asked to estimate premining ground-water chemistry at the Questa Mo mine, and the proximal analog approach was used because a mineralized but unmined area was located adjacent to the mine property. By comparing and contrasting water chemistry from different porphyry mineralized areas, this study not only documents the range in concentrations of constituents of interest but also provides insight into the primary controls of water chemistry.

Chemistry and Mineralogy of Antarctica Dry Valley Soils: Implications for Mars

NASA Technical Reports Server (NTRS)

Quinn, J. E.; Golden, D. C.; Graff, T. G.; Ming, D. W.; Morris, R. V.; Douglas, S.; Kounaves, S. P.; McKay, C. P.; Tamppari, L, K.; Smith, P. H.;

Thermally-Induced Chemistry and the Jovian Icy Satellites: A Laboratory Study of the Formation of Sulfur Oxyanions

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2011-01-01

Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Here we present new results on thermally-induced reactions at 50-100 K in solid H2O-SO2 mixtures, reactions that take place without the need for a high-radiation environment. We find that H2O and SO2 react to produce sulfur Oxyanions, such as bisulfite, that as much as 30% of the SO2 can be consumed through this reaction, and that the products remain in the ice when the temperature is lowered, indicating that these reactions are irreversible. Our results suggest that thermally-induced reactions can alter the chemistry at temperatures relevant to the icy satellites in the Jovian system.

CI chondrite-like clasts in the Nilpena polymict ureilite - Implications for aqueous alteration processes in CI chondrites

NASA Technical Reports Server (NTRS)

Brearley, Adrian J.; Prinz, Martin

1992-01-01

Petrographic studies of Nilpena polymict ureilite have revealed the presence of small quantities of carbonaceous chondrite matrix clasts. Detailed electron microprobe and TEM studies show that the chemistry and fine-scale mineralogy of one of these clasts is consistent with CI carbonaceous chondrite matrix. Compared to Orgeuil, the phyllosilicate, sulfide, and oxide mineralogy suggests that the Nilpena clasts may represent a less altered type of CI matrix. It is suggested that increased oxidation and aqueous alteration of Nilpena-type materials could result in the formation of the type of mineral assemblage observed in Orgueil. Increased alteration produces progressive more Mg-rich phyllosilicates and more Fe(3+)-rich iron oxides, such as ferrihydrite. As a function of increased alteration, Ca is also progressively leached from the matrix material to form carbonate veins. The depletion of Ca in CI chondrite matrices suggests the Ivuna and Alais may be intermediate in their degree of alteration to Nilpena and Orgueil.

Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

NASA Astrophysics Data System (ADS)

Hudson, R.; Loeffler, M. J.; Gerakines, P.

2017-12-01

The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

Understanding the role of hydrogen bonding in the aggregation of fumed silica particles in triglyceride solvents.

PubMed

Whitby, Catherine P; Krebsz, Melinda; Booty, Samuel J

2018-10-01

Fumed silica particles are thought to thicken organic solvents into gels by aggregating to form networks. Hydrogen bonding between silanol groups on different particle surfaces causes the aggregation. The gel structure and hence flow behaviour is altered by varying the proportion of silanol groups on the particle surfaces. However, characterising the gel using rheology measurements alone is not sufficient to optimise the aggregation. We have used confocal microscopy to characterise the changes in the network microstructure caused by altering the particle surface chemistry. Organogels were formed by dispersing fumed silica nanoparticles in a triglyceride solvent. The particle surface chemistry was systematically varied from oleophobic to oleophilic by functionalisation with hydrocarbons. We directly visualised the particle networks using confocal scanning laser microscopy and investigated the correlations between the network structure and the shear response of the organogels. Our key finding is that the sizes of the pore spaces in the networks depend on the fraction of silanol groups available to form hydrogen bonds. The reduction in the network elasticity of gels formed by methylated particles can be accounted for by the increasing pore size and tenuous nature of the networks. This is the first report that characterises the changes in the microstructure of fumed silica particle networks in non-polar solvents caused by manipulating the particle surface chemistry. Copyright © 2018 Elsevier Inc. All rights reserved.

Is atmospheric phosphorus pollution altering global alpine Lake stoichiometry?

NASA Astrophysics Data System (ADS)

Brahney, Janice; Mahowald, Natalie; Ward, Daniel S.; Ballantyne, Ashley P.; Neff, Jason C.

2015-09-01

Anthropogenic activities have significantly altered atmospheric chemistry and changed the global mobility of key macronutrients. Here we show that contemporary global patterns in nitrogen (N) and phosphorus (P) emissions drive large hemispheric variation in precipitation chemistry. These global patterns of nutrient emission and deposition (N:P) are in turn closely reflected in the water chemistry of naturally oligotrophic lakes (r2 = 0.81, p < 0.0001). Observed increases in anthropogenic N deposition play a role in nutrient concentrations (r2 = 0.20, p < 0.05) however, atmospheric deposition of P appears to be major contributor to this pattern (r2 = 0.65, p < 0.0001). Atmospheric simulations indicate a global increase in P deposition by 1.4 times the preindustrial rate largely due to increased dust and biomass burning emissions. Although changes in the mass flux of global P deposition are smaller than for N, the impacts on primary productivity may be greater because, on average, one unit of increased P deposition has 16 times the influence of one unit of N deposition. These stoichiometric considerations, combined with the evidence presented here, suggest that increases in P deposition may be a major driver of alpine Lake trophic status, particularly in the Southern Hemisphere. These results underscore the need for the broader scientific community to consider the impact of atmospheric phosphorus deposition on the water quality of naturally oligotrophic lakes.

Elevated CO2 alters birch resistance to Lagomorpha herbivores

Treesearch

William J. Mattson; Kari Kuokkanen; Pekka Niemela; Riitta Julkunen-Tiitto; Seppo Kellomaki; Jorma Tahvanainen

2004-01-01

We studied the three-way interaction of elevated CO2, nitrogen (N), and temperature (T), and the two-way interaction of elevated CO2 and early-season defoliation on the secondary chemistry and resistance of Eurasian silver birch (Betula pendula) and North American paper birch (B. papyrifera...

Chemistry of wood strength

Treesearch

Jerrold E. Winandy; Roger M. Rowell

2005-01-01

This chapter presents a theoretical model to explain the relationship between the mechanical properties and the chemical components of wood. This model is then used to describe the effects of altered composition on those mechanical properties. Many of the theories presented are only partially proven and just beginning to be understood. These theories should be...

Determining effects of multiple tannin manure applications on dairy forages and soil

USDA-ARS?s Scientific Manuscript database

Dietary choices for dairy cows have direct implications to nutrient availability from land-applied manure because of alterations to manure chemistry. Tannin additions to a dairy cow’s diet protect feed protein through rumen fermentation and digestion, resulting in reduced concentrations of urea nitr...

CARDIOVASCULAR RESPONSE OF BEAGLES TO A SUPRALETHAL DOSE OF MIXED GAMMA- NEUTRON RADIATION

DTIC Science & Technology

The cardiovascular response of the beagle and its alteration by shielding were evaluated. Arterial pressure, blood volume, heart rate, and some plasma ... chemistry values were determined before and for 1 hour following irradiation. Immediately after irradiation the blood pressure increased in all groups

Contemporary and temporal investigation of per- and polyfluorinated compounds in Cape Fear river, North Carolina surface water samples

EPA Science Inventory

Recent regulatory pressure has altered the chemistry of per- and polyfluorinated compounds being manufactured and used in industrial and consumer applications. Many manufacturers have been moving toward the production of shorter chain per- and polyfluorinated compounds. A series ...

Effects of sulfate deposition on pore water dissolved organic carbon, nutrients, and microbial enzyme activities in a northern peatland

EPA Science Inventory

Export of dissolved organic carbon from lakes and streams has increased throughout Europe and North America over the past several decades. One possible cause is altered deposition chemistry; specifically, decreasing sulfate inputs leading to changes in ionic strength and dissolve...

The Effect of Shock on the Amorphous Component in Altered Basalt

NASA Technical Reports Server (NTRS)

Eckley, S. A.; Wright, S. P.; Rampe, E. B.; Niles, P. B.

2017-01-01

Investigation of the geochemical and mineralogical composition of the Martian surface provides insight into the geologic history of the predominantly basaltic crust. The Chemistry and Mineralogy (CheMin) instrument onboard the Curiosity rover has returned the first X-Ray diffraction data from the Martian surface. However, large proportions (27 +/- 14 with some estimates as high as 50 weight percentage) of an amorphous component have been reported. As a remedy to this problem, mass balance equations using geochemistry, volatile chemistry, and mineralogy have been employed to constrain the geochemistry of the amorphous component. However, "the nature and number of amorphous phases that constitute the amorphous component is not unequivocally known". Multiple hypotheses have been proposed to explain the origin of this amorphous component: Allophane (Al2O); Basaltic glass (Volcanic and impact); Palagonite (Altered basaltic glass); Hisingerite (Fe (sup 3 plus)-bearing phyllosilicate); S/Cl-rich component (sulfates and/or akaganeite); Nanophase ferric oxide component (npOx). Establishing a multi-phase amorphous component from a basaltic precursor that has undergone physical and chemical weathering within geochemical constraints is of paramount importance to better understand the composition of a large portion of the Martian surface (up to 50 weight percentage). Shocked basalts from Lonar Crater in India are valuable analogs for the Martian surface because it is a well-preserved impact crater in a basaltic target. Having undergone pre- and post-shock aqueous alteration, these rocks provide crucial data regarding the effect of shock on the amorphous component in altered basalt. By conducting mass balance equations similar to what has been performed for Gale crater materials, we attempt to calculate the geochemistry of the amorphous component in altered basalts ranging from unshocked to Class 5 (Table 1). This has the potential to reveal the nature and origin (i.e. primary igneous, shock metamorphic, and/or aqueous alteration occurring before or after the impact event) of the amorphous component in shocked basalt with the goal of unravelling the history of the Martian surface.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

PubMed

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

Ocean acidification in the coastal zone from an organism's perspective: multiple system parameters, frequency domains, and habitats.

PubMed

Waldbusser, George G; Salisbury, Joseph E

2014-01-01

Multiple natural and anthropogenic processes alter the carbonate chemistry of the coastal zone in ways that either exacerbate or mitigate ocean acidification effects. Freshwater inputs and multiple acid-base reactions change carbonate chemistry conditions, sometimes synergistically. The shallow nature of these systems results in strong benthic-pelagic coupling, and marine invertebrates at different life history stages rely on both benthic and pelagic habitats. Carbonate chemistry in coastal systems can be highly variable, responding to processes with temporal modes ranging from seconds to centuries. Identifying scales of variability relevant to levels of biological organization requires a fuller characterization of both the frequency and magnitude domains of processes contributing to or reducing acidification in pelagic and benthic habitats. We review the processes that contribute to coastal acidification with attention to timescales of variability and habitats relevant to marine bivalves.

Climate Impacts on Tropospheric Ozone and Hydroxyl

NASA Technical Reports Server (NTRS)

Shindell, Drew T.; Bell, N.; Faluvegi, G.

2003-01-01

Climate change may influence tropospheric ozone and OH via several main pathways: (1) altering chemistry via temperature and humidity changes, (2) changing ozone and precursor sources via surface emissions, stratosphere-troposphere exchange, and light- ning, and (3) affecting trace gas sinks via the hydrological cycle and dry deposition. We report results from a set of coupled chemistry-climate model simulations designed to systematically study these effects. We compare the various effects with one another and with past and projected future changes in anthropogenic and natural emissions of ozone precursors. We find that white the overall impact of climate on ozone is probably small compared to emission changes, some significant seasonal and regional effects are apparent. The global effect on hydroxyl is quite large, however, similar in size to the effect of emission changes. Additionally, we show that many of the chemistry-climate links that are not yet adequately modeled are potentially important.

Impact of finite rate chemistry on the hydrodynamic stability of shear flows in turbulent lean premixed combustion

NASA Astrophysics Data System (ADS)

Dagan, Yuval; Ghoniem, Ahmed

2017-11-01

Recent experimental observations show that the dynamic response of a reactive flow is strongly impacted by the fuel chemistry. In order to gain insight into some of the underlying mechanisms we formulate a new linear stability model that incorporates the impact of finite rate chemistry on the hydrodynamic stability of shear flows. Contrary to previous studies which typically assume that the velocity field is independent of the kinetic rates, the velocity field in our study is coupled with the temperature field. Using this formulation, we reproduce previous results, e.g., most unstable global modes, obtained for non-reacting shear flow. Moreover, we show that these modes are significantly altered in frequency and gain by the presence of a reaction region within the shear layer. This qualitatively agrees with results of our recent experimental and numerical studies, which show that the flame surface location relative to the shear layer influences the stability characteristics in combustion tunnels. This study suggests a physical explanation for the observed impact of finite rate chemistry on shear flow stability.

Effects of oral powder electrolyte administration on packed cell volume, plasma chemistry parameters, and incidence of colic in horses participating in a 6-day 162-km trail ride

PubMed Central

Walker, Wade T.; Callan, Robert J.; Hill, Ashley E.; Tisher, Kelly B.

2014-01-01

This study evaluated the effects of administering oral powder electrolytes on packed cell volume (PCV), plasma chemistry parameters, and incidence of colic in horses participating on a 6-day 162-km trail ride in which water was not offered ad libitum. Twenty-three horses received grain with powder electrolytes daily while 19 control horses received grain only. Horses were ridden approximately 32 km a day at a walk or trot. Packed cell volume and plasma chemistry parameters were analyzed daily. Episodes of colic were diagnosed and treated by a veterinarian unaware of treatment group allocation. Blood parameters and incidence of colic were compared between treatment groups. Electrolyte administration did not alter PCV or plasma chemistry parameters compared to controls. The incidence of colic was significantly higher in treated horses (P = 0.05). Oral powder electrolytes did not enhance hydration status or electrolyte homeostasis and may be associated with colic in horses participating on long distance trail rides similar to this model. PMID:25082992

Effects of oral powder electrolyte administration on packed cell volume, plasma chemistry parameters, and incidence of colic in horses participating in a 6-day 162-km trail ride.

PubMed

Walker, Wade T; Callan, Robert J; Hill, Ashley E; Tisher, Kelly B

2014-08-01

This study evaluated the effects of administering oral powder electrolytes on packed cell volume (PCV), plasma chemistry parameters, and incidence of colic in horses participating on a 6-day 162-km trail ride in which water was not offered ad libitum. Twenty-three horses received grain with powder electrolytes daily while 19 control horses received grain only. Horses were ridden approximately 32 km a day at a walk or trot. Packed cell volume and plasma chemistry parameters were analyzed daily. Episodes of colic were diagnosed and treated by a veterinarian unaware of treatment group allocation. Blood parameters and incidence of colic were compared between treatment groups. Electrolyte administration did not alter PCV or plasma chemistry parameters compared to controls. The incidence of colic was significantly higher in treated horses (P = 0.05). Oral powder electrolytes did not enhance hydration status or electrolyte homeostasis and may be associated with colic in horses participating on long distance trail rides similar to this model.

Fluorescence Modulation of Green Fluorescent Protein Using Fluorinated Unnatural Amino Acids.

PubMed

Villa, Jordan K; Tran, Hong-Anh; Vipani, Megha; Gianturco, Stephanie; Bhasin, Konark; Russell, Brent L; Harbron, Elizabeth J; Young, Douglas D

2017-07-16

The ability to modulate protein function through minimal perturbations to amino acid structure represents an ideal mechanism to engineer optimized proteins. Due to the novel spectroscopic properties of green fluorescent protein, it has found widespread application as a reporter protein throughout the fields of biology and chemistry. Using site-specific amino acid mutagenesis, we have incorporated various fluorotyrosine residues directly into the fluorophore of the protein, altering the fluorescence and shifting the pKa of the phenolic proton associated with the fluorophore. Relative to wild type GFP, the fluorescence spectrum of the protein is altered with each additional fluorine atom, and the mutant GFPs have the potential to be employed as pH sensors due to the altered electronic properties of the fluorine atoms.

Environmental Nutrient Supply Directly Alters Plant Traits but Indirectly Determines Virus Growth Rate

PubMed Central

Lacroix, Christelle; Seabloom, Eric W.; Borer, Elizabeth T.

2017-01-01

Ecological stoichiometry and resource competition theory both predict that nutrient rates and ratios can alter infectious disease dynamics. Pathogens such as viruses hijack nutrient rich host metabolites to complete multiple steps of their epidemiological cycle. As the synthesis of these molecules requires nitrogen (N) and phosphorus (P), environmental supply rates, and ratios of N and P to hosts can directly limit disease dynamics. Environmental nutrient supplies also may alter virus epidemiology indirectly by changing host phenotype or the dynamics of coinfecting pathogens. We tested whether host nutrient supplies and coinfection control pathogen growth within hosts and transmission to new hosts, either directly or through modifications of plant tissue chemistry (i.e., content and stoichiometric ratios of nutrients), host phenotypic traits, or among-pathogen interactions. We examined two widespread plant viruses (BYDV-PAV and CYDV-RPV) in cultivated oats (Avena sativa) grown along a range of N and of P supply rates. N and P supply rates altered plant tissue chemistry and phenotypic traits; however, environmental nutrient supplies and plant tissue content and ratios of nutrients did not directly alter virus titer. Infection with CYDV-RPV altered plant traits and resulted in thicker plant leaves (i.e., higher leaf mass per area) and there was a positive correlation between CYDV-RPV titer and leaf mass per area. CYDV-RPV titer was reduced by the presence of a competitor, BYDV-PAV, and higher CYDV-RPV titer led to more severe chlorotic symptoms. In our experimental conditions, virus transmission was unaffected by nutrient supply rates, co-infection, plant stoichiometry, or plant traits, although nutrient supply rates have been shown to increase infection and coinfection rates. This work provides a robust test of the role of plant nutrient content and ratios in the dynamics of globally important pathogens and reveals a more complex relationship between within-host virus growth and alterations of plant traits. A deeper understanding of the differential effects of environmental nutrient supplies on virus epidemiology and ecology is particularly relevant given the rapid increase of nutrients flowing into Earth's ecosystems as a result of human activities. PMID:29163408

Spatio-temporal variation in stream water chemistry in a tropical urban watershed

Treesearch

A. Ramirez; K.G. Rosas; A.E. Lugo; O.M. Ramos-Gonzalez

2014-01-01

Urban activities and related infrastructure alter the natural patterns of stream physical and chemical conditions. According to the Urban Stream Syndrome, streams draining urban landscapes are characterized by high concentrations of nutrients and ions, and might have elevated water temperatures and variable oxygen concentrations. Here, we report temporal and spatial...

Effects of Temperature and Acidic Pre-Treatment on Fenton-Driven Oxidation of MTBE-Spent Granular Activated Carbon

EPA Science Inventory

Temperature-dependent mechanisms in the Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was investigated. Prior to iron (Fe) amendment to the GAC, acid-treatment altered the surface chemistry of the GAC and lowered the pH ...

Effects on temperature and acidic pre-treatment on Fenton-driven oxidation of MTBE-spent granular activated carbon

EPA Science Inventory

Temperature-dependent mechanisms in the Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was investigated. Prior to iron (Fe) amendment to the GAC, acid-treatment altered the surface chemistry of the GAC and lowered the p...

ALTERED SOIL-SOIL WATER INTERACTION INFERRED FROM STREAM WATER CHEMISTRY AT AN ARTIFICIALLY ACIDIFIED WATERSHED AT BEAR BROOK WATERSHED, MAINE. (R825762)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

ALTERED SOIL-SOIL WATER INTERACTIONS INFERRED FROM STREAMWATER CHEMISTRY AT AN ARTIFICALLY ACIDIFIED WATERSHED AT BEAR BROOK WATERSHED, MAINE USA. (R825762)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Changes in soil amino composition and microbial N acquisition strategies in response to woody plant invasion of grasslands

USDA-ARS?s Scientific Manuscript database

Changes in land cover have the potential to alter nutrient cycling through changes in carbon input chemistry, microbial community structure, and even soil structure. In the Rio Grande plains region of southern Texas, overgrazing and fire suppression have resulted in progressive encroachment of N-fix...

Litters of photosynthetically divergent grasses exhibit differential metabolic responses to warming and elevated CO2

USDA-ARS?s Scientific Manuscript database

Climatic stress induced by warming can alter plant metabolism, leading to changes in litter chemistry that can affect soil carbon cycling. Elevated CO2 could partly mitigate warming induced moisture stress, and the degree of this mitigation may vary with plant functional types. We hypothesized that,...

Global change and wilderness science

Treesearch

Peter M. Vitousek; John D. Aber; Christine L. Goodale; Gregory H. Aplet

2000-01-01

The breadth and scope of human-caused environmental change is well-established; the distribution and abundance of species, the vegetation cover of the land, and the chemistry of the atmosphere have been altered substantially and globally. How can science in wilderness areas contribute to the analysis of human-caused change? We use nitrate losses from forests to...

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

Treesearch

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

2004-01-01

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

Litter chemistry, community shift, and non-additive effects drive litter decomposition changes following invasion by a generalist pathogen

Treesearch

Richard C. Cobb; David M. Rizzo

2016-01-01

Forest pathogens have strong potential to shape ecosystem function by altering litterfall, microclimate, and changing community structure. We quantified changes in litter decomposition from a set of distinct diseases caused by Phytophthora ramorum, an exotic generalist pathogen. Phytophthora ramorum causes leaf blight and...

US experiments flown on the Soviet satellite COSMOS 936

NASA Technical Reports Server (NTRS)

Rosenzweig, S. N.; Souza, K. A.

1978-01-01

Results of spaceborne experiments onboard the Cosmos 936 satellite are reported. Alterations in normal bone chemistry, muscle structure, and general physiology resulting from spaceflight are covered along with measurements of cosmic radiation and its potential hazard to man during prolonged spaceflights. Postflight activities involving the seven U.S. experiments are emphasized.

Microbial metabolism alters pore water chemistry and increases consolidation of oil sands tailings.

PubMed

Arkell, Nicholas; Kuznetsov, Petr; Kuznetsova, Alsu; Foght, Julia M; Siddique, Tariq

2015-01-01

Tailings produced during bitumen extraction from surface-mined oil sands ores (tar sands) comprise an aqueous suspension of clay particles that remain dispersed for decades in tailings ponds. Slow consolidation of the clays hinders water recovery for reuse and retards volume reduction, thereby increasing the environmental footprint of tailings ponds. We investigated mechanisms of tailings consolidation and revealed that indigenous anaerobic microorganisms altered porewater chemistry by producing CO and CH during metabolism of acetate added as a labile carbon amendment. Entrapped biogenic CO decreased tailings pH, thereby increasing calcium (Ca) and magnesium (Mg) cations and bicarbonate (HCO) concentrations in the porewater through dissolution of carbonate minerals. Soluble ions increased the porewater ionic strength, which, with higher exchangeable Ca and Mg, decreased the diffuse double layer of clays and increased consolidation of tailings compared with unamended tailings in which little microbial activity was observed. These results are relevant to effective tailings pond management strategies. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Aromatic, Alphatic, Enigmatic: The Chemistry of Titan

NASA Astrophysics Data System (ADS)

Horst, Sarah

2017-10-01

The extraordinary complexity of Titan’s atmospheric chemistry far surpasses that of any other solar system atmosphere. With its thick N2 atmosphere and stable bodies of liquid on its surface, Titan also possesses many physical processes that are similar to those that occur on Earth. The connection between Titan’s surface and atmosphere is unique in our solar system; atmospheric chemistry produces materials that are deposited on the surface and subsequently altered by surface-atmosphere interactions such as aeolian and fluvial processes resulting in the formation of extensive dune fields and expansive lakes and seas. Titan’s atmosphere is favorable for organic haze formation, which combined with the presence of some oxygen-bearing molecules indicates that Titan’s atmosphere may produce molecules of prebiotic interest. The combination of organics and liquid, in the form of water in a subsurface ocean and methane/ethane in the surface lakes and seas, means that Titan may be the ideal place in the solar system to test ideas about habitability, prebiotic chemistry, and the ubiquity and diversity of life in the universe. I will review our current understanding of chemistry on Titan forged from the powerful combination of Earth-based observations, remote sensing and in situ spacecraft measurements, laboratory experiments, and models. I will conclude with some of the questions that remain after Cassini-Huygens.

A framework for expanding aqueous chemistry in the ...

EPA Pesticide Factsheets

This paper describes the development and implementation of an extendable aqueous-phase chemistry option (AQCHEM − KMT(I)) for the Community Multiscale Air Quality (CMAQ) modeling system, version 5.1. Here, the Kinetic PreProcessor (KPP), version 2.2.3, is used to generate a Rosenbrock solver (Rodas3) to integrate the stiff system of ordinary differential equations (ODEs) that describe the mass transfer, chemical kinetics, and scavenging processes of CMAQ clouds. CMAQ's standard cloud chemistry module (AQCHEM) is structurally limited to the treatment of a simple chemical mechanism. This work advances our ability to test and implement more sophisticated aqueous chemical mechanisms in CMAQ and further investigate the impacts of microphysical parameters on cloud chemistry. Box model cloud chemistry simulations were performed to choose efficient solver and tolerance settings, evaluate the implementation of the KPP solver, and assess the direct impacts of alternative solver and kinetic mass transfer on predicted concentrations for a range of scenarios. Month-long CMAQ simulations for winter and summer periods over the US reveal the changes in model predictions due to these cloud module updates within the full chemical transport model. While monthly average CMAQ predictions are not drastically altered between AQCHEM and AQCHEM − KMT, hourly concentration differences can be significant. With added in-cloud secondary organic aerosol (SOA) formation from bio

The effect of liquid hot water pretreatment on the chemical–structural alteration and the reduced recalcitrance in poplar

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

Li, Mi; Cao, Shilin; Meng, Xianzhi

Hydrothermal pretreatment using liquid hot water (LHW) is capable of substantially reducing the cell wall recalcitrance of lignocellulosic biomass. It enhances the saccharification of polysaccharides, particularly cellulose, into glucose with relatively low capital required. Due to the close association with biomass recalcitrance, the structural change of the components of lignocellulosic materials during the pretreatment is crucial to understand pretreatment chemistry and advance the bio-economy. Although the LHW pretreatment has been extensively applied and studied, the molecular structural alteration during pretreatment and its significance to reduced recalcitrance have not been well understood.

The effect of liquid hot water pretreatment on the chemical–structural alteration and the reduced recalcitrance in poplar

DOE PAGES

Li, Mi; Cao, Shilin; Meng, Xianzhi; ...

2017-11-30

Hydrothermal pretreatment using liquid hot water (LHW) is capable of substantially reducing the cell wall recalcitrance of lignocellulosic biomass. It enhances the saccharification of polysaccharides, particularly cellulose, into glucose with relatively low capital required. Due to the close association with biomass recalcitrance, the structural change of the components of lignocellulosic materials during the pretreatment is crucial to understand pretreatment chemistry and advance the bio-economy. Although the LHW pretreatment has been extensively applied and studied, the molecular structural alteration during pretreatment and its significance to reduced recalcitrance have not been well understood.

Groundwater and porewater as major sources of alkalinity to a fringing coral reef lagoon (Muri Lagoon, Cook Islands)

NASA Astrophysics Data System (ADS)

Cyronak, T.; Santos, I. R.; Erler, D. V.; Eyre, B. D.

2013-04-01

To better predict how ocean acidification will affect coral reefs, it is important to understand how biogeochemical cycles on reefs alter carbonate chemistry over various temporal and spatial scales. This study quantifies the contribution of shallow porewater exchange (as quantified from advective chamber incubations) and fresh groundwater discharge (as traced by 222Rn) to total alkalinity (TA) dynamics on a fringing coral reef lagoon along the southern Pacific island of Rarotonga over a tidal and diel cycle. Benthic alkalinity fluxes were affected by the advective circulation of water through permeable sediments, with net daily flux rates of carbonate alkalinity ranging from -1.55 to 7.76 mmol m-2 d-1, depending on the advection rate. Submarine groundwater discharge (SGD) was a source of TA to the lagoon, with the highest flux rates measured at low tide, and an average daily TA flux of 1080 mmol m-2 d-1 at the sampling site. Both sources of TA were important on a reef-wide basis, although SGD acted solely as a delivery mechanism of TA to the lagoon, while porewater advection was either a sink or source of TA dependent on the time of day. This study describes overlooked sources of TA to coral reef ecosystems that can potentially alter water column carbonate chemistry. We suggest that porewater and groundwater fluxes of TA should be taken into account in ocean acidification models in order to properly address changing carbonate chemistry within coral reef ecosystems.

Evaluation of a reduced centrifugation time and higher centrifugal force on various general chemistry and immunochemistry analytes in plasma and serum.

PubMed

Møller, Mette F; Søndergaard, Tove R; Kristensen, Helle T; Münster, Anna-Marie B

2017-09-01

Background Centrifugation of blood samples is an essential preanalytical step in the clinical biochemistry laboratory. Centrifugation settings are often altered to optimize sample flow and turnaround time. Few studies have addressed the effect of altering centrifugation settings on analytical quality, and almost all studies have been done using collection tubes with gel separator. Methods In this study, we compared a centrifugation time of 5 min at 3000 ×  g to a standard protocol of 10 min at 2200 ×  g. Nine selected general chemistry and immunochemistry analytes and interference indices were studied in lithium heparin plasma tubes and serum tubes without gel separator. Results were evaluated using mean bias, difference plots and coefficient of variation, compared with maximum allowable bias and coefficient of variation used in laboratory routine quality control. Results For all analytes except lactate dehydrogenase, the results were within the predefined acceptance criteria, indicating that the analytical quality was not compromised. Lactate dehydrogenase showed higher values after centrifugation for 5 min at 3000 ×  g, mean bias was 6.3 ± 2.2% and the coefficient of variation was 5%. Conclusions We found that a centrifugation protocol of 5 min at 3000 ×  g can be used for the general chemistry and immunochemistry analytes studied, with the possible exception of lactate dehydrogenase, which requires further assessment.

Associations of stream health to altered flow and water temperature in the Sierra Nevada, California

USGS Publications Warehouse

Carlisle, Daren M.; S. Mark Nelson,; May, Jason

2016-01-01

Alteration of streamflow and thermal conditions may adversely affect lotic invertebrate communities, but few studies have assessed these phenomena using indicators that control for the potentially confounding influence of natural variability. We designed a study to assess how flow and thermal alteration influence stream health – as indicated by the condition of invertebrate communities. We studied thirty streams in the Sierra Nevada, California, that span a wide range of hydrologic modification due to storage reservoirs and hydroelectric diversions. Daily water temperature and streamflows were monitored, and basic chemistry and habitat conditions were characterized when invertebrate communities were sampled. Streamflow alteration, thermal alteration, and invertebrate condition were quantified by predicting site-specific natural expectations using statistical models developed using data from regional reference sites. Monthly flows were typically depleted (relative to natural expectations) during fall, winter, and spring. Most hydrologically altered sites experienced cooled thermal conditions in summer, with mean daily temperatures as much 12 °C below natural expectations. The most influential predictor of invertebrate community condition was the degree of alteration of March flows, which suggests that there are key interactions between hydrological and biological processes during this month in Sierra Nevada streams. Thermal alteration was also an important predictor – particularly at sites with the most severe hydrological alteration.

Transmission electron microscope analyses of alteration phases in martian meteorite MIL 090032

NASA Astrophysics Data System (ADS)

Hallis, L. J.; Ishii, H. A.; Bradley, J. P.; Taylor, G. J.

2014-06-01

The nakhlite group of martian meteorites found in the Antarctic contain varying abundances of both martian and terrestrial secondary alteration phases. The aim of this study was to use transmission electron microscopy (TEM) to compare martian and terrestrial alteration embodied within a single nakhlite martian meteorite find - MIL 090032. Martian alteration veins in MIL 090032 are composed of poorly ordered Fe-smectite phyllosilicate. This poorly-ordered smectite appears to be equivalent to the nanocrystalline phyllosilicate/hydrated amorphous gel phase previously described in the martian alteration veins of other nakhlites. Chemical differences in this nanocrystalline phyllosilicate between different nakhlites imply localised alteration, which occurred close to the martian surface in MIL 090032. Both structurally and compositionally the nakhlite nanocrystalline phyllosilicate shows similarities to the amorphous/poorly ordered phase recently discovered in martian soil by the Mars Curiosity Rover at Rocknest, Gale Crater. Terrestrially derived alteration phases in MIL 090032 include jarosite and gypsum, amorphous silicates, and Fe-oxides and hydroxides. Similarities between the mineralogy and chemistry of the MIL 090032 terrestrial and martian alteration phases suggest the alteration conditions on Mars were similar to those in the Antarctic. At both sites a small amount of fluid at low temperatures infiltrated the rock and became acidic as a result of the conversion of Fe2+ to Fe3+ under oxidising conditions.

Feedbacks between Air-Quality, Meteorology, and the Forest Environment

NASA Astrophysics Data System (ADS)

Makar, Paul; Akingunola, Ayodeji; Stroud, Craig; Zhang, Junhua; Gong, Wanmin; Moran, Michael; Zheng, Qiong; Brook, Jeffrey; Sills, David

2017-04-01

The outcome of air quality forecasts depend in part on how the local environment surrounding the emissions regions influences chemical reaction rates and transport from those regions to the larger spatial scales. Forested areas alter atmospheric chemistry through reducing photolysis rates and vertical diffusivities within the forest canopy. The emitted pollutants, and their reaction products, are in turn capable of altering meteorology, through the well-known direct and indirect effects of particulate matter on radiative transfer. The combination of these factors was examined using version 2 of the Global Environmental Multiscale - Modelling Air-quality and CHemistry (GEM-MACH) on-line air pollution model. The model configuration used for this study included 12 aerosol size bins, eight aerosol species, homogeneous core Mie scattering, the Milbrandt-Yao two-moment cloud microphysics scheme with cloud condensation nuclei generated from model aerosols using the scheme of Abdul-Razzak and Ghan, and a new parameterization for forest canopy shading and turbulence. The model was nested to 2.5km resolution for a domain encompassing the lower Great Lakes, for simulations of a period in August of 2015 during the Pan American Games, held in Toronto, Canada. Four scenarios were carried out: (1) a "Base Case" scenario (the original model, in which coupling between chemistry and weather is not permitted; instead, the meteorological model's internal climatologies for aerosol optical and cloud condensation properties are used for direct and indirect effect calculations); (2) a "Feedback" scenario (the aerosol properties were derived from the internally simulated chemistry, and coupled to the meteorological model's radiative transfer and cloud formation modules); (3) a "Forest" scenario (canopy shading and turbulence were added to the Base Case); (4) a "Combined" scenario (including both direct and indirect effect coupling between meteorology and chemistry, as well as the forest canopy parameterization). The simulations suggest that the feedbacks between simulated aerosols and meteorology may strengthen the existing lake breeze circulation, modifying the resulting meteorological and air-quality forecasts, while the forest canopy's influence may extend throughout the planetary boundary layer, and may also influence the weather. The simulations will be compared to available observations, in order to determine their relative impact on model performance.

Characterization of seepage in the exploratory studies facility, Yucca Mountain, Nevada

USGS Publications Warehouse

Oliver, T.A.; Whelan, J.F.

2006-01-01

Following a 5-month period of above-average precipitation during the winter of 2004-2005, water was observed seeping into the South Ramp section of the Exploratory Studies Facility of the proposed repository for high-level radioactive waste at Yucca Mountain, Nevada. Samples of the seepage were collected and analyzed for major ions, trace metals, and delta deuterium and delta oxygen-18 values in an effort to characterize the water and assess the interaction of seepage with anthropogenic materials used in the construction of the proposed repository. As demonstrated by the changes in the chemistry of water dripping from a rock bolt, interaction of seepage with construction materials can alter solution chemistry and oxidation state.

Geology and geochemistry of the Arctic prospect, Ambler District, Alaska

NASA Astrophysics Data System (ADS)

Schmidt, J. M.

The Arctic volcanogenic massive sulfide prospect is the largest known (40 million ton) deposit hosted by the low greenschist grade, latest Devonian Ambler Sequence of bimodal, basaltic and rhyolitic volcanic and volcanoclastic rocks, pelitic, graphitic and calcareous metasediments. Detailed field mapping, core logging, petrography, X-ray diffractometry, electron microprobe analyses and whole-rock major element analyses of hydrothermally altered rocks were used to determine the emplacement history and setting of sulfide deposition. Low greenschist grade metamorphism was essentially isochemical on a macroscopic scale, and preserved volcanic compositions, the major element chemistry of alteration and the compositions of individual metamorphic, alteration and relict igneous minerals. Mineralization at Arctic was formed along a synvolcanic fault in a tectonically and volcanically active basin within a rifted continental margin, possibly related to an actively spreading oceanic rift.

Chemistry Practical Lessons: Altering Traditions for Students' Emancipation

ERIC Educational Resources Information Center

Nhalevilo, Emilia Afonso

2012-01-01

This paper is a response to Maria Andree's paper. Andree tells in the paper how mistakes in practical lessons may be critical events to change students' attitudes in regard science. While traditionally mistakes in practical lessons could obligate students to repeat the experiment in order to get the "right result" in the paper we have a good…

Fungal communities and functional guilds shift along an elevational gradient in the southern Appalachian Mountains

Treesearch

Allison M. Veach; C. Elizabeth Stokes; Jennifer Knoepp; Ari Jumpponen; Richard Baird

2017-01-01

Nitrogen deposition alters forest ecosystems particularly in high elevation, montane habitats where nitrogen deposition is greatest and continues to increase. We collected soils across an elevational (788–1940 m) gradient, encompassing both abiotic (soil chemistry) and biotic (vegetation community) gradients, at eight locations in the southern Appalachian...

Dendroecological applications in air pollution and environmental chemistry: research needs

Treesearch

Samuel B. McLaughlin; Walter C. Shortle; Kevin T. Smith

2002-01-01

During the past two decades, dendrochronology has evolved in new dimensions that have helped address both the extent and causes of impacts of regional scale environmental pollution on the productivity and function of forest ecosystems. Initial focus on the magnitude and timing of alterations of baseline growth levels of individual forest trees has now broadened to...

Effects of elevated CO2 leaf diet on gypsy moth (Lepidoptera: Lymantriidae) respiration rates

Treesearch

Anita R. Foss; William J. Mattson; Terry M. Trier

2013-01-01

Elevated levels of CO2 affect plant growth and leaf chemistry, which in turn can alter host plant suitability for insect herbivores. We examined the suitability of foliage from trees grown from seedlings since 1997 at Aspen FACE as diet for the gypsy moth (Lymantria dispar L.) Lepidoptera: Lymantriidae: paper birch (...

Effects of genotype, elevated CO2 and elevated O3 on aspen phytochemistry and aspen leaf beetle Chrysomela crotchi performance

Treesearch

Leanne M. Vigue; Richard L. Lindroth

2010-01-01

Trembling aspen Populus tremuloides Michaux is an important forest species in the Great Lakes region and displays tremendous genetic variation in foliar chemistry. Elevated carbon dioxide (CO2) and ozone (O3) may also influence phytochemistry and thereby alter the performance of insect herbivores such as...

Impact of harvesting and atmospheric pollution on nutrient depletion of eastern US hardwood forests

Treesearch

M.B. Adams; J.A. Burger; A.B. Jenkins; L. Zelazny

2000-01-01

The eastern hardwood forests of the US may be threatened by the changing atmospheric chemistry and by changes in harvesting levels. Many studies have documented accelerated base cation losses with intensive forest harvesting. Acidic deposition can also alter nutrient cycling in these forests. The combination of increased harvesting, shorter rotations, and more...

A localized model of spatial cognition in chemistry

NASA Astrophysics Data System (ADS)

Stieff, Mike

This dissertation challenges the assumption that spatial cognition, particularly visualization, is the key component to problem solving in chemistry. In contrast to this assumption, I posit a localized, or task-specific, model of spatial cognition in chemistry problem solving to locate the exact tasks in a traditional organic chemistry curriculum that require students to use visualization strategies to problem solve. Instead of assuming that visualization is required for most chemistry tasks simply because chemistry concerns invisible three-dimensional entities, I instead use the framework of the localized model to identify how students do and do not make use of visualization strategies on a wide variety of assessment tasks regardless of each task's explicit demand for spatial cognition. I establish the dimensions of the localized model with five studies. First, I designed two novel psychometrics to reveal how students selectively use visualization strategies to interpret and analyze molecular structures. The third study comprised a document analysis of the organic chemistry assessments that empirically determined only 12% of these tasks explicitly require visualization. The fourth study concerned a series of correlation analyses between measures of visuo-spatial ability and chemistry performance to clarify the impact of individual differences. Finally, I performed a series of micro-genetic analyses of student problem solving that confirmed the earlier findings and revealed students prefer to visualize molecules from alternative perspectives without using mental rotation. The results of each study reveal that occurrences of sophisticated spatial cognition are relatively infrequent in chemistry, despite instructors' ostensible emphasis on the visualization of three-dimensional structures. To the contrary, students eschew visualization strategies and instead rely on the use of molecular diagrams to scaffold spatial cognition. Visualization does play a key role, however, in problem solving on a select group of chemistry tasks that require students to translate molecular representations or fundamentally alter the morphology of a molecule. Ultimately, this dissertation calls into question the assumption that individual differences in visuo-spatial ability play a critical role in determining who succeeds in chemistry. The results of this work establish a foundation for defining the precise manner in which visualization tools can best support problem solving.

TESTING THE EFFECTS OF OCEAN ACIDIFICATION ON ALGAL METABOLISM: CONSIDERATIONS FOR EXPERIMENTAL DESIGNS(1).

PubMed

Hurd, Catriona L; Hepburn, Christopher D; Currie, Kim I; Raven, John A; Hunter, Keith A

2009-12-01

Ocean acidification describes changes in the carbonate chemistry of the ocean due to the increased absorption of anthropogenically released CO2 . Experiments to elucidate the biological effects of ocean acidification on algae are not straightforward because when pH is altered, the carbon speciation in seawater is altered, which has implications for photosynthesis and, for calcifying algae, calcification. Furthermore, photosynthesis, respiration, and calcification will themselves alter the pH of the seawater medium. In this review, algal physiologists and seawater carbonate chemists combine their knowledge to provide the fundamental information on carbon physiology and seawater carbonate chemistry required to comprehend the complexities of how ocean acidification might affect algae metabolism. A wide range in responses of algae to ocean acidification has been observed, which may be explained by differences in algal physiology, timescales of the responses measured, study duration, and the method employed to alter pH. Two methods have been widely used in a range of experimental systems: CO2 bubbling and HCl/NaOH additions. These methods affect the speciation of carbonate ions in the culture medium differently; we discuss how this could influence the biological responses of algae and suggest a third method based on HCl/NaHCO3 additions. We then discuss eight key points that should be considered prior to setting up experiments, including which method of manipulating pH to choose, monitoring during experiments, techniques for adding acidified seawater, biological side effects, and other environmental factors. Finally, we consider incubation timescales and prior conditioning of algae in terms of regulation, acclimation, and adaptation to ocean acidification. © 2009 Phycological Society of America.

Alteration mineralogy, mineral chemistry and stable isotope geochemistry of the Eocene pillow lavas from the Trabzon area, NE Turkey

NASA Astrophysics Data System (ADS)

Abdioğlu Yazar, Emel

2018-02-01

The Eocene subaqueous volcanic units in NE Turkey developed as pillow, closely packed pillow, isolated pillow, pillow breccia, hyaloclastite breccia and rare peperitic facies with red micritic limestones. They are locally set on volcaniclastic sandstone and claystone alternations and gradually pass to tuffs and volcanic breccias. The pillow lava samples generally exhibit intersertal, intergranular, microlitic porphyritic, variolitic, vesicular and glomeroporphyritic and glassy textures with clinopyroxene (Wo47-52En40-45Fs6-8), plagioclase (An10 to An96), olivine (Fo79-87) and Fe-Ti oxides (Usp0-0.27). Saponite, interlayered chlorite/saponite, rare beidellite and calcite were determined after olivine, rarely after plagioclase as well as in the glassy groundmass. Illite was restricted to plagioclase and the glassy groundmass. Na-Ca zeolites, chlorites/saponites, beidellite, dolomite and calcite occur as void infillings and in the glassy groundmass. Mineralogical, lithochemical and isotopic interpretations as well as thermometric calculations reveal a low-temperature seawater alteration in a semi-closed environment for the alteration of primary minerals and volcanic glass in addition to sealed vesicles and open systems for crosscutting veins. Due to the short exposure time intervals of seawater to rocks, the total chemistry of the rocks is not fully changed and most of the elements seem to be immobile, remaining in the system as a result of precipitation in voids and cracks. Thermometric estimations indicate that, the temperature of heated seawater is approximately 160 °C at the highest point especially in the vesicles, and decreases to approximately 85 °C due to circulation, resulting in alterations of the primary phases and volcanic glass.

Characterizing Martian Soils: Correlating Orbital Observations with Chemistry and Mineralogy from Landed Missions

NASA Astrophysics Data System (ADS)

Bishop, J. L.

2010-12-01

Great advances have been achieved recently in our understanding of the surface of Mars at global scales from orbital missions and at local scales from landed missions. This presentation seeks to provide links between the chemistry and mineralogy observed by landed missions with remote detections of minerals from orbit. Spectral data from CRISM, OMEGA and TES characterize a mostly basaltic planet with some outcrops of hematite, clays, sulfates and carbonates at the surface. Recent alteration of these rocks to form soils has likely been dominated by physical processes; however, martian soils probably also contain relicts of early alteration involving aqueous processes. Clays, hydroxides, sulfates, carbonates and perchlorates are examples of surface components that may have formed early in the planet’s history in the presence of liquid water. Some of these minerals have not been detected in the soil, but all have likely contributed to the current soil composition. The grain size, shape, chemistry, mineralogy, and magnetic properties of Martian soils are similar to altered volcanic ash found at many analog sites on Earth. Reflectance and emission spectra of some of these analog soils are consistent with the basic soil spectral properties observed from orbit. The cemented soil units observed by rovers may have formed through interaction of the soil grains with salts, clays, and hydroxides. Lab experiments have shown that cementing of analog grains darkens the VN reflectance, which could explain the low reflectance of Martian soils compared to analog sites. Reflectance spectra of an analog soil mixture containing altered ash and sulfate are shown in Figure 1. A pellet was made by adding water and allowing the sample to dry in air. Finally, the pellet was crushed and ground again to <125 µm. Both the dried pellet spectrum and the crushed pellet spectrum are darker than the original spectrum of the same composition. Erosion and weathering are likely the dominant processes forming the soils on Mars. However, reaction of surface grains with sulfates and perchlorates probably also influenced the soil grains. The perchlorates found by Phoenix are a strong oxidant. Consideration is being given to the interactions of perchlorates with minerals identified in surface rocks (pyroxene, olivine, feldspar, phyllosilicate, iron oxides, sulfate, silica, carbonate) and how perchlorates might be contributing to soil formation from these minerals and what their spectral properties might be.

Portable Diagnostics and Rapid Germination

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

Dunn, Zachary Spencer

In the Bioenergy and Defense Department of Sandia National Laboratories, characterization of the BaDx (Bacillus anthracis diagnostic cartridge) was performed and rapid germination chemistry was investigated. BaDx was tested with complex sample matrixes inoculated with Bacillus anthracis, and the trials proved that BaDx will detect Bacillus anthracis in a variety of the medium, such as dirt, serum, blood, milk, and horse fluids. The dimensions of the device were altered to accommodate an E. coli or Listeria lateral flow immunoassay, and using a laser printer, BaDx devices were manufactured to identify E. coli and Listeria. Initial testing with E. coli versionsmore » of BaDx indicate that the device will be viable as a portable diagnostic cartridge. The device would be more effective with faster bacteria germination; hence studies were performed the use of rapid germination chemistry. Trials with calcium dipicolinic acid displayed increased cell germination, as shown by control studies using a microplate reader. Upon lyophilization the rapid germination chemistry failed to change growth patterns, indicating that the calcium dipicolinic acid was not solubilized under the conditions tested. Although incompatible with the portable diagnostic device, the experiments proved that the rapid germination chemistry was effective in increasing cell germination.« less

The Influence of Phosphor and Binder Chemistry on the Aging Characteristics of Remote Phosphor Products

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

Davis, Lynn; Yaga, Robert; Lamvik, Michael

The influence of phosphor and binder layer chemistries on the lumen maintenance and color stability of remote phosphor disks were examined using wet high-temperature operational lifetime testing (WHTOL). As part of the experimental matrix, two different correlated color temperature (CCT) values, 2700 K and 5000 K, were studied and each had a different binder chemistry. The 2700 K samples used a urethane binder whereas the 5000 K samples used an acrylate binder. Experimental conditions were chosen to enable study of the binder and phosphor chemistries and to minimize photo-oxidation of the polycarbonate substrate. Under the more severe WHTOL conditions ofmore » 85°C and 85% relative humidity (RH), absorption in the binder layer significantly reduced luminous flux and produced a blue color shift. The milder WHTOL conditions of 75°C and 75% RH, resulted in chemical changes in the binder layer that may alter its index of refraction. As a result, lumen maintenance remained high, but a slight yellow shift was found. The aging of remote phosphor products provides insights into the impact of materials on the performance of phosphors in an LED lighting system.« less

Synergistic responses of superficial chemistry and micro topography of titanium created by wire-type electric discharge machining.

PubMed

Kataoka, Yu; Tamaki, Yukimichi; Miyazaki, Takashi

2011-01-01

Wire-type electric discharge machining has been applied to the manufacture of endosseous titanium implants as this computer associated technique allows extremely accurate complex sample shaping with an optimal micro textured surface during the processing. Since the titanium oxide layer is sensitively altered by each processing, the authors hypothesized that this technique also up-regulates biological responses through the synergistic effects of the superficial chemistry and micro topography. To evaluate the respective in vitro cellular responses on the superficial chemistry and micro topography of titanium surface processed by wire-type electric discharge, we used titanium-coated epoxy resin replica of the surface. An oxide layer on the titanium surface processed by wire-type electric discharge activated the initial responses of osteoblastic cells through an integrin-mediated mechanism. Since the mRNA expression of ALP on those replicas was up-regulated compared to smooth titanium samples, the micro topography of a titanium surface processed by wire-type electric discharge promotes the osteogenic potential of cells. The synergistic response of the superficial chemistry and micro topography of titanium processed by wire-type electric discharge was demonstrated in this study.

Compositionally heterogeneous podiform chromitite in the Shetland Ophiolite Complex (Scotland): Implications for chromitite petrogenesis and late-stage alteration in the upper mantle portion of a supra-subduction zone ophiolite

NASA Astrophysics Data System (ADS)

Derbyshire, E. J.; O'Driscoll, B.; Lenaz, D.; Gertisser, R.; Kronz, A.

2013-03-01

The mantle sequence of the ~ 492 Ma Shetland Ophiolite Complex (SOC; Scotland) contains abundant compositionally heterogeneous podiform chromitite bodies enclosed in elongate dunite lenses in the vicinity of the petrological Moho. Chromitite petrogenesis and late-stage alteration events recorded in these seams are examined here using petrography, mineral chemistry and crystal structural data. The resistant nature of Cr-spinel to serpentinisation and other late-stage alteration means that primary igneous compositions are preserved in unaltered crystal cores. Chromitite mineralogy and texture from five sampled localities at The Viels, Hagdale, Harold's Grave, Nikka Vord and Cliff reveal significant inter-pod chemical heterogeneity. The Cr-spinel mineral chemistry is consistent with supra-subduction zone melt extraction from the SOC peridotites. The occurrence of chromitite seams in the centres of the dunite lenses combined with variable Cr-spinel compositions at different chromitite seam localities supports a model of chromitite formation from spatially (and temporally?) fluctuating amounts of melt-rock interaction through channelised and/or porous melt flow. Pervasive serpentinisation of the SOC has led to the almost complete replacement of the primary (mantle) silicate mineral assemblages with serpentine (lizardite with minor chrysotile and antigorite). Magmatic sulphide (e.g., pentlandite) in dunite and chromitite is locally converted to reduced Ni-sulphide varieties (e.g., heazlewoodite and millerite). A post-serpentinisation (prograde) oxidisation event is recorded in the extensively altered Cliff chromitite seams in the west of the studied area, where chromitite Cr-spinel is extensively altered to ferritchromit. The ferritchromit may comprise > 50% of the volume of the Cliff Cr-spinels and contain appreciable quantities of 1-2 μm inclusions of sperrylite (PtAs2) and Ni-arsenide, signifying the coeval formation of these minerals with ferritchromit at temperatures of up to ~ 500 °C. The SOC chromitite Cr-spinels thus not only preserve key insights into the complex melting processes occurring in the upper mantle wedge but can also be utilised to construct a comprehensive alteration history of the lower mantle portions of such supra-subduction zone ophiolites.

Is Nitrogen Deposition Altering the Nitrogen Status of Northeastern Forests?

NASA Astrophysics Data System (ADS)

Aber, J. D.; Goodale, C. L.; Ollinger, S. V.; Smith, M.; Magill, A. H.; Martin, M. E.; Hallett, R. A.; Stoddard, J. L.; Participants, N.

2002-05-01

The nitrogen saturation hypothesis suggests that foliar and soil N concentration, nitrification rate, and nitrate leaching loss should all increase in response to increased N deposition. We tested this hypothesis with a major new synthesis of foliar (362 plots), soil (251 plots), and surface water (354 lakes and streams) chemistry from the northeastern U.S. Nitrogen deposition decreases across the Northeast from ~ 10-12 kg ha-1 yr-1 in the Mid-Atlantic region to ~ 4 kg ha-1 yr-1 in northern Maine. Foliar chemistry (%N and lignin:N ratio) of red spruce and sugar maple correlated more strongly with elevation than with N deposition, although these factors covary. Forest floor C:N ratio decreased with N deposition for both conifers and hardwoods although correlations were not strong (R2 < 0.20). Regardless of forest type or soil horizon, percent nitrification (as a fraction of N mineralization) increased as soil C:N decreased below ~25, and increased weakly with N deposition in hardwood stands. Across the Northeast, surface water seasonal nitrate concentrations and N export during the mid- to late-1990s increased with N deposition (R2 = 0.30-0.56), with two important patterns emerging: 1) nitrate rarely exceeded 1 μ mol/L in watersheds receiving <8-10 kg ha-1 yr-1; and 2) high nitrate concentrations occurred only in lakes and streams receiving relatively high N inputs. This pattern resembles that for European forests. Factors such as species composition, forest history, climate, and hydrology may affect foliar, soil, and stream chemistry at different spatial and temporal scales. Foliar and soil chemistry may be more strongly influenced by local heterogeneity, whereas surface water samples integrate over much larger areas. Using surface waters as the most comprehensive indicator of N saturation, it appears that N deposition is altering the N status of forests in the northeastern U.S.

Unconventional Constraints on Nitrogen Chemistry using DC3 Observations and Trajectory-based Chemical Modeling

NASA Astrophysics Data System (ADS)

Shu, Q.; Henderson, B. H.

2017-12-01

Chemical transport models underestimate nitrogen dioxide observations in the upper troposphere (UT). Previous research in the UT succeeded in combining model predictions with field campaign measurements to demonstrate that the nitric acid formation rate (HO + NO2 → HNO3 (R1)) is overestimated by 22% (Henderson et al., 2012). A subsequent publication (Seltzer et al., 2015) demonstrated that single chemical constraint alters ozone and aerosol formation/composition. This work attempts to replicate previous chemical constraints with newer observations and a different modeling framework. We apply the previously successful constraint framework to Deep Convection Clouds and Chemistry (DC3). DC3 is a more recent field campaign where simulated nitrogen imbalances still exist. Freshly convected air parcels, identified in the DC3 dataset, as initial coordinates to initiate Lagrangian trajectories. Along each trajectory, we simulate the air parcel chemical state. Samples along the trajectories will form ensembles that represent possible realizations of UT air parcels. We then apply Bayesian inference to constrain nitrogen chemistry and compare results to the existing literature. Our anticipated results will confirm overestimation of HNO3 formation rate in previous work and provide further constraints on other nitrogen reaction rate coefficients that affect terminal products from NOx. We will particularly focus on organic nitrate chemistry that laboratory literature has yet to fully address. The results will provide useful insights into nitrogen chemistry that affects climate and human health.

Modifying Surface Chemistry of Metal Oxides for Boosting Dissolution Kinetics in Water by Liquid Cell Electron Microscopy.

PubMed

Lu, Yue; Geng, Jiguo; Wang, Kuan; Zhang, Wei; Ding, Wenqiang; Zhang, Zhenhua; Xie, Shaohua; Dai, Hongxing; Chen, Fu-Rong; Sui, Manling

2017-08-22

Dissolution of metal oxides is fundamentally important for understanding mineral evolution and micromachining oxide functional materials. In general, dissolution of metal oxides is a slow and inefficient chemical reaction. Here, by introducing oxygen deficiencies to modify the surface chemistry of oxides, we can boost the dissolution kinetics of metal oxides in water, as in situ demonstrated in a liquid environmental transmission electron microscope (LETEM). The dissolution rate constant significantly increases by 16-19 orders of magnitude, equivalent to a reduction of 0.97-1.11 eV in activation energy, as compared with the normal dissolution in acid. It is evidenced from the high-resolution TEM imaging, electron energy loss spectra, and first-principle calculations where the dissolution route of metal oxides is dynamically changed by local interoperability between altered water chemistry and surface oxygen deficiencies via electron radiolysis. This discovery inspires the development of a highly efficient electron lithography method for metal oxide films in ecofriendly water, which offers an advanced technique for nanodevice fabrication.

Nucleophilic catalysis of acylhydrazone equilibration for protein-directed dynamic covalent chemistry

PubMed Central

Bhat, Venugopal T.; Caniard, Anne M.; Luksch, Torsten; Brenk, Ruth; Campopiano, Dominic J.; Greaney, Michael F.

2010-01-01

Dynamic covalent chemistry uses reversible chemical reactions to set up an equilibrating network of molecules at thermodynamic equilibrium, which can adjust its composition in response to any agent capable of altering the free energy of the system. When the target is a biological macromolecule, such as a protein, the process corresponds to the protein directing the synthesis of its own best ligand. Here, we demonstrate that reversible acylhydrazone formation is an effective chemistry for biological dynamic combinatorial library formation. In the presence of aniline as a nucleophilic catalyst, dynamic combinatorial libraries equilibrate rapidly at pH 6.2, are fully reversible, and may be switched on or off by means of a change in pH. We have interfaced these hydrazone dynamic combinatorial libraries with two isozymes from the glutathione S-transferase class of enzyme, and observed divergent amplification effects, where each protein selects the best-fitting hydrazone for the hydrophobic region of its active site. PMID:20489719

Consequences of enriched atmospheric CO{sub 2} and defoliation for foliar chemistry and gypsy moth performance

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

Lindroth, R.L.; Kinney, K.K.

1998-10-01

Elevated concentrations of atmospheric CO{sub 2} are likely to interact with other factors affecting plant physiology to alter plant chemical profiles and plant-herbivore interactions. The authors evaluated the independent and interactive effects of enriched CO{sub 2} and artificial defoliation on foliar chemistry of quaking aspen (Populus tremuloides) and sugar maple (Acer saccharum), and the consequences of such changes for short-term performance of the gypsy moth (Lymantria dispar). They grew aspen and maple seedlings in ambient and enriched CO{sub 2} environments at the University of wisconsin Biotron. Seven weeks after budbreak, trees in half of the rooms were subjected to 50%more » defoliation. Afterwards, foliage was collected for chemical analyses, and feeding trials were conducted with fourth-stadium gypsy moths. Enriched CO{sub 2} altered foliar levels of water, nitrogen, carbohydrates, and phenolics, and responses generally differed between the two tree species. Defoliation induced chemical changes only in aspen. They found no significant interactions between CO{sub 2} and defoliation for levels of carbon-based defenses (phenolic glycosides and tannins). CO{sub 2} treatment altered the performance of larvae fed aspen, but not maple, whereas defoliation had little effect on performance on insects. In general, results from this experimental system do not support the hypothesis that induction of carbon-based chemical defenses, and attendant effects on insects, will be stronger in a CO{sub 2}-enriched world.« less

The Myszkow porphyry copper-molybdenum deposit, Poland

USGS Publications Warehouse

Chaffee, M.A.; Eppinger, R.G.; Lason, K.; Slosarz, J.; Podemski, M.

1994-01-01

The porphyry copper-molybdenum deposit at Myszkow, south-central Poland, lies in the Cracow-Silesian orogenic belt, in the vicinity of a Paleozoic boundary between two tectonic plates. The deposit is hosted in a complex that includes early Paleozoic metasedimentary rocks intruded in the late Paleozoic by a predominantly granodioritic pluton. This deposit exhibits many features that are typical of porphyry copper deposits associated with calc-alkaline intrusive rocks, including ore- and alteration-mineral suites, zoning of ore and alteration minerals, fluid-inclusion chemistry, tectonic setting, and structural style of veining. Unusual features of the Myszkow deposit include high concentrations of tungsten and the late Paleozoic (Variscan) age. -Authors

Application of geologic map information to water quality issues in the southern part of the Chesapeake Bay watershed, Maryland and Virginia, eastern United States

USGS Publications Warehouse

McCartan, L.; Peper, J.D.; Bachman, L.J.; Horton, J. Wright

1999-01-01

Geologic map units contain much information about the mineralogy, chemistry, and physical attributes of the rocks mapped. This paper presents information from regional-scale geologic maps in Maryland and Virginia, which are in the southern part of the Chesapeake Bay watershed in the eastern United States. The geologic map information is discussed and analyzed in relation to water chemistry data from shallow wells and stream reaches in the area. Two environmental problems in the Chesapeake Bay watershed are used as test examples. The problems, high acidity and high nitrate concentrations in streams and rivers, tend to be mitigated by some rock and sediment types and not by others. Carbonate rocks (limestone, dolomite, and carbonate-cemented rocks) have the greatest capacity to neutralize acidic ground water and surface water in contact with them. Rocks and sediments having high carbon or sulfur contents (such as peat and black shale) potentially contribute the most toward denitrification of ground water and surface water in contact with them. Rocks and sediments that are composed mostly of quartz, feldspar, and light-colored clay (rocks such as granite and sandstone, sediments such as sand and gravel) tend not to alter the chemistry of waters that are in contact with them. The testing of relationships between regionally mapped geologic units and water chemistry is in a preliminary stage, and initial results are encouraging.Geologic map units contain much information about the mineralogy, chemistry, and physical attributes of the rocks mapped. This paper presents information from regional-scale geologic maps in Maryland and Virginia, which are in the southern part of the Chesapeake Bay watershed in the eastern United States. The geologic map information is discussed and analyzed in relation to water chemistry data from shallow wells and stream reaches in the area. Two environmental problems in the Chesapeake Bay watershed are used as test examples. The problems, high acidity and high nitrate concentrations in streams and rivers, tend to be mitigated by some rock and sediment types and not by others. Carbonate rocks (limestone, dolomite, and carbonate-cemented rocks) have the greatest capacity to neutralize acidic ground water and surface water in contact with them. Rocks and sediments having high carbon or sulfur contents (such as peat and black shale) potentially contribute the most toward denitrification of ground water and surface water in contact with them. Rocks and sediments that are composed mostly of quartz, feldspar, and light-colored clay (rocks such as granite and sandstone, sediments such as sand and gravel) tend not to alter the chemistry of waters that are in contact with them. The testing of relationships between regionally mapped geologic units and water chemistry is in a preliminary stage, and initial results are encouraging.

Antagonist effects of calcium on borosilicate glass alteration

NASA Astrophysics Data System (ADS)

Mercado-Depierre, S.; Angeli, F.; Frizon, F.; Gin, S.

2013-10-01

Numerous studies have been conducted on glass and cement durability in contact with water, but very little work to date has focused directly on interactions between the two materials. These interactions are mostly controlled by silicon-calcium reactivity. However, the physical and chemical processes involved remain insufficiently understood to predict the evolution of coupled glass-cement systems used in several industrial applications. Results are reported from borosilicate glass alteration in calcium-rich solutions. Our data show that four distinct behaviors can be expected according to the relative importance of three key parameters: the pH, the reaction progress (short- or long-term alteration) and the calcium concentration. Glass alteration is thus controlled by specific mechanisms depending on the solution chemistry: calcium complexation at the glass surface, precipitation of calcium silicate hydrates (C-S-H) or calcium incorporation in the altered layer. These findings highlight the impact of silicon-calcium interactions on glass durability and open the way for a better understanding of glass-cement mixing in civil engineering applications as well as in nuclear waste storage.

Groundwater and porewater as a major source of alkalinity to a fringing coral reef lagoon (Muri Lagoon, Cook Islands)

NASA Astrophysics Data System (ADS)

Cyronak, T.; Santos, I. R.; Erler, D. V.; Eyre, B. D.

2012-11-01

To better predict how ocean acidification will affect coral reefs, it is important to understand how biogeochemical cycles on reefs alter carbonate chemistry over various temporal and spatial scales. This study quantifies the contribution of fresh groundwater discharge (as traced by radon) and shallow porewater exchange (as quantified from advective chamber incubations) to total alkalinity (TA) dynamics on a fringing coral reef lagoon along the southern Pacific island of Rarotonga over a tidal and diel cycle. Benthic alkalinity fluxes were affected by the advective circulation of water through permeable sediments, with net daily flux rates of carbonate alkalinity ranging from -1.55 to 7.76 mmol m-2 d-1, depending on the advection rate. Submarine groundwater discharge (SGD) was a source of TA to the lagoon, with the highest flux rates measured at low tide, and an average daily TA flux of 1080 mmol m-2 d-1. Both sources of TA were important on a reef wide basis, although SGD acted solely as a delivery mechanism of TA to the lagoon, while porewater advection was either a sink or source of TA dependant on the time of day. On a daily basis, groundwater can contribute approximately 70% to 80% of the TA taken up by corals within the lagoon. This study describes overlooked sources of TA to coral reef ecosystems that can potentially alter water-column carbonate chemistry. We suggest that porewater and groundwater fluxes of TA should be taken into account in ocean acidification models in order to properly address changing carbonate chemistry within coral reef ecosystems.

Hydrothermal Venting at Hinepuia Submarine Volcano, Kermadec Arc: Understanding Magmatic-Hydrothermal Fluid Chemistry

NASA Astrophysics Data System (ADS)

Stucker, Valerie K.; Walker, Sharon L.; de Ronde, Cornel E. J.; Caratori Tontini, Fabio; Tsuchida, Shinji

2017-10-01

The Hinepuia volcanic center is made up of two distinct edifices aligned northwest to southeast, with an active cone complex in the SE. Hinepuia is one of several active volcanoes in the northern segment of the Kermadec arc. Regional magnetic data show no evidence for large-scale hydrothermal alteration at Hinepuia, yet plume data confirm present-day hydrothermal discharge, suggesting that the hydrothermal system may be too young to have altered the host rocks with respect to measurable changes in magnetic signal. Gravity data are consistent with crustal thinning and shallow mantle under the volcanic center. Following the discovery of hydrothermal plumes over Hinepuia, the submersible Shinkai 6500 was used to explore the SE cone and sample hydrothermal fluids. The chemistry of hydrothermal fluids from submarine arc and backarc volcanoes is typically dominated by water-rock interactions and/or magmatic degassing. Chemical analyses of vent fluids show that Hinepuia does not quite fit either traditional model. Moreover, the Hinepuia samples fall between those typically ascribed to both end-member fluid types when plotted on a K-Mg-SO4 ternary diagram. Due to evidence of strong degassing, abundant native sulfur deposition, and H2S presence, the vent sampled at Hinepuia is ultimately classified as a magmatic-hydrothermal system with a water-rock influence. This vent is releasing water vapor and magmatic volatiles with a notable lack of salinity due to subcritical boiling and phase separation. Magmatic-hydrothermal fluid chemistry appears to be controlled by a combination of gas flux, phase separation processes, and volcano evolution and/or distance from the magma source.

Abiotic Organic Chemistry in Hydrothermal Systems.

NASA Astrophysics Data System (ADS)

Simoneit, B. R.; Rushdi, A. I.

2004-12-01

Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

Performance of high temperature heat flux plates and soil moisture probes during controlled surface fires

Treesearch

W. J. Massman; J. M. Frank; S. M. Massman; W. D. Shepperd

2003-01-01

Natural and prescribed fires play an important role in managing and maintaining most ecosystems in the western United States. The high soil temperatures associated with fire influence forests and their ability to regenerate after a fire by altering soil properties and soil chemistry and by killing microbes, plant roots, and seeds. Because prescribed fire is frequently...

CHANGES IN EARTHWORM DENSITY AND COMMUNITY STRUCTURE DURING SECONDARY SUCCESSION IN ABANDONED TROPICAL PASTURES

Treesearch

Xiaoming Zou; Grizelle Gonzalez

1997-01-01

Plant community succession alters the quantity and chemistry of organic inputs to soils. These differences in organic input may trigger changes in soil fertility and fauna1 activity. We examined earthworm density and community structure along a successional sequence of plant communities in abandoned tropical pastures in Puerto Rico. The chronological sequence of these...

Effects of sulfate deposition on pore water dissolved organic carbon, nutrients, and microbial enzyme activities in a northern peatland

Treesearch

L.R. Seifert-Monson; B.H. Hill; R.K. Kolka; T.M. Jicha; L.L. Lehto; C.M. Elonen

2014-01-01

Export of dissolved organic carbon from lakes and streams has increased throughout Europe and North America over the past several decades. One possible cause is altered deposition chemistry; specifically, decreasing sulfate inputs leading to changes in ionic strength and dissolved organic carbon solubility. To further investigate the relationship between deposition...

Organic chemistry on Titan: Surface interactions

NASA Technical Reports Server (NTRS)

Thompson, W. Reid; Sagan, Carl

1992-01-01

The interaction of Titan's organic sediments with the surface (solubility in nonpolar fluids) is discussed. How Titan's sediments can be exposed to an aqueous medium for short, but perhaps significant, periods of time is also discussed. Interactions with hydrocarbons and with volcanic magmas are considered. The alteration of Titan's organic sediments over geologic time by the impacts of meteorites and comets is discussed.

Metal Catalyzed Fusion: Nuclear Active Environment vs. Process

NASA Astrophysics Data System (ADS)

Chubb, Talbot

2009-03-01

To achieve radiationless dd fusion and/or other LENR reactions via chemistry: some focus on environment of interior or altered near-surface volume of bulk metal; some on environment inside metal nanocrystals or on their surface; some on the interface between nanometal crystals and ionic crystals; some on a momentum shock-stimulation reaction process. Experiment says there is also a spontaneous reaction process.

Oral Pyridostigmine Administration in Rats: Effects on Thermoregulation, Clinical Chemistry, and Performance in the Heat

DTIC Science & Technology

1984-01-01

216, 1978. 13. Harris, L.W., D.L. Stitcher , and W.C. Heyl, The effects of pretreatment with carbamates, atropine and nacamylamine an survival and on...scman-induced- alterations in rat and rabbit brain acetylcholine. Life Sci. 26:1885-1891, 1980. 14. Harris, L.W., D.L. Stitcher , W.C. Heyl, C.N. Lieske

Influences of N-fixing and non-N-fixing vegetation and invasive fish on water chemistry of Hawaiian anchialine ponds

Treesearch

B. D. Dudley; Richard MacKenzie; T. S. Sakihara; H. Dulaiova; C. A. Waters; Flint Hughes; R. Ostertag

2014-01-01

In coastal waters, it remains unclear how terrestrial invasive species might alter nutrient availability and thus affect bottom-up control of primary production. Anchialine ponds are tidal- and groundwater-fed coastal water bodies without surface connections that provide convenient model systems in which to examine terrestrial to aquatic nutrient flow. To investigate...

Leaf litter processing in West Virginia mountain streams: effects of temperature and stream chemistry

Treesearch

Jacquelyn M. Rowe; William B. Perry; Sue A. Perry

1996-01-01

Climate change has the potential to alter detrital processing in headwater streams, which receive the majority of their nutrient input as terrestrial leaf litter. Early placement of experimental leaf packs in streams, one month prior to most abscission, was used as an experimental manipulation to increase stream temperature during leaf pack breakdown. We studied leaf...

Oleoresin, Chemistry and Spectral Reflectance in "Stressed" Lodgepole and White Bark Pine, Mammoth Mountain, California

NASA Technical Reports Server (NTRS)

Hickey, James C.; Birnie, Richard W.; Zhao, Mei-Xun

2001-01-01

Development of methods to identify the physical and chemical character of materials on the earth's surface is one of the foci of hyperspectral remote sensing activities. Enhancing the ability to elucidate changes in foliar chemistry that relate to the health of a plant is a benefit to plant physiologists, foresters, and plant ecologists, as well as geologist and environmental scientists. Vegetation covers the landscape throughout the temperate and tropical regions of the earth. The existence of vegetation in these areas presents special problems to remote sensing systems since geologic bedrock and alteration zones are masked. At times, however, alterations in the soil/sediment geochemical environment result in foliar chemical changes that are detectable via remote sensing. Examples include monitoring of chlorophyll reflectance/fluorescence and equivalent water thickness indices as indicators of drought-induced plant stress. Another processing and interpretation approach used with hyperspectral data has been principal components analysis (PCA). Rowan et al. used PCA to identify absorption feature patterns obtained from vegetated areas with discrete bedrock geology or mineralization as the substrate. Many researchers highlight the need to advance our ability for hyperspectral imaging in vegetated areas as a near-term priority.

Laser-assisted generation of periodic structures on a steel surface: A method for increasing microhardness

NASA Astrophysics Data System (ADS)

Razi, Sepehr; Ghasemi, Fatemeh

2018-02-01

Stainless steel grade 316L is a commonly used metal in various industrial applications because of its excellent resistance to corrosion and great welding and biocompatibility characteristics. Here, the laser-induced micro/nanostructures generation on the steel surface is investigated. A femtosecond ultrashort pulsed laser is selected in this regard, and various irradiation circumstances are considered for two groups of specimens possessing different initial roughness. It turns out that regular periodic ripples with spatial periodicities less than the laser wavelength are generated on both groups at irradiation fluences ≤ 2 J/cm2. Furthermore, it figures out that each ripple is composed of the closely created nano dimension structures. Vickers micro-hardness test is also utilized to examine the alterations of the surface hardness features. Moreover, variations of the surface chemistry are studied and discussions related to the most effective factors in surface hardness raise/decrease are presented. Results reveal the potential benefits of the femtosecond laser technique, such as its flexibility and ease of implementation in controlled modification of the surface features. Thus, it might be of interest to manufacturers looking for precise surface morphology, chemistry and hardness alterations.

Setting up a probe based, closed tube real-time PCR assay for focused detection of variable sequence alterations.

PubMed

Becságh, Péter; Szakács, Orsolya

2014-10-01

During diagnostic workflow when detecting sequence alterations, sometimes it is important to design an algorithm that includes screening and direct tests in combination. Normally the use of direct test, which is mainly sequencing, is limited. There is an increased need for effective screening tests, with "closed tube" during the whole process and therefore decreasing the risk of PCR product contamination. The aim of this study was to design such a closed tube, detection probe based screening assay to detect different kind of sequence alterations in the exon 11 of the human c-kit gene region. Inside this region there are variable possible deletions and single nucleotide changes. During assay setup, more probe chemistry formats were screened and tested. After some optimization steps the taqman probe format was selected.

Utilizing formative evaluation to enhance the understanding of chemistry and the methods and procedures of science

NASA Astrophysics Data System (ADS)

Pizzini, Edward L.; Treagust, David F.; Cody, John

The purpose of this study was to determine whether or not formative evaluation could facilitate goal attainment in a biochemistry course and produce desired learning outcomes consistently by altering course materials and/or instruction. Formative evaluation procedures included the administration of the Inorganic-Organic-Biological Chemistry Test Form 1974 and the Methods and Procedures of Science test to course participants over three consecutive years. A one group pretest-post-test design was used. The statistical analysis involved the use of the Wilcoxon matched-pairs signed-ranks test. The study involved 64 participants. The findings indicate that the use of formative evaluation can be effective in producing desired learning outcomes to facilitate goal attainment.

Nanochemistry of Protein-Based Delivery Agents

PubMed Central

Rajendran, Subin R. C. K.; Udenigwe, Chibuike C.; Yada, Rickey Y.

2016-01-01

The past decade has seen an increased interest in the conversion of food proteins into functional biomaterials, including their use for loading and delivery of physiologically active compounds such as nutraceuticals and pharmaceuticals. Proteins possess a competitive advantage over other platforms for the development of nanodelivery systems since they are biocompatible, amphipathic, and widely available. Proteins also have unique molecular structures and diverse functional groups that can be selectively modified to alter encapsulation and release properties. A number of physical and chemical methods have been used for preparing protein nanoformulations, each based on different underlying protein chemistry. This review focuses on the chemistry of the reorganization and/or modification of proteins into functional nanostructures for delivery, from the perspective of their preparation, functionality, stability and physiological behavior. PMID:27489854

Nanochemistry of protein-based delivery agents

NASA Astrophysics Data System (ADS)

Rajendran, Subin; Udenigwe, Chibuike; Yada, Rickey

2016-07-01

The past decade has seen an increased interest in the conversion of food proteins into functional biomaterials, including their use for loading and delivery of physiologically active compounds such as nutraceuticals and pharmaceuticals. Proteins possess a competitive advantage over other platforms for the development of nanodelivery systems since they are biocompatible, amphipathic, and widely available. Proteins also have unique molecular structures and diverse functional groups that can be selectively modified to alter encapsulation and release properties. A number of physical and chemical methods have been used for preparing protein nanoformulations, each based on different underlying protein chemistry. This review focuses on the chemistry of the reorganization and/or modification of proteins into functional nanostructures for delivery, from the perspective of their preparation, functionality, stability and physiological behavior.

The Growing Human Footprint on Coastal and Open-Ocean Biogeochemistry

NASA Astrophysics Data System (ADS)

Doney, Scott C.

2010-06-01

Climate change, rising atmospheric carbon dioxide, excess nutrient inputs, and pollution in its many forms are fundamentally altering the chemistry of the ocean, often on a global scale and, in some cases, at rates greatly exceeding those in the historical and recent geological record. Major observed trends include a shift in the acid-base chemistry of seawater, reduced subsurface oxygen both in near-shore coastal water and in the open ocean, rising coastal nitrogen levels, and widespread increase in mercury and persistent organic pollutants. Most of these perturbations, tied either directly or indirectly to human fossil fuel combustion, fertilizer use, and industrial activity, are projected to grow in coming decades, resulting in increasing negative impacts on ocean biota and marine resources.

The growing human footprint on coastal and open-ocean biogeochemistry.

PubMed

Doney, Scott C

2010-06-18

Climate change, rising atmospheric carbon dioxide, excess nutrient inputs, and pollution in its many forms are fundamentally altering the chemistry of the ocean, often on a global scale and, in some cases, at rates greatly exceeding those in the historical and recent geological record. Major observed trends include a shift in the acid-base chemistry of seawater, reduced subsurface oxygen both in near-shore coastal water and in the open ocean, rising coastal nitrogen levels, and widespread increase in mercury and persistent organic pollutants. Most of these perturbations, tied either directly or indirectly to human fossil fuel combustion, fertilizer use, and industrial activity, are projected to grow in coming decades, resulting in increasing negative impacts on ocean biota and marine resources.

Role of Integrin Subunits in Mesenchymal Stem Cell Differentiation and Osteoblast Maturation on Graphitic Carbon-coated Microstructured Surfaces

PubMed Central

Olivares-Navarrete, Rene; Rodil, Sandra E.; Hyzy, Sharon L.; Dunn, Ginger R.; Almaguer-Flores, Argelia; Schwartz, Zvi; Boyan, Barbara D.

2015-01-01

Surface roughness, topography, chemistry, and energy promote osteoblast differentiation and increase osteogenic local factor production in vitro and bone-to-implant contact in vivo, but the mechanisms involved are not well understood. Knockdown of integrin heterodimer alpha2beta1 (α2β1) blocks the osteogenic effects of the surface, suggesting signaling by this integrin homodimer is required. The purpose of the present study was to separate effects of surface chemistry and surface structure on integrin expression by coating smooth or rough titanium (Ti) substrates with graphitic carbon, retaining surface morphology but altering surface chemistry. Ti surfaces (smooth [Ra<0.4μm], rough [Ra≥3.4μm]) were sputter-coated using a magnetron sputtering system with an ultrapure graphite target, producing a graphitic carbon thin film. Human mesenchymal stem cells and MG63 osteoblast-like cells had higher mRNA for integrin subunits α1, α2, αv, and β1 on rough surfaces in comparison to smooth, and integrin αv on graphitic-carbon-coated rough surfaces in comparison to Ti. Osteogenic differentiation was greater on rough surfaces in comparison to smooth, regardless of chemistry. Silencing integrins β1, α1, or α2 decreased osteoblast maturation on rough surfaces independent of surface chemistry. Silencing integrin αv decreased maturation only on graphitic carbon-coated surfaces, not on Ti. These results suggest a major role of the integrin β1 subunit in roughness recognition, and that integrin alpha subunits play a major role in surface chemistry recognition. PMID:25770999

Characterizing Normal Groundwater Chemistry in Hawaii

NASA Astrophysics Data System (ADS)

Tachera, D.; Lautze, N. C.; Thomas, D. M.; Whittier, R. B.; Frazer, L. N.

2017-12-01

Hawaii is dependent on groundwater resources, yet how water moves through the subsurface is not well understood in many locations across the state. As marine air moves across the islands water evaporates from the ocean, along with trace amounts of sea-salt ions, and interacts with the anthropogenic and volcanic aerosols (e.g. sulfuric acid, ammonium sulfate, HCl), creating a slightly more acidic rain. When this rain falls, it has a chemical signature distinctive of past processes. As this precipitation infiltrates through soil it may pick up another distinctive chemical signature associated with land use and degree of soil development, and as it flows through the underlying geology, its chemistry is influenced by the host rock. We are currently conducting an investigation of groundwater chemistry in selected aquifer areas of Hawaii, having diverse land use, land cover, and soil development conditions, in an effort to investigate and document what may be considered a "normal" water chemistry for an area. Through this effort, we believe we better assess anomalies due to contamination events, hydrothermal alteration, and other processes; and we can use this information to better understand groundwater flow direction. The project has compiled a large amount of precipitation, soil, and groundwater chemistry data in the three focus areas distributed across in the State of Hawaii. Statistical analyses of these data sets will be performed in an effort to determine what is "normal" and what is anomalous chemistry for a given area. Where possible, results will be used to trace groundwater flow paths. Methods and preliminary results will be presented.

Abnormal brain chemistry in chronic back pain: an in vivo proton magnetic resonance spectroscopy study.

PubMed

Grachev, I D; Fredrickson, B E; Apkarian, A V

2000-12-15

The neurobiology of chronic pain, including chronic back pain, is unknown. Structural imaging studies of the spine cannot explain all cases of chronic back pain. Functional brain imaging studies indicate that the brain activation patterns are different between chronic pain patients and normal subjects, and the thalamus, and prefrontal and cingulate cortices are involved in some types of chronic pain. Animal models of chronic pain suggest abnormal spinal cord chemistry. Does chronic pain cause brain chemistry changes? We examined brain chemistry changes in patients with chronic back pain using in vivo single- voxel proton magnetic resonance spectroscopy ((1)H-MRS). In vivo (1)H-MRS was used to measure relative concentrations of N-acetyl aspartate, creatine, choline, glutamate, glutamine, gamma-aminobutyric acid, inositol, glucose and lactate in relation to the concentration of creatine. These measurements were performed in six brain regions of nine chronic low back pain patients and 11 normal volunteers. All chronic back pain subjects underwent clinical evaluation and perceptual measures of pain and anxiety. We show that chronic back pain alters the human brain chemistry. Reductions of N-acetyl aspartate and glucose were demonstrated in the dorsolateral prefrontal cortex. Cingulate, sensorimotor, and other brain regions showed no chemical concentration differences. In chronic back pain, the interrelationship between chemicals within and across brain regions was abnormal, and there was a specific relationship between regional chemicals and perceptual measures of pain and anxiety. These findings provide direct evidence of abnormal brain chemistry in chronic back pain, which may be useful in diagnosis and future development of more effective pharmacological treatments.

The Toxicity of Depleted Uranium

PubMed Central

Briner, Wayne

2010-01-01

Depleted uranium (DU) is an emerging environmental pollutant that is introduced into the environment primarily by military activity. While depleted uranium is less radioactive than natural uranium, it still retains all the chemical toxicity associated with the original element. In large doses the kidney is the target organ for the acute chemical toxicity of this metal, producing potentially lethal tubular necrosis. In contrast, chronic low dose exposure to depleted uranium may not produce a clear and defined set of symptoms. Chronic low-dose, or subacute, exposure to depleted uranium alters the appearance of milestones in developing organisms. Adult animals that were exposed to depleted uranium during development display persistent alterations in behavior, even after cessation of depleted uranium exposure. Adult animals exposed to depleted uranium demonstrate altered behaviors and a variety of alterations to brain chemistry. Despite its reduced level of radioactivity evidence continues to accumulate that depleted uranium, if ingested, may pose a radiologic hazard. The current state of knowledge concerning DU is discussed. PMID:20195447

Source water controls on the character and origin of dissolved organic matter in streams of the Yukon River basin, Alaska

Treesearch

Jonathan A. O' Donnell; George R. Aiken; Evan S. Kane; Jeremy B. Jones

2010-01-01

Climate warming and permafrost degradation at high latitudes will likely impact watershed hydrology, and consequently, alter the concentration and character of dissolved organic carbon (DOC) in northern rivers. We examined seasonal variation of DOC chemistry in 16 streams of the Yukon River basin, Alaska. Our primary objective was to evaluate DOC chemical composition....

Carbon stocks in urban forest remnants: Atlanta and Baltimore as case studies. Chapter 5.

Treesearch

Ian D. Yesilonis; Richard V. Pouyat

2012-01-01

Urban environments influence carbon (C) and nitrogen (N) cycles of forest ecosystems by altering plant biomass, litter mass and chemistry, passive and active pools of C and N, and the occurrence and activity of decomposer organisms. It is difficult to determine the net effect of C storage due to the number of environmental factors exerting stress on urban forests....

Tundra fire alters stream water chemistry and benthic invertebrate communities, North Slope, Alaska

NASA Astrophysics Data System (ADS)

Allen, A. R.; Bowden, W. B.; Kling, G. W.; Schuett, E.; Kostrzewski, J. M.; Kolden Abatzoglou, C.; Findlay, R. H.

2010-12-01

Increased fire frequency and severity are potentially important consequences of climate change in high latitude ecosystems. The 2007 Anaktuvuk River fire, which burned from July until October, is the largest recorded tundra fire from Alaska's north slope (≈1,000 km2). The immediate effects of wildfire on water chemistry and biotic assemblages in tundra streams are heretofore unknown. We hypothesized that a tundra fire would increase inorganic nutrient inputs to P-limited tundra streams, increasing primary production and altering benthic macroinvertebrate community structure. We examined linkages among: 1) percentage of riparian zone and overall watershed vegetation burned, 2) physical, chemical and biological stream characteristics, and 3) macroinvertebrate communities in streams draining burned and unburned watersheds during the summers of 2008 and 2009. Streams in burned watersheds contained higher mean concentrations of soluble reactive phosphorus (SRP), ammonium (NH4+), and dissolved organic carbon (DOC). In contrast, stream nitrate (NO3-) concentrations were lower in burned watersheds. The net result was that the tundra fire did not affect concentrations of dissolved inorganic nitrogen (NH4+ + NO3-). In spite of increased SRP, benthic chlorophyll-a biomass was not elevated. Macroinvertebrate abundances were 1.5 times higher in streams draining burned watersheds; Chironomidae midges, Nematodes, and Nemoura stoneflies showed the greatest increases in abundance. Multivariate multiple regression identified environmental parameters associated with the observed changes in the macroinvertebrate communities. Since we identified stream latitude as a significant predictor variable, latitude was included in the model as a covariate. After removing the variation associated with latitude, 67.3 % of the variance in macroinvertebrate community structure was explained by a subset of 7 predictor variables; DOC, conductivity, mean temperature, NO3-, mean discharge, SRP and NH4+. The percentage of riparian vegetation burned, the percentage of watershed vegetation burned and total suspended solids were not included in the model as these parameters correlated with DOC concentration at r > 0.90. These results indicate that tundra fire not only alters stream water chemistry, it also affects benthic macroinvertebrate community structure.

Do biofilms and clays alter the chemistry and fabric of a hyper-alklaine, saline, non-marine carbonate precipitate?

NASA Astrophysics Data System (ADS)

Rogerson, Michael; Saunders, Paul; Mercedes-Martin, Ramon; Brasier, Alex; Pedley, Martyn

2015-04-01

Non-marine carbonates comprise a hugely diverse family of deposits, which reflect a constellation of forcing factors from local hydraulics to regional climatology. However, the two dominant controls on precipitation are solution chemistry and benthic microbial biogeochemistry. Here, we present a unifying concept for understanding how these controls influence deposit characteristics, and re-emphasise the importance of biofilms. It is generally accepted that biofilms play an important part in the precipitation of authigenic minerals in a wide variety of settings. In carbonate settings, biofilms are recognised to increase the amount of calcite precipitation and alter the geometry and coarse scale petrography of the precipitate. They determine at what water marginal water chemistries calcite starts to precipitate and microbialites give way to chemical limestones. Biofilms also interact with ambient water, controlling chemical accumulation transport. New evidence, drawn from unique experimental approaches, is demonstrating that biofilm influence extends to control of calcite trace element composition, and crystal scale fabric. Under tightly controlled temperature and chemical conditions, fully replicated experiments show that Mg incorporation into tufa carbonate defies the expected thermodynamic control. However, there is a pronounced influence on (Mg/Ca)calcite from precipitation rate, so that rapidly forming precipitates develop with very low magnesium content indicating kinetic control on fractionation. Calcite precipitation rate in these experiments is controlled by biofilm growth rate and reflects kinetic fractionation arises from the electrochemical activity of extracellular organic acids. These effects are therefore likely to occur wherever these molecules occur, including stromatolites, soil and lake carbonates and (via colloidal organic acids) speleothems. The presence of Extracellular polymeric substances (EPS), even without the presence of cells, also alters precipitation style. Spherular and shrubby calcite growths are well known from the geological record, but their environmental significance is not clear. Sterile, microcosm experiments have shown that these forms occur in saline, hyperalkaline settings ' but only in the presence of organic acid molecules in solution. The presence of inorganic materials (hydrated magnesium clays) does not impact on precipitate morphology, and reduces the precipitation rate of calcite.

Across and along arc geochemical variations in altered volcanic rocks: Evidence from mineral chemistry of Jurassic lavas in northern Chile, and tectonic implications

NASA Astrophysics Data System (ADS)

Rossel, Pablo; Oliveros, Verónica; Ducea, Mihai N.; Hernandez, Laura

2015-12-01

Postmagmatic processes mask the original whole-rock chemistry of most Mesozoic igneous rocks from the Andean arc and back-arc units preserved in Chile. Mineral assemblages corresponding to subgreenschist metamorphic facies and/or propylitic hydrothermal alteration are ubiquitous in volcanic and plutonic rocks, suggesting element mobility at macroscopic and microscopic scale. However, fresh primary phenocrysts of clinopyroxene and plagioclase do occur in some of the altered rocks. We use major and trace element chemistry of such mineral phases to infer the geochemical variations of four Jurassic arc and four back-arc units from northern Chile. Clinopyroxene belonging to rocks of the main arc and two units of the bark-arc are augites with low contents of HFSE and REE; they originated from melting of an asthenospheric mantle source. Clinopyroxenes from a third back-arc unit show typical OIB affinities, with high Ti and trace element contents and low Si. Trace elemental variations in clinopyroxenes from these arc and back-arc units suggest that olivine and clinopyroxene were the main fractionating phases during early stages of magma evolution. The last back-arc unit shows a broad spectrum of clinopyroxene compositions that includes depleted arc-like augite, high Al and high Sr-Ca diopside (adakite-like signature). The origin of these lavas is the result of melting of a mixture of depleted mantle plus Sr-rich sediments and subsequent high pressure fractionation of garnet. Thermobarometric calculations suggest that the Jurassic arc and back-arc magmatism had at least one crustal stagnation level where crystallization and fractionation took place, located at ca. ~ 8-15 km. The depth of this stagnation level is consistent with lower-middle crust boundary in extensional settings. Crystallization conditions calculated for high Al diopsides suggest a deeper stagnation level that is not consistent with a thinned back-arc continental crust. Thus minor garnet fractionation occurred before these magmas reached the base of the crust. The presented data support the existence of a heterogeneous sub arc mantle and complex magmatic processes in the early stages of the Andean subduction.

Direction discovery: A science enrichment program for high school students.

PubMed

Sikes, Suzanne S; Schwartz-Bloom, Rochelle D

2009-03-01

Launch into education about pharmacology (LEAP) is an inquiry-based science enrichment program designed to enhance competence in biology and chemistry and foster interest in science careers especially among under-represented minorities. The study of how drugs work, how they enter cells, alter body chemistry, and exit the body engages students to conceptualize fundamental precepts in biology, chemistry, and math. Students complete an intensive three-week course in the fundamentals of pharmacology during the summer followed by a mentored research component during the school year. Following a 5E learning paradigm, the summer course captures student interest by introducing controversial topics in pharmacology and provides a framework that guides them to explore topics in greater detail. The 5E learning cycle is recapitulated as students extend their knowledge to design and to test an original research question in pharmacology. LEAP students demonstrated significant gains in biology and chemistry knowledge and interests in pursuing science. Several students earned honors for the presentation of their research in regional and state science fairs. Success of the LEAP model in its initial 2 years argues that coupling college-level coursework of interest to teens with an authentic research experience enhances high school student success in and enthusiasm for science. Copyright © 2009 International Union of Biochemistry and Molecular Biology, Inc.

Coral calcifying fluid pH is modulated by seawater carbonate chemistry not solely seawater pH

PubMed Central

Tambutté, E.; Carpenter, R. C.; Edmunds, P. J.; Evensen, N. R.; Allemand, D.; Ferrier-Pagès, C.; Tambutté, S.; Venn, A. A.

2017-01-01

Reef coral calcification depends on regulation of pH in the internal calcifying fluid (CF) in which the coral skeleton forms. However, little is known about calcifying fluid pH (pHCF) regulation, despite its importance in determining the response of corals to ocean acidification. Here, we investigate pHCF in the coral Stylophora pistillata in seawater maintained at constant pH with manipulated carbonate chemistry to alter dissolved inorganic carbon (DIC) concentration, and therefore total alkalinity (AT). We also investigate the intracellular pH of calcifying cells, photosynthesis, respiration and calcification rates under the same conditions. Our results show that despite constant pH in the surrounding seawater, pHCF is sensitive to shifts in carbonate chemistry associated with changes in [DIC] and [AT], revealing that seawater pH is not the sole driver of pHCF. Notably, when we synthesize our results with published data, we identify linear relationships of pHCF with the seawater [DIC]/[H+] ratio, [AT]/ [H+] ratio and []. Our findings contribute new insights into the mechanisms determining the sensitivity of coral calcification to changes in seawater carbonate chemistry, which are needed for predicting effects of environmental change on coral reefs and for robust interpretations of isotopic palaeoenvironmental records in coral skeletons. PMID:28100813

Human Fetal Osteoblast Response on Poly(Methyl Methacrylate)/Polystyrene Demixed Thin Film Blends: Surface Chemistry Vs Topography Effects.

PubMed

D'Sa, Raechelle A; Raj, Jog; Dickinson, Peter J; McCabe, Fiona; Meenan, Brian J

2016-06-22

Recent advances in materials sciences have allowed for the development and fabrication of biomaterials that are capable of providing requisite cues to instigate cells to respond in a predictable fashion. We have developed a series of poly(methyl methacrylate)/polystyrene (PMMA/PS) polymer demixed thin films with nanotopographies ranging from nanoislands to nanopits to study the response of human fetal osteoblast cells (hFOBs). When PMMA was in excess in the blend composition, a nanoisland topography dominated, whereas a nanopit topography dominated when PS was in excess. PMMA was found to segregate to the top of the nanoisland morphology with PS preferring the substrate interface. To further ascertain the effects of surface chemistry vs topography, we plasma treated the polymer demixed films using an atmospheric pressure dielectric barrier discharge reactor to alter the surface chemistry. Our results have shown that hFOBs did not have an increased short-term cellular response on pristine polymer demixed surfaces. However, increasing the hydrophilicty/wettability of the surfaces by oxygen functionalization causes an increase in the cellular response. These results indicate that topography alone is not sufficient to induce a positive cellular response, but the underlying surface chemistry is also important in regulating cell function.

The Bridge of Mandolin County

NASA Astrophysics Data System (ADS)

Lantz, Juliette M.; Feindt, Jenny E.; Lewellyn, Eric P. B.; Walczak, Mary M.

1999-12-01

The Bridge of Mandolin County is a case designed to teach the general chemistry principles of molar mass, ions and aqueous reactions, solubility rules, and inorganic nomenclature. Through the instructor-facilitated class discussion, students consider the options before the Mandolin Town Council regarding deicing the newly constructed bridge connecting Mandolin with a large nearby city. The students must decipher contradictory claims made on behalf of sodium chloride, the traditional deicer, and calcium magnesium acetate, a new environmentally friendly deicer, to arrive at the most cost-effective and environmentally appropriate deicing product. As they work through the analysis they raise questions that can be addressed in a laboratory setting. Four optional role-playing experiments are included, which can be used by the students to gather information helpful to resolution of the case. The case is intended to be used over two class periods, with a laboratory period in between, though suggestions for other models are provided. Laboratory procedures include an EDTA titration for Ca2+ and Mg2+, a gravimetric analysis, a qualitative examination of ions and solubility, an introduction to freezing point depression and measurement, and an experimental design activity. This case can also successfully be used without alteration in non-majors chemistry or environmental chemistry courses, or upper-level analytical or environmental chemistry courses.

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry.

PubMed

Szakal, Christopher; McCarthy, James A; Ugelow, Melissa S; Konicek, Andrew R; Louis, Kacie; Yezer, Benjamin; Herzing, Andrew A; Hamers, Robert J; Holbrook, R David

2012-07-01

Despite best efforts at controlling nanoparticle (NP) surface chemistries, the environment surrounding nanomaterials is always changing and can impart a permanent chemical memory. We present a set of preparation and measurement methods to be used as the foundation for studying the surface chemical memory of engineered NP aggregates. We attempt to bridge the gap between controlled lab studies and real-world NP samples, specifically TiO(2), by using well-characterized and consistently synthesized NPs, controllably producing NP aggregates with precision drop-on-demand inkjet printing for subsequent chemical measurements, monitoring the physical morphology of the NP aggregate depositions with scanning electron microscopy (SEM), acquiring "surface-to-bulk" mass spectra of the NP aggregate surfaces with time-of-flight secondary ion mass spectrometry (ToF-SIMS), and developing a data analysis scheme to interpret chemical signatures more accurately from thousands of data files. We present differences in mass spectral peak ratios for bare TiO(2) NPs compared to NPs mixed separately with natural organic matter (NOM) or pond water. The results suggest that subtle changes in the local environment can alter the surface chemistry of TiO(2) NPs, as monitored by Ti(+)/TiO(+) and Ti(+)/C(3)H(5)(+) peak ratios. The subtle changes in the absolute surface chemistry of NP aggregates vs. that of the subsurface are explored. It is envisioned that the methods developed herein can be adapted for monitoring the surface chemistries of a variety of engineered NPs obtained from diverse natural environments.

Mixtures in the real world: The importance of plant self-defense toxicants, mycotoxins, and the human diet

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

Mattsson, Joel L., E-mail: jmattsson@indy.rr.com

2007-09-01

A perusal of research presented at the Annual Society of Toxicology Meetings, or in nearly any toxicology journal, will show that the overwhelming emphasis of toxicology research is on synthetic chemistries. Because of substantial potency and exposure to natural chemicals, the overwhelming focus on synthetic chemistries cannot lead to a realistic understanding of chemical risk to the general population. Natural chemicals, simply because of their abundance and potency, may be as likely to be a public health concern and to be involved in chemical interactions (natural:natural, natural:pharmaceutical; or natural:synthetic) as are environmental levels of synthetic chemicals. All plants have amore » mix of natural self-defense chemistries and mycotoxins that, when tested in a manner comparable to synthetic pesticides, cause the entire spectrum of toxic effects. As a further complication, plants also escalate much of their self-defense chemistry when attacked by insects and fungi, and damaged crops often have higher mycotoxins levels. Effective crop protection will typically reduce the plant's levels of self-defense toxicants and mycotoxins, but may add residues of synthetic pesticides or add some other risk variable. In addition, cooking may also alter the food chemistry (e.g., acrylamide). The mixtures toxicologist needs to address the real world mixture of natural and synthetic chemicals. Public policy on crop-food safety cannot be sensibly guided without these data and large voids in our understanding of risks from real-world mixtures cannot be in the public interest.« less

Mixtures in the real world: the importance of plant self-defense toxicants, mycotoxins, and the human diet.

PubMed

Mattsson, Joel L

2007-09-01

A perusal of research presented at the Annual Society of Toxicology Meetings, or in nearly any toxicology journal, will show that the overwhelming emphasis of toxicology research is on synthetic chemistries. Because of substantial potency and exposure to natural chemicals, the overwhelming focus on synthetic chemistries cannot lead to a realistic understanding of chemical risk to the general population. Natural chemicals, simply because of their abundance and potency, may be as likely to be a public health concern and to be involved in chemical interactions (natural:natural, natural:pharmaceutical; or natural:synthetic) as are environmental levels of synthetic chemicals. All plants have a mix of natural self-defense chemistries and mycotoxins that, when tested in a manner comparable to synthetic pesticides, cause the entire spectrum of toxic effects. As a further complication, plants also escalate much of their self-defense chemistry when attacked by insects and fungi, and damaged crops often have higher mycotoxins levels. Effective crop protection will typically reduce the plant's levels of self-defense toxicants and mycotoxins, but may add residues of synthetic pesticides or add some other risk variable. In addition, cooking may also alter the food chemistry (e.g., acrylamide). The mixtures toxicologist needs to address the real world mixture of natural and synthetic chemicals. Public policy on crop-food safety cannot be sensibly guided without these data and large voids in our understanding of risks from real-world mixtures cannot be in the public interest.

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

The snake geothermal drilling project. Innovative approaches to geothermal exploration

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

Shervais, John W.; Evans, James P.; Liberty, Lee M.

2014-02-21

The goal of our project was to test innovative technologies using existing and new data, and to ground-truth these technologies using slim-hole core technology. The slim-hole core allowed us to understand subsurface stratigraphy and alteration in detail, and to correlate lithologies observed in core with surface based geophysical studies. Compiled data included geologic maps, volcanic vent distribution, structural maps, existing well logs and temperature gradient logs, groundwater temperatures, and geophysical surveys (resistivity, magnetics, gravity). New data included high-resolution gravity and magnetic surveys, high-resolution seismic surveys, three slimhole test wells, borehole wireline logs, lithology logs, water chemistry, alteration mineralogy, fracture distribution,more » and new thermal gradient measurements.« less

Geomorphic and Aqueous Chemistry of a Portion of the Upper Rio Tinto System, Spain

NASA Technical Reports Server (NTRS)

Osburn, M. R.; Fernandez-Remolar, D. C.; Arvidson, R. E.; Morris, R. V.; Ming, D.; Prieto-Ballesteros, O.; Amils, R.; Stein, T. C.; Heil-Chapdelaine, V.; Friedlander, L. R.;

OCEANOGRAPHY. Contrasting futures for ocean and society from different anthropogenic CO₂ emissions scenarios.

PubMed

Gattuso, J-P; Magnan, A; Billé, R; Cheung, W W L; Howes, E L; Joos, F; Allemand, D; Bopp, L; Cooley, S R; Eakin, C M; Hoegh-Guldberg, O; Kelly, R P; Pörtner, H-O; Rogers, A D; Baxter, J M; Laffoley, D; Osborn, D; Rankovic, A; Rochette, J; Sumaila, U R; Treyer, S; Turley, C

2015-07-03

The ocean moderates anthropogenic climate change at the cost of profound alterations of its physics, chemistry, ecology, and services. Here, we evaluate and compare the risks of impacts on marine and coastal ecosystems—and the goods and services they provide—for growing cumulative carbon emissions under two contrasting emissions scenarios. The current emissions trajectory would rapidly and significantly alter many ecosystems and the associated services on which humans heavily depend. A reduced emissions scenario—consistent with the Copenhagen Accord's goal of a global temperature increase of less than 2°C—is much more favorable to the ocean but still substantially alters important marine ecosystems and associated goods and services. The management options to address ocean impacts narrow as the ocean warms and acidifies. Consequently, any new climate regime that fails to minimize ocean impacts would be incomplete and inadequate. Copyright © 2015, American Association for the Advancement of Science.

Chemistry of Martian Soils from the Mars Exploration Rover APXS Instruments

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Gellert, R.; Yen, A.

2007-01-01

The martian surface is covered with debris formed by several mechanisms and mobilized by various processes. Volcanism, impact, physical weathering and chemical alteration combine to produce particles of sizes from dust to boulders composed of primary mineral and rock fragments, partially altered primary materials, alteration minerals and shock-modified materials from all of these. Impacts and volcanism produce localized deposits. Winds transport roughly sand-sized material over intermediate distances, while periodic dust storms deposit a global dust layer of the finest fraction. The compositions of clastic sediments can be used to evaluate regional differences in crustal composition and/or weathering processes. Here we examine the growing body of chemical data on soils in Gusev crater and Meridiani Planum returned by the Alpha Particle X-ray Spectrometer (APXS) instruments on the rovers Spirit (MERA) and Opportunity (MERB), following on earlier results based on smaller data sets [1-4].

Inhalation of Silver Nanomaterials—Seeing the Risks

PubMed Central

Theodorou, Ioannis G.; Ryan, Mary P.; Tetley, Teresa D.; Porter, Alexandra E.

2014-01-01

Demand for silver engineered nanomaterials (ENMs) is increasing rapidly in optoelectronic and in health and medical applications due to their antibacterial, thermal, electrical conductive, and other properties. The continued commercial up-scaling of ENM production and application needs to be accompanied by an understanding of the occupational health, public safety and environmental implications of these materials. There have been numerous in vitro studies and some in vivo studies of ENM toxicity but their results are frequently inconclusive. Some of the variability between studies has arisen due to a lack of consistency between experimental models, since small differences between test materials can markedly alter their behaviour. In addition, the propensity for the physicochemistry of silver ENMs to alter, sometimes quite radically, depending on the environment they encounter, can profoundly alter their bioreactivity. Consequently, it is important to accurately characterise the materials before use, at the point of exposure and at the nanomaterial-tissue, or “nanobio”, interface, to be able to appreciate their environmental impact. This paper reviews current literature on the pulmonary effects of silver nanomaterials. We focus our review on describing whether, and by which mechanisms, the chemistry and structure of these materials can be linked to their bioreactivity in the respiratory system. In particular, the mechanisms by which the physicochemical properties (e.g., aggregation state, morphology and chemistry) of silver nanomaterials change in various biological milieu (i.e., relevant proteins, lipids and other molecules, and biofluids, such as lung surfactant) and affect subsequent interactions with and within cells will be discussed, in the context not only of what is measured but also of what can be visualized. PMID:25535082

Effects of Elevated Atmospheric Carbon Dioxide and Tropospheric Ozone on Phytochemical Composition of Trembling Aspen ( Populus tremuloides ) and Paper Birch ( Betula papyrifera ).

PubMed

Couture, John J; Meehan, Timothy D; Rubert-Nason, Kennedy F; Lindroth, Richard L

2017-01-01

Anthropogenic activities are altering levels of atmospheric carbon dioxide (CO 2 ) and tropospheric ozone (O 3 ). These changes can alter phytochemistry, and in turn, influence ecosystem processes. We assessed the individual and combined effects of elevated CO 2 and O 3 on the phytochemical composition of two tree species common to early successional, northern temperate forests. Trembling aspen (Populus tremuloides) and paper birch (Betula papyrifera) were grown at the Aspen FACE (Free-Air Carbon dioxide and ozone Enrichment) facility under four combinations of ambient and elevated CO 2 and O 3 . We measured, over three years (2006-08), the effects of CO 2 and O 3 on a suite of foliar traits known to influence forest functioning. Elevated CO 2 had minimal effect on foliar nitrogen and carbohydrate levels in either tree species, and increased synthesis of condensed tannins and fiber in aspen, but not birch. Elevated O 3 decreased nitrogen levels in both tree species and increased production of sugar, condensed tannins, fiber, and lignin in aspen, but not birch. The magnitude of responses to elevated CO 2 and O 3 varied seasonally for both tree species. When co-occurring, CO 2 offset most of the changes in foliar chemistry expressed under elevated O 3 alone. Our results suggest that levels of CO 2 and O 3 predicted for the mid-twenty-first century will alter the foliar chemistry of northern temperate forests with likely consequences for forest community and ecosystem dynamics.

Single voxel proton magnetic resonance spectroscopy in women with and without intimate partner violence-related posttraumatic stress disorder.

PubMed

Seedat, Soraya; Videen, John S; Kennedy, Colleen M; Stein, Murray B

2005-08-30

Preliminary in vivo proton magnetic spectroscopic ((1)H-MRS) studies of N-acetylaspartate (a putative marker of neuronal viability and function) in combat veterans and maltreated children with posttraumatic stress disorder (PTSD) suggest altered neuronal integrity in anterior cingulate and medial temporal lobe structures. In this study, (1)H-MRS was used to measure N-acetylaspartate (NAA), choline (Cho) and myo-inositol (mI) relative to creatine (Cr) in the anterior cingulate of 16 women with histories of intimate partner violence (7 with a DSM-IV diagnosis of PTSD, 9 without PTSD) and 11 healthy, non-abused comparison subjects. The relationship between anterior cingulate chemistry and performance on the Stroop Color-Word task and Part B of the Trail Making Test was also examined. There were no significant differences in anterior cingulate or occipital gray matter metabolite ratios of NAA/Cr and Cho/Cr between intimate partner violence and healthy comparison subjects. Intimate partner violence subjects with PTSD had significantly higher anterior cingulate Cho/Cr than intimate partner violence subjects without PTSD. There was evidence that the subjects with PTSD suffered more severe intimate partner violence as measured by the Conflict Tactics Scale-Revised. Metabolite ratios were not significantly correlated with performance on the Stroop or Trails B. Our findings, in agreement with earlier studies, showed significant alterations in anterior cingulate chemistry in women with PTSD. In contrast to other studies, we found an increase in Cho/Cr rather than a decrease in NAA/Cr, indicating alterations in glia, instead of neuronal dropout.

Influence of centrifugation conditions on the results of 77 routine clinical chemistry analytes using standard vacuum blood collection tubes and the new BD-Barricor tubes

PubMed Central

Cadamuro, Janne; Mrazek, Cornelia; Leichtle, Alexander B.; Kipman, Ulrike; Felder, Thomas K.; Wiedemann, Helmut; Oberkofler, Hannes; Fiedler, Georg M.; Haschke-Becher, Elisabeth

2017-01-01

Introduction Although centrifugation is performed in almost every blood sample, recommendations on duration and g-force are heterogeneous and mostly based on expert opinions. In order to unify this step in a fully automated laboratory, we aimed to evaluate different centrifugation settings and their influence on the results of routine clinical chemistry analytes. Materials and methods We collected blood from 41 healthy volunteers into BD Vacutainer PST II-heparin-gel- (LiHepGel), BD Vacutainer SST II-serum-, and BD Vacutainer Barricor heparin-tubes with a mechanical separator (LiHepBar). Tubes were centrifuged at 2000xg for 10 minutes and 3000xg for 7 and 5 minutes, respectively. Subsequently 60 and 21 clinical chemistry analytes were measured in plasma and serum samples, respectively, using a Roche COBAS instrument. Results High sensitive Troponin T, pregnancy-associated plasma protein A, ß human chorionic gonadotropin and rheumatoid factor had to be excluded from statistical evaluation as many of the respective results were below the measuring range. Except of free haemoglobin (fHb) measurements, no analyte result was altered by the use of shorter centrifugation times at higher g-forces. Comparing LiHepBar to LiHepGel tubes at different centrifugation setting, we found higher lactate-dehydrogenase (LD) (P = 0.003 to < 0.001) and lower bicarbonate values (P = 0.049 to 0.008) in the latter. Conclusions Serum and heparin samples may be centrifuged at higher speed (3000xg) for a shorter amount of time (5 minutes) without alteration of the analytes tested in this study. When using LiHepBar tubes for blood collection, a separate LD reference value might be needed. PMID:29187797

Trichoderma Biofertilizer Links to Altered Soil Chemistry, Altered Microbial Communities, and Improved Grassland Biomass.

PubMed

Zhang, Fengge; Huo, Yunqian; Cobb, Adam B; Luo, Gongwen; Zhou, Jiqiong; Yang, Gaowen; Wilson, Gail W T; Zhang, Yingjun

2018-01-01

In grasslands, forage and livestock production results in soil nutrient deficits as grasslands typically receive no nutrient inputs, leading to a loss of grassland biomass. The application of mature compost has been shown to effectively increase grassland nutrient availability. However, research on fertilization regime influence and potential microbial ecological regulation mechanisms are rarely conducted in grassland soil. We conducted a two-year experiment in meadow steppe grasslands, focusing on above- and belowground consequences of organic or Trichoderma biofertilizer applications and potential soil microbial ecological mechanisms underlying soil chemistry and microbial community responses. Grassland biomass significantly ( p = 0.019) increased following amendment with 9,000 kg ha -1 of Trichoderma biofertilizer (composted cattle manure + inoculum) compared with other assessed organic or biofertilizer rates, except for BOF3000 (fertilized with 3,000 kg ha -1 biofertilizer). This rate of Trichoderma biofertilizer treatment increased soil antifungal compounds that may suppress pathogenic fungi, potentially partially responsible for improved grassland biomass. Nonmetric multidimensional scaling (NMDS) revealed soil chemistry and fungal communities were all separated by different fertilization regime. Trichoderma biofertilizer (9,000 kg ha -1 ) increased relative abundances of Archaeorhizomyces and Trichoderma while decreasing Ophiosphaerella . Trichoderma can improve grassland biomass, while Ophiosphaerella has the opposite effect as it may secrete metabolites causing grass necrosis. Correlations between soil properties and microbial genera showed plant-available phosphorus may influence grassland biomass by increasing Archaeorhizomyces and Trichoderma while reducing Ophiosphaerella . According to our structural equation modeling (SEM), Trichoderma abundance was the primary contributor to aboveground grassland biomass. Our results suggest Trichoderma biofertilizer could be an important tool for management of soils and ultimately grassland plant biomass.

Trichoderma Biofertilizer Links to Altered Soil Chemistry, Altered Microbial Communities, and Improved Grassland Biomass

PubMed Central

Zhang, Fengge; Huo, Yunqian; Cobb, Adam B.; Luo, Gongwen; Zhou, Jiqiong; Yang, Gaowen; Wilson, Gail W. T.; Zhang, Yingjun

2018-01-01

In grasslands, forage and livestock production results in soil nutrient deficits as grasslands typically receive no nutrient inputs, leading to a loss of grassland biomass. The application of mature compost has been shown to effectively increase grassland nutrient availability. However, research on fertilization regime influence and potential microbial ecological regulation mechanisms are rarely conducted in grassland soil. We conducted a two-year experiment in meadow steppe grasslands, focusing on above- and belowground consequences of organic or Trichoderma biofertilizer applications and potential soil microbial ecological mechanisms underlying soil chemistry and microbial community responses. Grassland biomass significantly (p = 0.019) increased following amendment with 9,000 kg ha−1 of Trichoderma biofertilizer (composted cattle manure + inoculum) compared with other assessed organic or biofertilizer rates, except for BOF3000 (fertilized with 3,000 kg ha−1 biofertilizer). This rate of Trichoderma biofertilizer treatment increased soil antifungal compounds that may suppress pathogenic fungi, potentially partially responsible for improved grassland biomass. Nonmetric multidimensional scaling (NMDS) revealed soil chemistry and fungal communities were all separated by different fertilization regime. Trichoderma biofertilizer (9,000 kg ha−1) increased relative abundances of Archaeorhizomyces and Trichoderma while decreasing Ophiosphaerella. Trichoderma can improve grassland biomass, while Ophiosphaerella has the opposite effect as it may secrete metabolites causing grass necrosis. Correlations between soil properties and microbial genera showed plant-available phosphorus may influence grassland biomass by increasing Archaeorhizomyces and Trichoderma while reducing Ophiosphaerella. According to our structural equation modeling (SEM), Trichoderma abundance was the primary contributor to aboveground grassland biomass. Our results suggest Trichoderma biofertilizer could be an important tool for management of soils and ultimately grassland plant biomass. PMID:29760689

Influence of centrifugation conditions on the results of 77 routine clinical chemistry analytes using standard vacuum blood collection tubes and the new BD-Barricor tubes.

PubMed

Cadamuro, Janne; Mrazek, Cornelia; Leichtle, Alexander B; Kipman, Ulrike; Felder, Thomas K; Wiedemann, Helmut; Oberkofler, Hannes; Fiedler, Georg M; Haschke-Becher, Elisabeth

2018-02-15

Although centrifugation is performed in almost every blood sample, recommendations on duration and g-force are heterogeneous and mostly based on expert opinions. In order to unify this step in a fully automated laboratory, we aimed to evaluate different centrifugation settings and their influence on the results of routine clinical chemistry analytes. We collected blood from 41 healthy volunteers into BD Vacutainer PST II-heparin-gel- (LiHepGel), BD Vacutainer SST II-serum-, and BD Vacutainer Barricor heparin-tubes with a mechanical separator (LiHepBar). Tubes were centrifuged at 2000xg for 10 minutes and 3000xg for 7 and 5 minutes, respectively. Subsequently 60 and 21 clinical chemistry analytes were measured in plasma and serum samples, respectively, using a Roche COBAS instrument. High sensitive Troponin T, pregnancy-associated plasma protein A, ß human chorionic gonadotropin and rheumatoid factor had to be excluded from statistical evaluation as many of the respective results were below the measuring range. Except of free haemoglobin (fHb) measurements, no analyte result was altered by the use of shorter centrifugation times at higher g-forces. Comparing LiHepBar to LiHepGel tubes at different centrifugation setting, we found higher lactate-dehydrogenase (LD) (P = 0.003 to < 0.001) and lower bicarbonate values (P = 0.049 to 0.008) in the latter. Serum and heparin samples may be centrifuged at higher speed (3000xg) for a shorter amount of time (5 minutes) without alteration of the analytes tested in this study. When using LiHepBar tubes for blood collection, a separate LD reference value might be needed.

Frugivory by Brown Marmorated Stink Bug (Hemiptera: Pentatomidae) Alters Blueberry Fruit Chemistry and Preference by Conspecifics.

PubMed

Zhou, Yucheng; Giusti, M Monica; Parker, Joyce; Salamanca, Jordano; Rodriguez-Saona, Cesar

2016-10-01

The brown marmorated stink bug, Halyomorpha halys (Stål), is an invasive pest from Asia that feeds on many agricultural crops in the United States, including blueberries. Yet, the effects of H. halys feeding on fruit chemistry and induced resistance to insects remain unknown. Here we hypothesized that frugivory by H. halys changes fruit chemical composition, which in turn affects insect feeding behavior. In field experiments, blueberry fruit was either mechanically injured or injured by 0 (control), 2, 5, or 10 H. halys Total soluble solids (°Brix) and anthocyanin and phenolic content in injured and uninjured fruits, as well as their effects on feeding behavior by conspecifics, were measured subsequently in the laboratory. Results showed lower °Brix values in injured fruit as compared with uninjured fruit. Fruit injured by 2 and 5 H. halys also had 32 and 20% higher total phenolics, respectively, than the uninjured controls. The proportions of the anthocyanins derived from delphinidin, cyanidin, and petunidin increased, whereas those from malvidin decreased, in fruit after mechanical wounding and frugivory by H. halys In dual-choice tests, H. halys fed more often on uninjured fruit than those previously injured by conspecifics. These results show that frugivory by H. halys reduces the amounts of soluble solids, alters anthocyanin ratios, and increases levels of phenolics, and, as a result, injured fruits were a less preferred food source for conspecifics. To our knowledge, this is the first study to investigate the effects of frugivory on fruit chemistry and induced fruit resistance against a fruit-eating herbivore. © The Authors 2016. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Effects of depletion sampling by standard three-pass pulsed DC electrofishing on blood chemistry parameters of fishes from Appalachian streams

USGS Publications Warehouse

Densmore, Christine L.; Panek, Frank M.

2013-01-01

Adverse effects on fishes captured by electrofishing techniques have long been recognized, although the extent of associated physical injury and behavioral alterations are highly variable and dependent on a number of factors. We examined the effects of three-pass pulsed DC (PDC) electrofishing on two salmonid species (Rainbow Trout Oncorhynchus mykiss and Brook Trout Salvelinus fontinalis) and five other genera (Green Sunfish Lepomis cyanellus, Potomac Sculpin Cottus girardi, Fathead Minnow Pimephales promelas, Largemouth Bass Micropterus salmoides, and Channel Catfish Ictalurus punctatus) common to Appalachian streams. We examined the corresponding effects of PDC electroshock on the following physiological indicators of stress and trauma: blood glucose and serum lactate, as well as on other blood chemistry, namely, enzymes, electrolytes, minerals, and proteins. All species demonstrated physiological responses to PDC electroshock, indicated by the biochemical differences in blood parameters in unshocked and shocked groups of fish with or without gross evidence of hemorrhagic trauma. Serum lactate was the most consistent indicator of these effects. Significant differences in whole blood glucose levels were also noted in treatment groups in all species except Green Sunfish, although the patterns observed were not as consistent as for serum lactate. Elevations in the serum enzymes, aspartate aminotransferase and creatine kinase, in the electroshocked fish occurred only in the two salmonid species. In many instances, although blood parameters were elevated in electroshocked fish compared with the unshocked controls for a given species, there were no differences in those levels in electroshocked fish based on the presence of gross hemorrhagic trauma to axial musculature. While some of the blood parameters examined correlated with both the occurrence of electroshock and the resultant tissue injury, there was no apparent link between the altered blood chemistry and increased mortality 30 d after electrofishing.

A framework for expanding aqueous chemistry in the Community Multiscale Air Quality (CMAQ) model version 5.1

NASA Astrophysics Data System (ADS)

Fahey, Kathleen M.; Carlton, Annmarie G.; Pye, Havala O. T.; Baek, Jaemeen; Hutzell, William T.; Stanier, Charles O.; Baker, Kirk R.; Wyat Appel, K.; Jaoui, Mohammed; Offenberg, John H.

2017-04-01

This paper describes the development and implementation of an extendable aqueous-phase chemistry option (AQCHEM - KMT(I)) for the Community Multiscale Air Quality (CMAQ) modeling system, version 5.1. Here, the Kinetic PreProcessor (KPP), version 2.2.3, is used to generate a Rosenbrock solver (Rodas3) to integrate the stiff system of ordinary differential equations (ODEs) that describe the mass transfer, chemical kinetics, and scavenging processes of CMAQ clouds. CMAQ's standard cloud chemistry module (AQCHEM) is structurally limited to the treatment of a simple chemical mechanism. This work advances our ability to test and implement more sophisticated aqueous chemical mechanisms in CMAQ and further investigate the impacts of microphysical parameters on cloud chemistry. Box model cloud chemistry simulations were performed to choose efficient solver and tolerance settings, evaluate the implementation of the KPP solver, and assess the direct impacts of alternative solver and kinetic mass transfer on predicted concentrations for a range of scenarios. Month-long CMAQ simulations for winter and summer periods over the US reveal the changes in model predictions due to these cloud module updates within the full chemical transport model. While monthly average CMAQ predictions are not drastically altered between AQCHEM and AQCHEM - KMT, hourly concentration differences can be significant. With added in-cloud secondary organic aerosol (SOA) formation from biogenic epoxides (AQCHEM - KMTI), normalized mean error and bias statistics are slightly improved for 2-methyltetrols and 2-methylglyceric acid at the Research Triangle Park measurement site in North Carolina during the Southern Oxidant and Aerosol Study (SOAS) period. The added in-cloud chemistry leads to a monthly average increase of 11-18 % in cloud SOA at the surface in the eastern United States for June 2013.

Coral calcifying fluid pH is modulated by seawater carbonate chemistry not solely seawater pH.

PubMed

Comeau, S; Tambutté, E; Carpenter, R C; Edmunds, P J; Evensen, N R; Allemand, D; Ferrier-Pagès, C; Tambutté, S; Venn, A A

2017-01-25

Reef coral calcification depends on regulation of pH in the internal calcifying fluid (CF) in which the coral skeleton forms. However, little is known about calcifying fluid pH (pH CF ) regulation, despite its importance in determining the response of corals to ocean acidification. Here, we investigate pH CF in the coral Stylophora pistillata in seawater maintained at constant pH with manipulated carbonate chemistry to alter dissolved inorganic carbon (DIC) concentration, and therefore total alkalinity (A T ). We also investigate the intracellular pH of calcifying cells, photosynthesis, respiration and calcification rates under the same conditions. Our results show that despite constant pH in the surrounding seawater, pH CF is sensitive to shifts in carbonate chemistry associated with changes in [DIC] and [A T ], revealing that seawater pH is not the sole driver of pH CF Notably, when we synthesize our results with published data, we identify linear relationships of pH CF with the seawater [DIC]/[H + ] ratio, [A T ]/ [H + ] ratio and [[Formula: see text

Investigation of Diffusion Characteristics through Microfluidic Channels for Passive Drug Delivery Applications

PubMed Central

Ghuman, Alyssa P.; Collins, Stephanie B.; Handa, Hitesh

2016-01-01

Microfluidics has many drug delivery applications due to the ability to easily create complex device designs with feature sizes reaching down to the 10s of microns. In this work, three different microchannel designs for an implantable device are investigated for treatment of ocular diseases such as glaucoma, age-related macular degeneration (AMD), and diabetic retinopathy. Devices were fabricated using polydimethylsiloxane (PDMS) and soft lithography techniques, where surface chemistry of the channels was altered using 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (PEG-silane). An estimated delivery rate for a number of common drugs was approximated for each device through the ratio of the diffusion coefficients for the dye and the respective drug. The delivery rate of the model drugs was maintained at a physiological condition and the effects of channel design and surface chemistry on the delivery rate of the model drugs were recorded over a two-week period. Results showed that the surface chemistry of the device had no significant effect on the delivery rate of the model drugs. All designs were successful in delivering a constant daily dose for each model drug. PMID:27313895

Diagenesis Along Fractures in an Eolian Sandstone, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Ming, D. W.; Yen, A. S.; Rampe, E. B.; Grotzinger, J. P.; Blake, D. F.; Bristow, T. F.; Chipera, S. J.; Downs, R.; Morris, R. V.; Morrison, S. M.;

Two Generations of Sodic Metasomatism in an Allende Type B CAI

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

2015-01-01

Calcium-Aluminum rich inclusions (CAI) in Allende, along with other chondritic compo-nents, experienced variable amounts and types of alter-ation of their mineralogy and chemistry. In CAIs, one of the principal types of alteration led to the depo-sition of nepheline and sodalite. Here we extend initial obervations of alteration in an Allende CAI, focus-ing on occurences of nepheline and a nepheline-like phase with unusally high Ca (referred to as "calcic nepheline" in this abstract). Detailed petrographic and microchemical observations of alteration phases in an Allende Type B CAI (TS4) show that two separate generations of "nepheline", with very distinct composi-tions, crystallized around the margins and in the interi-or of this CAI. We use observations of micro-faults as potential temporal markers, in order to place constraints on the timing of alteration events in Allende. These observa-tions of micro-faulting that truncate and offset one gen-eration of "nepheline" indicate that some "nepheline" crystallized before incorporation of the CAI into the Allende parent-body. Some of the sodic metasomatism in some Allende CAIs occurred prior to Allende par-ent-body assembly. The earlier generation of "calcic-nepheline" has a very distinctive, calcium-rich compo-sition, and the second generation is low in calcium, and matches the compositions of nephelines found in near-by altered chondrules, and in the Allende matrix.

Spectral analysis of Deccan intrabasaltic bole beds: Implications for the formation and alteration of phyllosilicates on Mars

NASA Astrophysics Data System (ADS)

Craig, Patricia; Chevrier, Vincent; Sayyed, M. R. G.; Islam, R.

2017-01-01

To fully understand phyllosilicates on Mars, it is beneficial to study analog deposits on Earth. One attractive candidate for martian phyllosilicates is the intrabasaltic bole beds (palaeosols) from the Deccan Volcanic Province of India. Eleven samples from the upper-layer red Deccan bole beds and underlying yellow and green Deccan bole beds were analyzed by X-ray diffraction (XRD), near-infrared (1.0-2.5 μm) and mid-infrared (5-15 μm) reflectance spectroscopy. Analysis of the bole beds indicated that the red boles are composed of a mixture of montmorillonite and hematite, yellow boles contain vermiculite and minor montmorillonite and green boles are composed mainly of nontronite (smectite) and celadonite (mica). While the bole beds are all chemically similar to each other and to the underlying basalt from which they were weathered, they are mineralogically different. This suggests transformation from one mineral to the next without ion transfer or loss which could be indicative of a limited-water environment. In fact, celadonite can transform into smectites (such as montmorillonite), often with vermiculite as an intermediate step. This not only explains the stratigraphy and mineralogy of the Deccan bole beds but may also explain the layered phyllosilicates identified in various, global locations on Mars. The transition observed in the Deccan bole beds suggests an evolution of the alteration process from deuteric alteration to low-temperature weathering, likely due to changes in temperature, in a closed system (no significant ion transfer) as evidenced by the minerals' similar chemistry. Thus, the Deccan bole beds are a good analog for the phyllosilicates layers on Mars and by studying the chemistry, mineralogy and spectral properties of the Deccan bole beds, we can link their formation and alteration processes to those of martian phyllosilicates. This will provide a clearer understanding of the environmental conditions on Mars at the time of the phyllosilicates' formation and hence during Mars' earliest history.

Geochemical Properties of Rocks and Soils in Gusev Crater, Mars: APXS Results from Cumberland Ridge to Home Plate

NASA Technical Reports Server (NTRS)

Ming, D. W.; Gellert, R.; Morris, R. V.; Yen, A. S.; Arvidson, E.; Brueckner, J.; Clark, B. C.; Cohen, B. A.; Fleischer, I.; Klingelhoefer, G.;

Mechanical changes caused by CO2-driven cement dissolution in the Morrow B Sandstone at reservoir conditions: Experimental observations

NASA Astrophysics Data System (ADS)

Wu, Z.; Luhmann, A. J.; Rinehart, A. J.; Mozley, P.; Dewers, T. A.

2017-12-01

Carbon Capture, Utilization and Storage (CCUS) in transmissive reservoirs is a proposed mechanism in reducing CO2 emissions. Injection of CO2 perturbs reservoir chemistry, and can modify porosity and permeability and alter mineralogy. However, little work has been done on the coupling of rock alteration by CO2 injection and the mechanical integrity of the reservoir. In this study, we perform flow-through experiments on calcite- and dolomite-cemented Pennsylvanian Morrow B Sandstone (West Texas, USA) cores. We hypothesize that poikilotopic calcite cement has a larger impact on chemo-mechanical alteration than disseminated dolomite cement given similar CO2 exposure. With one control brine flow-through experiment and two CO2-plus-brine flow-through experiments for each cement composition, flow rates of 0.1 and 0.01 ml/min were applied under 4200 psi pore fluid pressure and 5000 psi confining pressure at 71 °C. Fluid chemistry and permeability data enable monitoring of mineral dissolution. Ultrasonic velocities were measured pre-test using 1.2 MHz source-receiver pairs at 0.5 MPa axial load and show calcite-cemented samples with higher dynamic elastic moduli than dolomite-cemented samples. Velocities measured post-experiment will identify changes from fluid-rock interaction. We plan to conduct cylinder-splitting destructive mechanical test (Brazil test) to measure the pristine and altered tensile strength of different cemented sandstones. The experiments will identify extents to which cement composition and texture control chemo-mechanical degradation of CCUS reservoirs. Funding for this project is provided by the U.S. Department of Energy's (DOE) National Energy Technology Laboratory (NETL) through the Southwest Regional Partnership on Carbon Sequestration (SWP) under Award No. DE-FC26-05NT42591. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.

MSL SAM-like Analyses of Hawaiian Altered Basaltic Materials: Implications for Analyses by the Mars Science Laboratory

NASA Astrophysics Data System (ADS)

McAdam, A.; Eigenbrode, J. L.; Young, K. E.; Bleacher, J. E.; Knudson, C. A.; Rogers, D.; Glotch, T. D.; Sutter, B.; Mahaffy, P. R.; Navarro-Gonzalez, R.; Downs, R. T.

2015-12-01

Samples of basaltic materials were collected during several traverses of the Kau Desert on the leeward side of the Kilauea Volcano, Hawaii, conducted by the Remote, In Situ, and Synchrotron Studies for Science and Exploration (RIS4E) team, a node of the Solar System Exploration and Research Virtual Institute (SSERVI) program. Some of these samples had been exposed to circumneutral to slightly acidic alteration conditions from exposure to fog/rain, and acidic fog/rain, while others had been exposed to more acidic conditions due to proximity to fumaroles. The samples consisted of basalts with coatings, sands and soils, and ash, and were collected using organically clean protocols to enable investigation of organic chemistry and organic-mineral associations, in addition to mineralogy. The Mars Science Laboratory (MSL) rover has analyzed basaltic materials inferred to have been altered under conditions ranging from circumneutral to acidic, but several aspects of the Sample Analysis at Mars (SAM) instrument suite results are still being investigated and analyses of relevant terrestrial analogs can play an important role in interpretation of the data. For example, all materials analyzed to date have a significant amorphous component. Comparisons of the mineralogy obtained with the MSL CheMin instrument and volatiles evolved during SAM analyses indicate that, by mass balance, some portion of the volatiles, such as SO2 and H2O, are likely associated with this component. Many of the RIS4E samples also have a significant amorphous component, and field x-ray diffraction (XRD) and x-ray fluorescence (XRF) data indicate differences in the chemistry of this material in samples exposed to different alteration conditions. Preliminary SAM-like analyses indicate that the amorphous materials in some of these samples evolve volatiles such as H2O and SO2 during heating. Here we will discuss these results, and others, obtained through SAM-like analyses of selected samples.

An in situ investigation of the influence of a controlled burn on the thermophysical properties of a dry soil

Treesearch

W. J. Massman; J. M. Frank

2004-01-01

High soil temperatures associated with fire influence forests and their ability to regenerate after a fire by altering soil properties and soil chemistry and by killing microbes, plant roots, and seeds. Because intense wild fires are an increasingly common component of the landscape (Graham 2003) and because fire is frequently used by land managers to reduce surface...

Tailoring nanocrystalline diamond coated on titanium for osteoblast adhesion.

PubMed

Pareta, Rajesh; Yang, Lei; Kothari, Abhishek; Sirinrath, Sirivisoot; Xiao, Xingcheng; Sheldon, Brian W; Webster, Thomas J

2010-10-01

Diamond coatings with superior chemical stability, antiwear, and cytocompatibility properties have been considered for lengthening the lifetime of metallic orthopedic implants for over a decade. In this study, an attempt to tailor the surface properties of diamond films on titanium to promote osteoblast (bone forming cell) adhesion was reported. The surface properties investigated here included the size of diamond surface features, topography, wettability, and surface chemistry, all of which were controlled during microwave plasma enhanced chemical-vapor-deposition (MPCVD) processes using CH4-Ar-H2 gas mixtures. The hardness and elastic modulus of the diamond films were also determined. H2 concentration in the plasma was altered to control the crystallinity, grain size, and topography of the diamond coatings, and specific plasma gases (O2 and NH3) were introduced to change the surface chemistry of the diamond coatings. To understand the impact of the altered surface properties on osteoblast responses, cell adhesion tests were performed on the various diamond-coated titanium. The results revealed that nanocrystalline diamond (grain sizes <100 nm) coated titanium dramatically increased surface hardness, and the introduction of O2 and NH3 during the MPCVD process promoted osteoblast adhesion on diamond and, thus, should be further studied for improving orthopedic applications. Copyright 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2010.

Benthic metabolic feedbacks to carbonate chemistry on coral reefs:implications for ocean acidification

NASA Astrophysics Data System (ADS)

Price, N.; Rohwer, F. L.; Stuart, S. A.; Andersson, A.; Smith, J.

2012-12-01

The metabolic activity of resident organisms can cause spatio-temporal variability in carbonate chemistry within the benthic boundary layer, and thus potentially buffer the global impacts of ocean acidification. But, little is known about the capacity for particular species assemblages to contribute to natural daily variability in carbonate chemistry. We encapsulated replicate areas (~3m2) of reef across six Northern Line Islands in the central Pacific for 24 hrs to quantify feedbacks to carbonate chemistry within the benthic boundary layer from community metabolism. Underneath each 'tent', we quantified relative abundance and biomass of each species of corals and algae. We coupled high temporal resolution time series data on the natural diurnal variability in pH, dissolved oxygen, salinity, and temperature (using autonomous sensors) with resident organisms' net community calcification and productivity rates (using change in total dissolved carbon and total alkalinity over time) to examine feedbacks from reef metabolism to boundary layer carbonate chemistry. These reefs experienced large ranges in pH (> 0.2 amplitude) each day, similar to the magnitude of 'acidification' expected over the next century. Daily benthic pH, pCO2, and aragonite saturation state (Ωaragonite) were contrasted with seasonal threshold values estimated from open ocean climatological data extrapolated at each island to determine relative inter-island feedbacks. Diurnal amplitude in pH, pCO2, and Ωaragonite at each island was dependent upon the resident species assemblage of the benthos and was particularly reliant upon the biomass, productivity, and calcification rate of Halimeda. Net primary productivity of fleshy algae (algal turfs and Lobophora spp.) predominated on degraded, inhabited islands where net community calcification was negligible. In contrast, the chemistry over reefs on 'pristine', uninhabited islands was driven largely by net calcification of calcareous algae and stony corals. Knowledge about species specific physiological rates and relative abundances of key taxa whose metabolism significantly alters carbonate chemistry may give insight to the ability for a reef to buffer against or exacerbate ocean acidification.

Fluvial wood function downstream of beaver versus man-made dams in headwater streams in Massachusetts, USA

NASA Astrophysics Data System (ADS)

David, G. C.; DeVito, L. F.; Munz, K. T.; Lisius, G.

2014-12-01

Fluvial wood is an essential component of stream ecosystems by providing habitat, increasing accumulation of organic matter, and increasing the processing of nutrients and other materials. However, years of channel alterations in Massachusetts have resulted in low wood loads despite the afforestation that has occurred since the early 1900s. Streams have also been impacted by a large density of dams, built during industrialization, and reduction of the beaver population. Beavers were reintroduced to Massachusetts in the 1940s and they have since migrated throughout the state. Beaver dams impound water, which traps sediment and results in the development of complex channel patterns and more ecologically productive and diverse habitats than those found adjacent to man-made dams. To develop better management practices for dam removal it is essential that we understand the geomorphic and ecologic function of wood in these channels and the interconnections with floodplain dynamics and stream water chemistry. We investigate the connections among fluvial wood, channel morphology, floodplain soil moisture dynamics, and stream water chemistry in six watersheds in Massachusetts that have been impacted by either beaver or man-made dams. We hypothesize that wood load will be significantly higher below beaver dams, subsequently altering channel morphology, water chemistry, and floodplain soil moisture. Reaches are surveyed up- and downstream of each type of dam to better understand the impact dams have on the fluvial system. Surveys include a longitudinal profile, paired with dissolved oxygen and ammonium measurements, cross-section and fluvial wood surveys, hydraulic measurements, and floodplain soil moisture mapping. We found that dissolved oxygen mirrored the channel morphology, but did not vary significantly between reaches. Wood loads were significantly larger downstream of beaver dams, which resulted in significant changes to the ammonium levels. Floodplain soil moisture dynamics revealed that wood loads increased the channel complexity and strengthened connections between the stream channel and floodplain. Future work will continue to explore the complex interconnections between beaver dams, channel morphology, hydraulics, floodplain dynamics and water chemistry.

Experimentally Shocked and Altered Basalt: Laboratory Analogs for Calibration of Mars Remote Sensing and In Situ Data

NASA Technical Reports Server (NTRS)

Bell, M. S.

2015-01-01

Calciumphosphate (likely chloroapatite) is formed in the alteration experiments and is more abundant in the altered and shocked sample probably due to increased surface area exposed to alteration fluids resulting from shock damage in the form of both brittle and structural deformation to the starting material (Figs 1 & 3). Apatite forms in basic conditions so the closed system alteration experiment must be buffered by the basalt starting material to create a fluid chemistry environment evolving from neutral at the start to alkaline after 21 days at 160 C. Plagioclase feldspar in the unshocked sample (Fig. 2) has undergone a solid-state transformation to maskelynite, a disordered phase that is not manifest in the XRD pattern of the shocked sample (Fig.4). Olivine and ulvospinel that are present in the starting material can be detected by XRD in the shocked and altered sample (Fig. 4). Tungsten from the sample holder used in the shock experiments dominates the XRD pattern of the shocked and altered sample (Fig. 4). Samples were weighed after the alteration experiments to determine mass loss and predict the amount of material available for the planned analyses from the shock experiments. Within the constraints of these experiments, mass loss is negligible. The samples will next be characterized by Moessbauer and Vis-Near IR spectroscopy, the results of which will be compared to the Mars Exploration Rovers and Mars Reconnaissance Orbiter data sets respectively.

Experimentally Shocked and Altered Basalt: Laboratory Analogs for Calibration of Mars Remote Sensing and In Situ Data

NASA Technical Reports Server (NTRS)

Bell, M. S.

2015-01-01

Calcium phosphate (likely chloroapatite) is formed in the alteration experiments and is more abundant in the altered and shocked sample probably due to increased surface area exposed to alteration fluids resulting from shock damage in the form of both brittle and structural deformation to the starting material (Figs 1 & 3). Apatite forms in basic conditions so the closed system alteration experiment must be buffered by the basalt starting material to create a fluid chemistry environment evolving from neutral at the start to alkaline after 21 days at 160 degrees Centigrade. Plagioclase feldspar in the unshocked sample (Fig. 2) has undergone a solid-state transformation to maskelynite, a disordered phase that is not manifest in the X-ray diffraction pattern of the shocked sample (Fig.4). Olivine and ulvospinel that are present in the starting material can be detected by X-ray diffraction in the shocked and altered sample (Fig. 4). Tungsten from the sample holder used in the shock experiments dominates the X-ray diffraction pattern of the shocked and altered sample (Fig. 4). Samples were weighed after the alteration experiments to determine mass loss and predict the amount of material available for the planned analyses from the shock experiments. Within the constraints of these experiments, mass loss is negligible. The samples will next be characterized by Moessbauer and Vis-Near Infrared spectroscopy, the results of which will be compared to the Mars Exploration Rovers and Mars Reconnaissance Orbiter data sets respectively.

Questa baseline and pre-mining ground-water quality investigation. 14. Interpretation of ground-water geochemistry in catchments other than the Straight Creek catchment, Red River Valley, Taos County, New Mexico, 2002-2003

USGS Publications Warehouse

Nordstrom, D. Kirk; McCleskey, R. Blaine; Hunt, Andrew G.; Naus, Cheryl A.

2005-01-01

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site but proximal analog. The Straight Creek catchment, chosen for this purpose, consists of the same Tertiary-age quartz-sericite-pyrite altered andesite and rhyolitic volcanics as the mine site. Straight Creek is about 5 kilometers east of the eastern boundary of the mine site. Both Straight Creek and the mine site are at approximately the same altitude, face south, and have the same climatic conditions. Thirteen wells in the proximal analog drainage catchment were sampled for ground-water chemistry. Eleven wells were installed for this study and two existing wells at the Advanced Waste-Water Treatment (AWWT) facility were included in this study. Eight wells were sampled outside the Straight Creek catchment: one each in the Hansen, Hottentot, and La Bobita debris fans, four in a well cluster in upper Capulin Canyon (three in alluvial deposits and one in bedrock), and an existing well at the U.S. Forest Service Questa Ranger Station in Red River alluvial deposits. Two surface waters from the Hansen Creek catchment and two from the Hottentot drainage catchment also were sampled for comparison to ground-water compositions. In this report, these samples are evaluated to determine if the geochemical interpretations from the Straight Creek ground-water geochemistry could be extended to other ground waters in the Red River Valley , including the mine site. Total-recoverable major cations and trace metals and dissolved major cations, selected trace metals, anions, alkalinity; and iron-redox species were determined for all surface- and ground-water samples. Rare-earth elements and low-level As, Bi, Mo, Rb, Re, Sb, Se, Te, Th, U, Tl, V, W, Y, and Zr were determined on selected samples. Dissolved organic carbon (DOC), mercury, sulfate stable isotope composition (d34S and d18O of sulfate), stable isotope composition of water (d2H and d18O of water) were measured for selected samples. Chlorofluorocarbons (CFC) and 3He and 3H were measured for age dating on selected samples. Linear regressions from the Straight Creek ground-water data were used to compare ground-water chemistry trends in non-Straight Creek ground waters with Straight Creek alluvial ground-water chemistry dilution trends. Most of the solute trends for the ground waters are similar to those for Straight Creek but there are some notable exceptions. In lithologies that contain substantial pyrite mineralization, acid waters form with similar chemistries to those in Straight Creek and all the waters tend to be calcium-sulfate type. Hottentot ground waters contain substantially lower calcium concentrations relative to those in Straight Creek. This anomaly results from the exposure of rhyolite porphyry in the Hottentot scar and weathering zone. The rhyolite contains less calcium than the altered andesites and tuffs in the Straight Creek catchment and probably does not have the abundant gypsum and calcite. The Hansen ground waters have reached gypsum saturation and have similar calcium, magnesium, and beryllium concentrations as Straight Creek ground waters but have lower concentrations of fluoride, manganese, zinc, cobalt, nickel, copper, and lithium. Lower concentrations of elements related to mineralization at Hansen likely reflect the more distal location of Hansen with respect to intrusive centers that provided the heat source for hydrothermal alteration. The other ground water with water chemistry trends that are outside the Straight Creek trends was from an alluvial well from Capulin Canyon (CC2A). Although it had pH values near 6.0 and most major ions similar to the other Capulin Canyon ground waters, it contained high concentrations

Isotope hydrology and baseflow geochemistry in natural and human-altered watersheds in the Inland Pacific Northwest, USA.

PubMed

Sánchez-Murillo, Ricardo; Brooks, Erin S; Elliot, William J; Boll, Jan

2015-01-01

This study presents a stable isotope hydrology and geochemical analysis in the inland Pacific Northwest (PNW) of the USA. Isotope ratios were used to estimate mean transit times (MTTs) in natural and human-altered watersheds using the FLOWPC program. Isotope ratios in precipitation resulted in a regional meteoric water line of δ(2)H = 7.42·δ(18)O + 0.88 (n = 316; r(2) = 0.97). Isotope compositions exhibited a strong temperature-dependent seasonality. Despite this seasonal variation, the stream δ(18)O variation was small. A significant regression (τ = 0.11D(-1.09); r(2) = 0.83) between baseflow MTTs and the damping ratio was found. Baseflow MTTs ranged from 0.4 to 0.6 years (human-altered), 0.7 to 1.7 years (mining-altered), and 0.7 to 3.2 years (forested). Greater MTTs were represented by more homogenous aqueous chemistry whereas smaller MTTs resulted in more dynamic compositions. The isotope and geochemical data presented provide a baseline for future hydrological modelling in the inland PNW.

Cardiopulmonary, blood and peritoneal fluid alterations associated with abdominal insufflation of carbon dioxide in standing horses.

PubMed

Latimer, F G; Eades, S C; Pettifer, G; Tetens, J; Hosgood, G; Moore, R M

2003-05-01

Abdominal insufflation is performed routinely during laparoscopy in horses to improve visualisation and facilitate instrument and visceral manipulations during surgery. It has been shown that high-pressure pneumoperitoneum with carbon dioxide (CO2) has deleterious cardiopulmonary effects in dorsally recumbent, mechanically ventilated, halothane-anaesthetised horses. There is no information on the effects of CO2 pneumoperitoneum on cardiopulmonary function and haematology, plasma chemistry and peritoneal fluid (PF) variables in standing sedated horses during laparoscopic surgery. To determine the effects of high pressure CO2 pneumoperitoneum in standing sedated horses on cardiopulmonary function, blood gas, haematology, plasma chemistry and PF variables. Six healthy, mature horses were sedated with an i.v. bolus of detomidine (0.02 mg/kg bwt) and butorphanol (0.02 mg/kg bwt) and instrumented to determine the changes in cardiopulmonary function, haematology, serum chemistry and PF values during and after pneumoperitoneum with CO2 to 15 mmHg pressure for standing laparoscopy. Each horse was assigned at random to either a standing left flank exploratory laparoscopy (LFL) with CO2 pneumoperitoneum or sham procedure (SLFL) without insufflation, and instrumented for measurement of cardiopulmonary variables. Each horse underwent a second procedure in crossover fashion one month later so that all 6 horses had both an LFL and SLFL performed. Cardiopulmonary variables and blood gas analyses were obtained 5 mins after sedation and every 15 mins during 60 mins baseline (BL), insufflation (15 mmHg) and desufflation. Haematology, serum chemistry analysis and PF analysis were performed at BL, insufflation and desufflation, and 24 h after the conclusion of each procedure. Significant decreases in heart rate, cardiac output and cardiac index and significant increases in mean right atrial pressure, systemic vascular resistance and pulmonary vascular resistance were recorded immediately after and during sedation in both groups of horses. Pneumoperitoneum with CO2 at 15 mmHg had no significant effect on cardiopulmonary function during surgery. There were no significant differences in blood gas, haematology or plasma chemistry values within or between groups at any time interval during the study. There was a significant increase in the PF total nucleated cell count 24 h following LFL compared to baseline values for LFL or SLFL at 24 h. There were no differences in PF protein concentrations within or between groups at any time interval. Pneumoperitoneum with CO2 during standing laparoscopy in healthy horses does not cause adverse alterations in cardiopulmonary, haematology or plasma chemistry variables, but does induce a mild inflammatory response within the peritoneal cavity. High pressure (15 mmHg) pneumoperitoneum in standing sedated mature horses for laparoscopic surgery can be performed safely without any short-term or cumulative adverse effects on haemodynamic or cardiopulmonary function.

Minimizing artifact formation in magnetorheological finishing of chemical vapor deposition ZnS flats.

PubMed

Kozhinova, Irina A; Romanofsky, Henry J; Maltsev, Alexander; Jacobs, Stephen D; Kordonski, William I; Gorodkin, Sergei R

2005-08-01

The polishing performance of magnetorheological (MR) fluids prepared with a variety of magnetic and nonmagnetic ingredients was studied on four types of initial surface for chemical vapor deposition (CVD) ZnS flats from domestic and foreign sources. The results showed that it was possible to greatly improve smoothing performance of magnetorheological finishing (MRF) by altering the fluid composition, with the best results obtained for nanoalumina abrasive used with soft carbonyl iron and altered MR fluid chemistry. Surface roughness did not exceed 20 nm peak to valley and 2 nm rms after removal of 2 microm of material. The formation of orange peel and the exposure of a pebblelike structure inherent in ZnS from the CVD process were suppressed.

New ligand platforms featuring boron-rich clusters as organomimetic substituents*,**

PubMed Central

Spokoyny, Alexander M.

2013-01-01

200 years of research with carbon-rich molecules have shaped the development of modern chemistry. Research pertaining to the chemistry of boron-rich species has historically trailed behind its more distinguished neighbor (carbon) in the periodic table. Notably, a potentially rich and, in many cases, unmatched field of coordination chemistry using boronrich clusters remains fundamentally underdeveloped. Our work has been devoted to examining several basic concepts related to the functionalization of icosahedral boron-rich clusters and their use as ligands, aimed at designing fundamentally new hybrid molecular motifs and materials. Particularly interesting are icosahedral carboranes, which can be regarded as 3D analogs of benzene. These species comprise a class of boron-rich clusters that were discovered in the 1950s during the “space race” while researchers were developing energetic materials for rocket fuels. Ultimately, the unique chemical and physical properties of carborane species, such as rigidity, indefinite stability to air and moisture, and 3D aromaticity, may allow one to access a set of properties not normally available in carbon-based chemistry. While technically these species are considered as inorganic clusters, the chemical properties they possess make these boron-rich species suitable for replacing and/or altering structural and functional features of the organic and organometallic molecules—a phenomenon best described as “organomimetic”. Aside from purely fundamental features associated with the organomimetic chemistry of icosahedral carboranes, their use can also provide new avenues in the development of systems relevant to solving current problems associated with energy production, storage, and conversion. PMID:24311823

Antibacterial Metallic Touch Surfaces

PubMed Central

Villapún, Victor M.; Dover, Lynn G.; Cross, Andrew; González, Sergio

2016-01-01

Our aim is to present a comprehensive review of the development of modern antibacterial metallic materials as touch surfaces in healthcare settings. Initially we compare Japanese, European and US standards for the assessment of antimicrobial activity. The variations in methodologies defined in these standards are highlighted. Our review will also cover the most relevant factors that define the antimicrobial performance of metals, namely, the effect of humidity, material geometry, chemistry, physical properties and oxidation of the material. The state of the art in contact-killing materials will be described. Finally, the effect of cleaning products, including disinfectants, on the antimicrobial performance, either by direct contact or by altering the touch surface chemistry on which the microbes attach, will be discussed. We offer our outlook, identifying research areas that require further development and an overview of potential future directions of this exciting field. PMID:28773856

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

Mossaad, Christina; Starr, Matthew; Payzant, E Andrew

The objective of the present paper was to produce nanoscale hydroxyapatite at room temperature under 10 nm through a simple method that requires no specialized equipment, surfactants, or additives. The Ca(C2H3O2)2-K3PO4-H2O synthesis system explored in previous literature was employed and the nanoscale powder product completely characterized through x-ray diffraction, transmission electron microscopy, BET nitrogen surface area adsorption, helium pycnometry, TGA and Karl Fisher titration. In accordance with other materials, it was found that hydroxyapatite under 5 nm produced by this chemistry undergoes an uphill phase transformation when left in dry storage over 5 months. Although it is possible to producemore » hydroxyapatite (and other materials) in this size range, it is imperative that care is taken through storage alterations to prevent any undesirable changes in structure or surface chemistry« less

Mineralogy and Genesis of the Windjana Sandstone, Kimberley Area, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Treiman, A. H.; Bish, D.; Ming, D. W.; Grotzinger, J.; Vaniman, D. T.; Baker, M. B.; Farmer, J.; Chipera, S.; Downs, R. T.; Morris, R. V.;

Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

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

Alvarado, Samuel R.; Guo, Yijun; Ruberu, T. Purnima A.

2014-03-15

The optoelectronic and chemical properties of semiconductor nanocrystals heavily depend on their composition, size, shape and internal structure, surface functionality, etc. Available strategies to alter these properties through traditional colloidal syntheses and ligand exchange methods place a premium on specific reaction conditions and surfactant combinations. In this invited review, we apply a molecular-level understanding of chemical precursor reactivity to reliably control the morphology, composition and intimate architecture (core/shell vs. alloyed) of semiconductor nanocrystals. We also describe our work aimed at achieving highly selective, low-temperature photochemical methods for the synthesis of semiconductor–metal and semiconductor–metal oxide photocatalytic nanocomposites. In addition, we describemore » our work on surface modification of semiconductor nanocrystal quantum dots using new approaches and methods that bypass ligand exchange, retaining the nanocrystal's native ligands and original optical properties, as well as on spectroscopic methods of characterization useful in determining surface ligand organization and chemistry. Using recent examples from our group and collaborators, we demonstrate how these efforts have lead to faster, wider and more systematic application of semiconductor nanocrystal-based materials to biological imaging and tracking, and to photocatalysis of unconventional substrates. We believe techniques and methods borrowed from inorganic chemistry (including coordination, organometallic and solid state chemistry) have much to offer in reaching a better understanding of the synthesis, functionalization and real-life application of such exciting materials as semiconductor nanocrystals (quantum dots, rods, tetrapods, etc.).« less

Influence of macromer molecular weight and chemistry on poly(beta-amino ester) network properties and initial cell interactions.

PubMed

Brey, Darren M; Erickson, Isaac; Burdick, Jason A

2008-06-01

A library of photocrosslinkable poly(beta-amino ester)s (PBAEs) was recently synthesized to expand the number of degradable polymers that can be screened and developed for a variety of biological applications. In this work, the influence of variations in macromer chemistry and macromer molecular weight (MMW) on network reaction behavior, overall bulk properties, and cell interactions were investigated. The MMW was controlled through alterations in the initial diacrylate to amine ratio (> or =1) during synthesis and decreased with an increase in this ratio. Lower MMWs reacted more quickly and to higher double bond conversions than higher MMWs, potentially due to the higher concentration of reactive groups. Additionally, the lower MMWs led to networks with higher compressive and tensile moduli that degraded slower than networks formed from higher MMWs because of an increase in the crosslinking density and decrease in the number of degradable units per crosslink. The adhesion and spreading of osteoblast-like cells on polymer films was found to be dependent on both the macromer chemistry and the MMW. In general, the number of cells was similar on networks formed from a range of MMWs, but the spreading was dramatically influenced by MMW (higher spreading with lower MMWs). These results illustrate further diversity in photocrosslinkable PBAE properties and that the chemistry and macromer structure must be carefully selected for the desired application. Copyright 2007 Wiley Periodicals, Inc.

Effects of 100-μT extremely low frequency electromagnetic fields exposure on hematograms and blood chemistry in rats

PubMed Central

Lai, Jinsheng; Zhang, Yemao; Zhang, Jiangong; Liu, Xingfa; Ruan, Guoran; Chaugai, Sandip; Tang, Jiarong; Wang, Hong; Chen, Chen; Wang, Dao Wen

2016-01-01

The aim of this study was to test whether extremely low frequency electromagnetic fields (ELF EMFs) affect health or not. Here, we constructed a 100-μT/50 Hz electromagnetic field atmosphere. A total of 128 rats were randomly assigned into two groups: the ELF EMF group and the sham group. The ELF EMF group was exposed to 100-μT/50-Hz ELF EMF for 20 h per day for three months; at the same time the other group was exposed to a sham device without ELF EMF. During the three months, the weight was recorded every 2 weeks, and the water intake and food intake of the animals were recorded weekly. The hematologic parameters were detected before and after the exposure, whereas blood chemistry analysis was performed every 4 weeks. The general condition of the exposed rats was not affected by ELF EMF. Compared with the sham group, the hematograms were not significantly altered in the ELF EMF group. Similarly, the blood chemistry (including lipid profile, blood glucose, liver function and renal function of rats) from the ELF EMF group showed no difference compared with rats from the control group during the three months exposure. The present study indicated that short-term exposure of 100-μT/50-Hz ELF EMF may not affect hematograms and blood chemistry in rats. PMID:26404558

Chemistry of the Burning Surface

DTIC Science & Technology

1993-10-12

simulated combustion and explo- the temperature is nonuniform along the filament length sion events. SUFKS V~V 100 IWAQ10 0 t 1 10 CABRAM OIRV...temperature. Ilee filament is slightly altered by the sample, the power results clearly show that it is the nonuniform temper%- dissipation is essentially...sample explosive and propellant material, was chosen because it is presnt on the filamenL Liquefaction of AMMO is illustrates the laIr amount of chemical

Hydrothermal Alteration Mineralogy Characterized Through Multiple Analytical Methods: Implications for Mars

NASA Astrophysics Data System (ADS)

Black, S.; Hynek, B. M.; Kierein-Young, K. S.; Avard, G.; Alvarado-Induni, G.

2015-12-01

Proper characterization of mineralogy is an essential part of geologic interpretation. This process becomes even more critical when attempting to interpret the history of a region remotely, via satellites and/or landed spacecraft. Orbiters and landed missions to Mars carry with them a wide range of analytical tools to aid in the interpretation of Mars' geologic history. However, many instruments make a single type of measurement (e.g., APXS: elemental chemistry; XRD: mineralogy), and multiple data sets must be utilized to develop a comprehensive understanding of a sample. Hydrothermal alteration products often exist in intimate mixtures, and vary widely across a site due to changing pH, temperature, and fluid/gas chemistries. These characteristics require that we develop a detailed understanding regarding the possible mineral mixtures that may exist, and their detectability in different instrument data sets. This comparative analysis study utilized several analytical methods on existing or planned Mars rovers (XRD Raman, LIBS, Mössbauer, and APXS) combined with additional characterization (thin section, VNIR, XRF, SEM-EMP) to develop a comprehensive suite of data for hydrothermal alteration products collected from Poás and Turrialba volcanoes in Costa Rica. Analyzing the same samples across a wide range of instruments allows for direct comparisons of results, and identification of instrumentation "blind spots." This provides insight into the ability of in-situ analyses to comprehensively characterize sites on Mars exhibiting putative hydrothermal characteristics, such as the silica and sulfate deposits at Gusev crater [eg: Squyres et al., 2008], as well as valuable information for future mission planning and data interpretation. References: Squyres et al. (2008), Detection of Silica-Rich Deposits on Mars, Science, 320, 1063-1067, doi:10.1126/science.1155429.

Porosity and Permeability Evolution in Cemented Rock Cores under Reactive Flowing Conditions: Comparative Analysis between Limestone and Sandstone Host Rocks

NASA Astrophysics Data System (ADS)

Cao, P.; Karpyn, Z.; Li, L.

2013-12-01

CO2-brine has the potential to alter wellbore cement in depleted oil and gas reservoirs under geological CO2 sequestration conditions. A better understanding of CO2-brine-cement-rock interaction is needed to evaluate the seal integrity of candidate sequestration formation in the long run. This work investigates possible alteration of wellbore cement when bonded by different host formation rock upon exposure to CO2-saturated brine. Composite cement-sandstone and cement-limestone core samples were created to perform reactive coreflood experiments. After an eight-day dynamic flow-through period, both cores had a similar extent of porosity increase, while the cement-limestone core experienced a ten-fold higher increase in permeability. With the aid of X-ray Micro-CT imaging and Scanning Electron Microscopy, it is observed that cement underwent greater degradation at the cement-sandstone interface. Degradation of cement-limestone core mainly took place on the host rock matrix. Worm holes were developed and a solution channel was formed in the limestone, creating a dominant flow path that altered both flow and reaction behavior. Limestone buffered the injected acidic brine preventing further deterioration of cement near the core outlet. Changes in fluid chemistry of limestone and sandstone coreflood effluents are compared. Results from this work are aimed at assisting the development and validation of robust reactive transport models through direct measurement of cemented rock core porosity and permeability evolution as well as the effluent aqueous chemistry change. This will subsequently improve predictive capabilities of reactive transport models associated with CO2 sequestration in geologic environments. Permeability Evolution of Cement-Rock Core Sample during Dynamic Flow of CO2-Brine

Investigations on the osmoregulation of freshwater fish (Oreochromis niloticus) following exposures to metals (Cd, Cu) in differing hardness.

PubMed

Saglam, Dilek; Atli, Gülüzar; Canli, Mustafa

2013-06-01

Hardness is one of the most important factors in water chemistry as it affects fish physiology and metal toxicity. The aim of this study was to investigate osmoregulatory responses in the Nile tilapia Oreochromis niloticus exposed to copper and cadmium (1.0μg/mL) in soft water (SW) (hardness 80mg CaCO3/L and conductivity 1.77mS/cm) and hard water (HW) (hardness 320mg CaCO3/L and conductivity 5.80mS/cm) for 0, 1, 7 and 14 days. Following the exposures, Na(+)/K(+)-ATPase activity, ion and Cu levels in the gill, kidney and intestine were measured. There was no fish mortality within 14 days, except Cu exposure in SW which killed all fish between 8 and 12 days. Generally, Na(+)/K(+)-ATPase activity was altered by both metal exposures in the gill and kidney as it increased in HW condition, but decreased in SW condition. There were also alterations in Na(+)/K(+)-ATPase activity in the intestine as its activity generally decreased. Data, in general, showed that Cd was more effective on Na(+)/K(+)-ATPase activity comparing to Cu. However, ion levels altered mainly in the kidney and intestine. Tissue metal accumulation was higher in fish tissues from SW condition comparing to HW condition. Data represented here showed that the effects of metals differed in differing water hardness. This suggests that special attention should be paid to the water chemistry when natural monitoring studies are carried out. This study also suggests that the response of osmoregulation system of fish may be a sensitive indicator under stressful conditions in different natural waters. Copyright © 2013 Elsevier Inc. All rights reserved.

Fire Events and Soil Thermometry: The Applications of Clay Chemistry for Tracing Temperature Changes in Soils and Sediments Below Surface Fires

NASA Astrophysics Data System (ADS)

Watson, E.; Werts, S. P.; Gelabert, M.

2016-12-01

Fires in the natural environment affect the physical, chemical, and biological properties of soils. However, fires may also alter the mineralogy of the geologic material in which it comes in contact. Previous experiments on high temperature alteration of clays indicate that dehydration, oxidation, and hydroxylation in clay minerals can occur progressively in that order at increasing temperatures up to 500°C. It is also well known that wildfire events can heat soils to these temperature ranges several centimeters deep. In this experiment, alterations in clay chemistry were used as a tool to investigate fire intensity along with the changing morphology of clay minerals. For data collection, small camp fires were set in York County, SC and temperatures were recorded using a datalogger system to 5 cm deep during the fire event. Control samples were taken adjacent to the fires to compare the changing morphology of the minerals when heated. Powder x-ray diffraction and scanning electron microscopy were used to identify the clay mineralogy. The clay from soil samples was identified as hydrous kaolinite, anhydrous kaolinite, and varying types of goethite. To observe the dehydration, oxidation, and hydroxylation of clay minerals, scanning electron microscopy with emission dispersive spectroscopy was used to identify the O/cation ratios present, which would indicate changes in the oxidation state of the clay minerals. By mapping the changes in O/cation ratios with temperature in silicates, we are able to trace the temperature of the sediments during fire events. This research suggests it may be possible to utilize these geochemical trends to aid in soil and sediment temperature investigations in both archeological and modern soil and surface process investigations.

Canopy structural alterations to nitrogen functions of the soil microbial community in a Quercus virginiana forest

NASA Astrophysics Data System (ADS)

Moore, L. D.; Van Stan, J. T., II; Rosier, C. L.; Gay, T. E.; Wu, T.

2014-12-01

Forest canopy structure controls the timing, amount and chemical character of precipitation supply to soils through interception and drainage along crown surfaces. Yet, few studies have examined forest canopy structural connections to soil microbial communities (SMCs), and none have measured how this affects SMC N functions. The maritime Quercus virginiana Mill. (southern live oak) forests of St Catherine's Island, GA, USA provide an ideal opportunity to examine canopy structural alterations to SMCs and their functioning, as their throughfall varies substantially across space due to dense Tillandsia usneoides L. (spanish moss) mats bestrewn throughout. To examine the impact of throughfall variability on SMC N functions, we examined points along the canopy coverage continuum: large canopy gaps (0%), bare canopy (50-60%), and canopy of heavy T. usneoides coverage (>=85%). Five sites beneath each of the canopy cover types were monitored for throughfall water/ions and soil leachates chemistry for one storm each month over the growing period (7 months, Mar-2014 to Sep-2014) to compare with soil chemistry and SMC communities sampled every two months throughout that same period (Mar, May, Jul, Sep). DGGE and QPCR analysis of the N functioning genes (NFGs) to characterize the ammonia oxidizing bacterial (AOB-amoA), archaea (AOA-amoA), and ammonification (chiA) communities were used to determine the nitrification and decomposition potential of these microbial communities. PRS™-probes (Western Ag Innovations Inc., Saskatoon, Canada) were then used to determine the availability of NO3-N and NH4+N in the soils over a 6-week period to evaluate whether the differing NFG abundance and community structures resulted in altered N cycling.

Relationship Between Iron Valence States of Serpentine in CM Chondrites and Their Aqueous Alteration Degrees

NASA Technical Reports Server (NTRS)

Mikouchi, T.; Zolensky, M.; Satake, W.; Le, L.

2012-01-01

The 0.6-0.7 micron absorption band observed for C-type asteroids is caused by the presence of Fe(3+) in phyllosilicates . Because Fe-bearing phyllosilicates, especially serpentine, are the most dominant product of aqueous alteration in the most abundant carbonaceous chondrites, CM chondrites, it is important to understand the crystal chemistry of serpentine in CM chondrites to better understand spectral features of C-type asteroids. CM chondrites show variable degrees of aqueous alteration, which should be related to iron valences in serpentine. It is predicted that the Fe(3+)/Sum of (Fe) ratios of serpentine in CM chondrites decrease as alteration proceeds by Si and Fe(3+) substitutions from end-member cronstedtite to serpentine, which should be apparent in the absorption intensity of the 0.6-0.7 micron band from C-type asteroids. In fact, the JAXA Hayabusa 2 target (C-type asteroid: 1993 JU3) exhibits heterogeneous spectral features (0.7 micron absorption band disappears by rotation). From these points of view, we have analyzed iron valences of matrix serpentine in several CM chondrites which span the entire observed range of aqueous alteration using Synchrotron Radiation X-ray Absorption Near-Edge Structure (SR-XANES). In this abstract we discuss the relationship between obtained Fe(3+)/Sum of (Fe) ratios and alteration degrees by adding new data to our previous studies

Titanium Mass-balance Analysis of Paso Robles Soils: Elemental Gains and Losses as Affected by Acid Alteration Fluids

NASA Technical Reports Server (NTRS)

Sutter, Brad; Ming, Douglas W.

2010-01-01

The Columbia Hills soils have been exposed to aqueous alteration in alkaline [1] as well as acid conditions [2,3]. The Paso Robles class soils are bright soils that possess the highest S concentration of any soil measured on Mars [2]. Ferric-sulfate detection by Moessbauer analysis indicated that acid solutions were involved in forming these soils [4]. These soils are proposed to have formed by alteration of nearby rock by volcanic hydrothermal or fumarolic activity. The Paso Robles soils consist of the original Paso Robles-disturbed-Pasadena (PR-dist), Paso Robles- PasoLight (PR-PL), Arad-Samra, Arad-Hula, Tyrone- Berker Island1 and Tyrone-MountDarwin [2 ,3. ]Chemical characteristics indicate that the PR-dist and PR-PL soils could be derived from acid weathering of local Wishstone rocks while the Samra and Hula soils are likely derived from local Algonquin-Iroquet rock [3]. The Paso Robles soils were exposed to acidic sulfur bearing fluids; however, little else is known about the chemistry of the alteration fluid and its effects on the alteration of the proposed parent materials. The objectives of this work are to conduct titanium normalized mass-balance analysis to1) assess elemental gains and losses from the parent materials in the formation of the Paso Robles soils and 2) utilize this information to indicate the chemical nature of the alteration fluids.

Macroinvertebrate community change associated with the severity of streamflow alteration

USGS Publications Warehouse

Carlisle, Daren M.; Eng, Kenny; Nelson, S.M.

2014-01-01

Natural streamflows play a critical role in stream ecosystems, yet quantitative relations between streamflow alteration and stream health have been elusive. One reason for this difficulty is that neither streamflow alteration nor ecological responses are measured relative to their natural expectations. We assessed macroinvertebrate community condition in 25 mountain streams representing a large gradient of streamflow alteration, which we quantified as the departure of observed flows from natural expectations. Observed flows were obtained from US Geological Survey streamgaging stations and discharge records from dams and diversion structures. During low-flow conditions in September, samples of macroinvertebrate communities were collected at each site, in addition to measures of physical habitat, water chemistry and organic matter. In general, streamflows were artificially high during summer and artificially low throughout the rest of the year. Biological condition, as measured by richness of sensitive taxa (Ephemeroptera, Plecoptera and Trichoptera) and taxonomic completeness (O/E), was strongly and negatively related to the severity of depleted flows in winter. Analyses of macroinvertebrate traits suggest that taxa losses may have been caused by thermal modification associated with streamflow alteration. Our study yielded quantitative relations between the severity of streamflow alteration and the degree of biological impairment and suggests that water management that reduces streamflows during winter months is likely to have negative effects on downstream benthic communities in Utah mountain streams. 

The impact of transport processes on rare earth element patterns in marine authigenic and biogenic phosphates

NASA Astrophysics Data System (ADS)

Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

2017-04-01

Rare earth elements (REEs) are commonly used proxies to reconstruct water chemistry and oxygen saturation during the formation of authigenic and biogenic phosphates in marine environments. In the modern ocean REEs exhibit a distinct pattern with enrichment of heavy REEs and strong depletion in cerium (Ce). The wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry has been very different in the Earth's past. However, both early and late diagenesis are known to affect REE signatures in phosphates altering primary marine signals. Herein we present a dataset of REE signatures in 38 grain specific LA-ICP-MS measurements of isolated phosphate and carbonate grains in three discrete rock samples. The phosphates mainly consist of authigenic phosphates and phosphatized microfossils that formed in a microbially mediated micro-milieu. In addition, isolated biogenic and reworked phosphatic grains are also present. The phosphates are emplaced in bioclastic grain- to packstones deposited on a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene Monterey event. The results reveal markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Grain shape and REE patterns together indicate that authigenic, biogenic and reworked phosphates have distinct REE patterns irrespective of the sample. Our study shows that while REE patterns in phosphates do reflect water chemistry during authigenesis, they are often already heavily altered during reworking, a process, which can occur in geologically negligible timespans. REE patterns are therefore more likely to reflect complex enrichment processes after their formation. Similarities in the REE patterns of reworked and biogenic phosphate further suggest that the frequently observed hat-shaped pattern in biogenic phosphates can result from increased middle REE (Neodymium to Holmium) scavenging during taphonomic processes prior to final deposition. Cluster analysis coupled with sedimentological and previously published geochemical data (bulk carbon isotope and X-ray fluorescence spectrometry) allowed the characterization of REE patterns of phosphates in terms of their formation conditions and depositional history, such as the distinction of phosphates formed in situ from reworked and transported phosphate grains.

Host-guest chemistry of dendrimer-drug complexes. 4. An in-depth look into the binding/encapsulation of guanosine monophosphate by dendrimers.

PubMed

Hu, Jingjing; Fang, Min; Cheng, Yiyun; Zhang, Jiahai; Wu, Qinglin; Xu, Tongwen

2010-06-03

In the present study, we investigated the host-guest chemistry of dendrimer/guanosine monophosphate (GMP) and present an in-depth look into the binding/encapsulation of GMP by dendrimers using NMR studies. (1)H NMR spectra showed a significant downfield shift of methylene protons in the outmost layer of the G5 dendrimer, indicating the formation of ion pairs between cationic amine groups of dendrimer and anionic phosphate groups of GMP. Chemical shift titration results showed that the binding constant between G5 dendrimer and GMP is 17,400 M(-1) and each G5 dendrimer has 107 binding sites. The binding of GMP to dendrimers prevents its aggregation in aqueous solutions and thereby enhances its stability. Nuclear Overhauser effect measurements indicated that a GMP binding and encapsulation balance occurs on the surface and in the interior of dendrimer. The binding/encapsulation transitions can be easily tailored by altering the surface and interior charge densities of the dendrimer. All these findings provide a new insight into the host-guest chemistry of dendrimer/guest complexes and may play important roles in the study of dendrimer/DNA aggregates by a "bottom-up" strategy.

Changes in optical properties, chemistry, and micropore and mesopore characteristics of bituminous coal at the contact with dikes in the Illinois Basin

USGS Publications Warehouse

Mastalerz, Maria; Drobniak, A.; Schimmelmann, A.

2009-01-01

Changes in high-volatile bituminous coal (Pennsylvanian) near contacts with two volcanic intrusions in Illinois were investigated with respect to optical properties, coal chemistry, and coal pore structure. Vitrinite reflectance (Ro) increases from 0.62% to 5.03% within a distance of 5.5??m from the larger dike, and from 0.63% to 3.71% within 3.3??m from the small dike. Elemental chemistry of the coal shows distinct reductions in hydrogen and nitrogen content close to the intrusions. No trend was observed for total sulfur content, but decreases in sulfate content towards the dikes indicate thermochemical sulfate reduction (TSR). Contact-metamorphism has a dramatic effect on coal porosity, and microporosity in particular. Around the large dike, the micropore volume, after a slight initial increase, progressively decreases from 0.0417??cm3/g in coal situated 4.7??m from the intrusive contact to 0.0126??cm3/g at the contact. Strongly decreasing mesopore and micropore volumes in the altered zone, together with frequent cleat and fracture filling by calcite, indicate deteriorating conditions for both coalbed gas sorption and gas transmissibility. ?? 2008 Elsevier B.V. All rights reserved.

Shock and Laser Induced Non-Equilibrium Chemistry in Molecular Energetics

NASA Astrophysics Data System (ADS)

Wood, Mitchell; Cherukara, Mathew; Kober, Edward; Strachan, Alejandro

2015-06-01

In this study, we have used large scale reactive molecular dynamics (MD) simulations to study how contrasting initiation mechanisms from either shock or electromagnetic insults compare to traditional thermal initiation. We will show how insults of equal strength but different character can yield vastly different reaction profiles and thus the evolution of hot-spots. For shocked RDX (Up = 2km/s), we find that the collapse of a cylindrical 40 nm diameter pore leads to a significant amount of non-equilibrium reactions followed by the formation of a sustained deflagration wave. In contrast, a hot spot that is seeded into a statically compressed crystal with matching size and temperature will quench over the same timescale, highlighting the importance of insult type. Furthermore, MD simulations of electromagnetic insults coupled to intramolecular vibrations have shown, in some cases, mode specific initial chemistry and altered kinetics of the subsequent decomposition. By leveraging spectroscopic and chemical information gathered in our MD simulations, we have been able to identify and track non-equilibrium vibrational states of these materials and correlate them to these observed changes. Implications of insult dependent reactivity and non-equilibrium chemistry will be discussed.

Vertical variability in saturated zone hydrochemistry near Yucca Mountain, Nevada

USGS Publications Warehouse

Patterson, G.L.; Striffler, P.S.

2006-01-01

The differences in the saturated zone hydrochemistry with depth at borehole NC-EWDP-22PC reflect the addition of recharge along Fortymile Wash. The differences in water chemistry with depth at borehole NC-EWDP-19PB appear to indicate that other processes are involved. Water from the lower part of NC-EWDP-19PB possesses chemical characteristics that clearly indicate that it has undergone cation exchange that resulted in the removal of calcium and magnesium and the addition of sodium. This water is very similar to water from the Western Yucca Mountain facies that has previously been thought to flow west of NC-EWDP-19PB. Water from the lower zone in NC-EWDP-19PB also could represent water from the Eastern Yucca Mountain fades that has moved through day-bearing or zeolitized aquifer material resulting in the altered chemistry. Water chemistry from the upper part of the saturated zone at NC-EWDP-19PB, both zones at NC-EWDP-22PC, and wells in the Fortymile Wash facies appears to be the result of recharge through the alluvium south of Yucca Mountain and within the Fortymile Wash channel.

Elemental Gains/Losses Associated with Alteration Fractures in an Eolian Sandstone, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Ming, D. W.; Yen, A. S.; Gellert, R.; Sutter, B.; Berger, J. A.; Thompson, L. M.; Schmidt, M. E.; Morris, R. V.; Treiman, A. H.

2016-01-01

The Mars Science Laboratory rover Curiosity has traversed up section through approximately 100 m of sedimentary rocks deposited in fluvial, deltaic, lacustrine, and eolian environments (Bradbury group and overlying Mount Sharp group). The Stimson formation unconformably overlies a lacustrine mudstone at the base of the Mount Sharp group and has been interpreted to be a cross-bedded sandstone of lithified eolian dunes. Unaltered Stimson sandstone has a basaltic composition similar to the average Mars crustal composition, but is more variable and ranges to lower K and higher Al. Fluids passing through alteration "halos" adjacent to fractures have altered the chemistry and mineralogy of the sandstone. Elemental mass gains and losses in the alteration halos were quantified using immobile element concentrations, i.e., Ti (taus). Alteration halos have elemental gains in Si, Ca, S, and P and large losses in Al, Fe, Mn, Mg, Na, K, Ni, and Zn. Mineralogy of the altered Stimson is dominated by Ca-sulfates, Si-rich X-ray amorphous materials along with plagioclase feldspar, magnetite, and pyroxenes. The igneous phases were less abundant in the altered sandstone with a lower pyroxene/plagioclase feldspar. Large elemental losses suggest acidic fluids initially removed these elements (Al mobile under acid conditions). Enrichments in Si, Ca, and S suggest secondary fluids (possibly alkaline) passed through these fractures leaving behind X-ray amorphous Si and Ca-sulfates. The mechanism for the large elemental gains in P is unclear. The geochemistry and mineralogy of the altered sandstone suggests a complicated diagenetic history with multiple episodes of aqueous alteration under a variety of environmental conditions (e.g., acidic, alkaline).

Alteration of immature sedimentary rocks on Earth and Mars. Recording Aqueous and Surface-atmosphere Processes

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

Cannon, Kenneth M.; Mustard, John F.; Salvatore, Mark R.

The rock alteration and rind formation in analog environments like Antarctica may provide clues to rock alteration and therefore paleoclimates on Mars. Clastic sedimentary rocks derived from basaltic sources have been studied in situ by martian rovers and are likely abundant on the surface of Mars. Moreover, how such rock types undergo alteration when exposed to different environmental conditions is poorly understood compared with alteration of intact basaltic flows. Here we characterize alteration in the chemically immature Carapace Sandstone from Antarctica, a terrestrial analog for martian sedimentary rocks. We employ a variety of measurements similar to those used on previousmore » and current Mars missions. Laboratory techniques included bulk chemistry, powder X-ray diffraction (XRD), hyperspectral imaging and X-ray absorption spectroscopy. Through these methods we find that primary basaltic material in the Carapace Sandstone is pervasively altered to hydrated clay minerals and palagonite as a result of water–rock interaction. A thick orange rind is forming in current Antarctic conditions, superimposing this previous aqueous alteration signature. The rind exhibits a higher reflectance at visible-near infrared wavelengths than the rock interior, with an enhanced ferric absorption edge likely due to an increase in Fe 3+ of existing phases or the formation of minor iron (oxy)hydroxides. This alteration sequence in the Carapace Sandstone results from decreased water–rock interaction over time, and weathering in a cold, dry environment, mimicking a similar transition early in martian history. This transition may be recorded in sedimentary rocks on Mars through a similar superimposition mechanism, capturing past climate changes at the hand sample scale. These results also suggest that basalt-derived sediments could have sourced significant volumes of hydrated minerals on early Mars due to their greater permeability compared with intact igneous rocks.« less

Development of a sensitive monitor for hydrazine

NASA Technical Reports Server (NTRS)

Eiceman, Gary A.; Limero, Thomas; James, John T.

1991-01-01

The development of hand-held, ambient-temperature instruments that utilize ion mobility spectrometry (IMS) in the detection of hydrazine and monomethylhydrazine is reviewed. A development effort to eliminate ammonia interference through altering the ionization chemistry, based on adding 5-nonanone as dopant in the ionization region of the IMS, is presented. Calibration of this instrument conducted before and after STS-37 revealed no more than a 5 percent difference between calibration curves, without any appreciable loss of equipment function.

Understanding improved osteoblast behavior on select nanoporous anodic alumina

PubMed Central

Ni, Siyu; Li, Changyan; Ni, Shirong; Chen, Ting; Webster, Thomas J

2014-01-01

The aim of this study was to prepare different sized porous anodic alumina (PAA) and examine preosteoblast (MC3T3-E1) attachment and proliferation on such nanoporous surfaces. In this study, PAA with tunable pore sizes (25 nm, 50 nm, and 75 nm) were fabricated by a two-step anodizing procedure in oxalic acid. The surface morphology and elemental composition of PAA were characterized by field emission scanning electron microscopy and X-ray photoelectron spectroscopy analysis. The nanopore arrays on all of the PAA samples were highly regular. X-ray photoelectron spectroscopy analysis suggested that the chemistry of PAA and flat aluminum surfaces were similar. However, contact angles were significantly greater on all of the PAA compared to flat aluminum substrates, which consequently altered protein adsorption profiles. The attachment and proliferation of preosteoblasts were determined for up to 7 days in culture using field emission scanning electron microscopy and a Cell Counting Kit-8. Results showed that nanoporous surfaces did not enhance initial preosteoblast attachment, whereas preosteoblast proliferation dramatically increased when the PAA pore size was either 50 nm or 75 nm compared to all other samples (P<0.05). Thus, this study showed that one can alter surface energy of aluminum by modifying surface nano-roughness alone (and not changing chemistry) through an anodization process to improve osteoblast density, and, thus, should be further studied as a bioactive interface for orthopedic applications. PMID:25045263

Using fish communities to assess streams in Romania: Initial development of an index of biotic integrity

USGS Publications Warehouse

Angermeier, P.L.; Davideanu, G.

2004-01-01

Multimetric biotic indices increasingly are used to complement physicochemical data in assessments of stream quality. We initiated development of multimetric indices, based on fish communities, to assess biotic integrity of streams in two physiographic regions of central Romania. Unlike previous efforts to develop such indices for European streams, our metrics and scoring criteria were selected largely on the basis of empirical relations in the regions of interest. We categorised 54 fish species with respect to ten natural-history attributes, then used this information to compute 32 candidate metrics of five types (taxonomic, tolerance, abundance, reproductive, and feeding) for each of 35 sites. We assessed the utility of candidate metrics for detecting anthropogenic impact based on three criteria: (a) range of values taken, (b) relation to a site-quality index (SQI), which incorporated information on hydrologic alteration, channel alteration, land-use intensity, and water chemistry, and (c) metric redundancy. We chose seven metrics from each region to include in preliminary multimetric indices (PMIs). Both PMIs included taxonomic, tolerance, and feeding metrics, but only two metrics were common to both PMIs. Although we could not validate our PMIs, their strong association with the SQI in each region suggests that such indices would be valuable tools for assessing stream quality and could provide more comprehensive assessments than the traditional approaches based solely on water chemistry.

Chemistry-driven structural alterations in short-term retrieved ceramic-on-metal hip implants: Evidence for in vivo incompatibility between ceramic and metal counterparts.

PubMed

Zhu, Wenliang; Pezzotti, Giuseppe; Boffelli, Marco; Chotanaphuti, Thanainit; Khuangsirikul, Saradej; Sugano, Nobuhiko

2017-08-01

Ceramic-on-metal (CoM) hip implants were reported to experience lower wear rates in vitro as compared to metal-on-metal (MoM) bearings, thus hinting metal-ion release at lower levels in vivo. In this article, we show a spectroscopic study of two short-term retrieval cases of zirconia-toughened alumina (ZTA) femoral heads belonging to CoM hip prostheses, which instead showed poor wear performances in vivo. Metal contamination and abnormally high fractions of tetragonal-to-monoclinic (t→m) polymorphic transformation of the zirconia phase could be found on both ZTA heads, which contrasted with the optimistic predictions of in vitro experiments. At the molecular scale, incorporation of metal ions into the ceramic lattices could be recognized as due to frictionally assisted phenomena occurring at the ceramic surface. Driven by abnormal friction, diffusion of metal ions induced lattice shrinkage in the zirconia phases, while residual stress fields became stored at the surface of the femoral head. Diffusional alterations destabilized the chemistry of the ceramic surface and resulted in an abnormal increase in t→m phase transformation in vivo. Frictionally driven metal transfer to the ceramic lattice thus hinders the in vivo performance of CoM prostheses. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1469-1480, 2017. © 2016 Wiley Periodicals, Inc.

Effects of multiple climate change factors on the tall fescue-fungal endophyte symbiosis: infection frequency and tissue chemistry.

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

Brosi, Glade; McCulley, Rebecca L; Bush, L P

Climate change (altered CO{sub 2}, warming, and precipitation) may affect plant-microbial interactions, such as the Lolium arundinaceum-Neotyphodium coenophialum symbiosis, to alter future ecosystem structure and function. To assess this possibility, tall fescue tillers were collected from an existing climate manipulation experiment in a constructed old-field community in Tennessee (USA). Endophyte infection frequency (EIF) was determined, and infected (E+) and uninfected (E-) tillers were analysed for tissue chemistry. The EIF of tall fescue was higher under elevated CO{sub 2} (91% infected) than with ambient CO{sub 2} (81%) but was not affected by warming or precipitation treatments. Within E+ tillers, elevated CO{submore » 2} decreased alkaloid concentrations of both ergovaline and loline, by c. 30%; whereas warming increased loline concentrations 28% but had no effect on ergovaline. Independent of endophyte infection, elevated CO{sub 2} reduced concentrations of nitrogen, cellulose, hemicellulose, and lignin. These results suggest that elevated CO{sub 2}, more than changes in temperature or precipitation, may promote this grass-fungal symbiosis, leading to higher EIF in tall fescue in old-field communities. However, as all three climate factors are likely to change in the future, predicting the symbiotic response and resulting ecological consequences may be difficult and dependent on the specific atmospheric and climatic conditions encountered.« less

Synthesis of Amino Acid Precursors with Organic Solids in Planetesimals with Liquid Water

NASA Technical Reports Server (NTRS)

Kebukawa, Y; Misawa, S.; Matsukuma, J.; Chan, Q. H. S.; Kobayashi, J.; Tachibana, S.; Zolensky, M. E.

2017-01-01

Amino acids are important ingredients of life that would have been delivered to Earth by extraterrestrial sources, e.g., comets and meteorites. Amino acids are found in aqueously altered carbonaceous chondrites in good part in the form of precursors that release amino acids after acid hydrolysis. Meanwhile, most of the organic carbon (greater than 70 weight %) in carbonaceous chondrites exists in the form of solvent insoluble organic matter (IOM) with complex macromolecular structures. Complex macromolecular organic matter can be produced by either photolysis of interstellar ices or aqueous chemistry in planetesimals. We focused on the synthesis of amino acids during aqueous alteration, and demonstrated one-pot synthesis of a complex suite of amino acids simultaneously with IOM via hydrothermal experiments simulating the aqueous processing

Evidence of Phyllosilicate in Wooly Patch+: An Altered Rock Encountered on the Spirit Rover Traverse

NASA Technical Reports Server (NTRS)

Wang, Alian; Haskin, Larry A.; Korotev, Randy L.; Jolliff, Brad L.; deSouza, Paulo, Jr.; Kusack, Alastair G.

2005-01-01

In the course of examining rocks along the traverse of the Spirit rover toward the Columbia Hills [1, 9], we noticed that the chemistry of a rock named "Wooly Patch" was neither basaltic as the rocks near the landing site [8] nor slightly altered basalt inferred from regolith in plains trenches [10]. The major cation ratios appear to match those of phyllosilicates [11]. The presence of phyllosilicate minerals on Mars has been predicted [12]; reasons for the rarity or absence of phyllosilicates have also been discussed [13]. We have thus done as detailed an analysis of Wooly Patch as the data enable, which suggests phyllosilicates of kaolinite, serpentine, and chlorite types, plus some feldspar and pyroxene are prime candidates to constitute Wooly Patch.

Can oral rehydration solution be safely flavored at home?

PubMed

Nijssen-Jordan, C

1997-12-01

To determine the concentration of sodium, potassium, glucose, and osmolality of oral rehydration solutions (ORS) which have been flavored with varying amounts of unsweetened Kool-Aid powder, Jell-O powder, apple juice, or orange juice. Descriptive. Alberta Children's Hospital Chemistry Laboratory. None. Addition of varying amounts of flavoring easily available in all households to commercially available unsweetened ORS. Concentrations of electrolytes, glucose, and osmolality. Addition of fruit juices or flavor powders to commercially produced ORS does alter the electrolyte content and osmolality. When limited amounts of flavoring or juice is added, the osmolality of the solution approaches iso-osmolality. Small amounts of unsweetened Kool-Aid powder, Jell-O powder, and apple or orange juice can be added to oral rehydration solutions without significantly altering electrolyte composition and osmolality.

Water chemistry at Snowshoe Mountain, Colorado: mixed processes in a common bedrock

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.

2001-01-01

At Snowshoe Mountain the primary bedrock is quite homogeneous, but weathering processes vary as waters moves through the soils, vadose zone and phreatic zone of the subsurface. In the thin soil, physical degradation of tuff facilitates preferential dissolution of potassium ion from glass within the rock matrix, while other silicate minerals remain unaltered. In the vadose zone, in the upper few meters of fractured bedrock, dilute water infiltrates during spring snowmelt and summer storms, leading to preferential dissolution of augite exposed on fracture surfaces. Deeper yet, in the phreatic zone of the fractured bedrock, Pleistocene calcite fracture fillings dissolve, and dioctahedral and trioctahedral clays form as penetrative weathering alters feldspar and pyroxene. Alkalinity is generated and silica concentrations are buffered by mineral alteration reactions.

The NOx dependence of bromine chemistry in the Arctic atmospheric boundary layer

NASA Astrophysics Data System (ADS)

Custard, K. D.; Thompson, C. R.; Pratt, K. A.; Shepson, P. B.; Liao, J.; Huey, L. G.; Orlando, J. J.; Weinheimer, A. J.; Apel, E.; Hall, S. R.; Flocke, F.; Mauldin, L.; Hornbrook, R. S.; Pöhler, D.; General, S.; Zielcke, J.; Simpson, W. R.; Platt, U.; Fried, A.; Weibring, P.; Sive, B. C.; Ullmann, K.; Cantrell, C.; Knapp, D. J.; Montzka, D. D.

2015-03-01

Arctic boundary layer nitrogen oxides (NOx = NO2 + NO) are naturally produced in and released from the sunlit snowpack and range between 10 to 100 pptv in the remote background surface layer air. These nitrogen oxides have significant effects on the partitioning and cycling of reactive radicals such as halogens and HOx (OH + HO2). However, little is known about the impacts of local anthropogenic NOx emission sources on gas-phase halogen chemistry in the Arctic, and this is important because these emissions can induce large variability in ambient NOx and thus local chemistry. In this study, a zero-dimensional photochemical kinetics model was used to investigate the influence of NOx on the unique springtime halogen and HOx chemistry in the Arctic. Trace gas measurements obtained during the 2009 OASIS (Ocean-Atmosphere-Sea Ice-Snowpack) field campaign at Barrow, AK were used to constrain many model inputs. We find that elevated NOx significantly impedes gas-phase radical chemistry, through the production of a variety of reservoir species, including HNO3, HO2NO2, peroxyacetyl nitrate (PAN), BrNO2, ClNO2 and reductions in BrO and HOBr, with a concomitant, decreased net O3 loss rate. The effective removal of BrO by anthropogenic NOx was directly observed from measurements conducted near Prudhoe Bay, AK during the 2012 Bromine, Ozone, and Mercury Experiment (BROMEX). Thus, while changes in snow-covered sea ice attributable to climate change may alter the availability of molecular halogens for ozone and Hg depletion, predicting the impact of climate change on polar atmospheric chemistry is complex and must take into account the simultaneous impact of changes in the distribution and intensity of anthropogenic combustion sources. This is especially true for the Arctic, where NOx emissions are expected to increase because of increasing oil and gas extraction and shipping activities.

The origin of soil organic matter controls its composition and bioreactivity across a mesic boreal forest latitudinal gradient

NASA Astrophysics Data System (ADS)

Kohl, L.; Philben, M. J.; Edwards, K. A.; Podrebarac, F. A.; Jamie, W.; Ziegler, S. E.

2017-12-01

Warmer climates have been associated with reduced soil organic matter (SOM) bioreactivity, lower respiration rates at a given temperature, which is typically attributed to the presence of more decomposed SOM. Cross site studies, however, indicate that ecosystem regime shifts associated with long-term climate warming can affect SOM properties through changes in vegetation and plant litter inputs to soils. The relative importance of these two controls, diagenesis and inputs, on SOM properties as ecosystems experience climate warming remains poorly understood. To address this, we characterized the elemental, chemical (nuclear magnetic resonance spectroscopy and total hydrolysable amino acids), and isotopic composition of plant litter and SOM across a well-constrained mesic boreal forest latitudinal transect in Atlantic Canada. Results across forest sites within each of three climate regions indicated that (1) climate history and diagenesis affect distinct parameters of SOM chemistry, (2) increases in SOM bioreactivity with latitude were associated with elevated proportions of carbohydrates relative to plant waxes and lignin, and (3) despite the common forest type across regions, differences in SOM chemistry by climate region were associated with chemically distinct litter inputs and not different degrees of diagenesis. Climate effects on vascular plant litter chemistry explained only part of the regional differences in SOM chemistry, most notably the higher protein content of SOM from warmer regions. Greater proportions of lignin and aliphatic compounds and smaller proportions of carbohydrates in warmer sites' soils were explained by the higher proportion of vascular plant relative to moss litter in the warmer forests. These results indicate that a climate induced decrease in the proportion of moss inputs will not only impact SOM chemistry but also increase the resistance of SOM to decomposition, thus significantly altering SOM cycling in these boreal forest soils.

Effects of tropical cyclones on river chemistry: A case study of the lower Pearl River during Hurricanes Gustav and Ike

NASA Astrophysics Data System (ADS)

Cai, Yihua; Guo, Laodong; Wang, Xuri; Lohrenz, Steven E.; Mojzis, Allison K.

2013-09-01

To investigate the effects of tropical cyclones on the water chemistry of Gulf of Mexico coastal rivers, time series samples from the lower Pearl River at Stennis Space Center, Mississippi, were collected on August and September, 2008, during Hurricanes Gustav and Ike. Hurricane Gustav, which landed near the sampling site, caused intensive storm surge and strong seawater intrusion, resulting in an elevated salinity of 7.5 in the lower Pearl River and subsequent flooding induced by heavy rainfall. Hurricane Ike, which passed further away from the sampling site, caused only a mild seawater intrusion with a salinity of 1.2 at the sampling site. The river showed distinct variations in water chemistry corresponding to different hydrographic disturbance of hurricanes. Abrupt increase of suspended particulate matter and associated organic carbon and nitrogen concentrations coincided with the intensive storm surge due to coastal sediment resuspension. A remarkable drop in the concentrations of phosphate and dissolved organic matter was also observed during the intense seawater intrusion, a result of both dilution by seawater and resultant flocculation of dissolved organic matter. During hurricane-induced flooding, the river showed a mild increase in the concentrations of organic matter, reflecting a dominant contribution of terrestrial inputs from the watershed by surface runoffs while the concentrations of inorganic nutrient species in the river water decreased. In contrast, water chemistry in the Pearl River underwent little change in most carbon and nutrient species under the mild seawater intrusion. Overall, tropical cyclones could induce unique variations in coastal river water chemistry and variable material export which would further alter the coastal water quality.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

2016-06-01

Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

Evolution of Early Paleoproterozoic Ocean Chemistry as Recorded by Black Shales

NASA Astrophysics Data System (ADS)

Scott, C.; Bekker, A.; Lyons, T. W.; Planavsky, N. J.; Wing, B. A.

2010-12-01

In recent years, Precambrian biogeochemists have focused largely on the abundance, speciation and isotopic composition of major and trace elements preserved in organic carbon-rich black shales in order to track the co-evolution of ocean chemistry and life on Earth. Despite the fact that the period from 2.5 to 2.0 Ga hosted major events in Earth’s history, such as the Great Oxidation Event (GOE), an era of global glaciations, a massive and long-lived carbon isotope excursion and the end to banded iron formation (BIF) deposition, each with the potential to directly alter global biogeochemical cycles, it is perhaps best known for its unknowns. In order to help close this gap in our understanding of the evolution of Precambrian ocean chemistry we present a detailed biogeochemical study of Paleoproterozoic black shales deposited between 2.5 and 2.0 Ga. Our study integrates Fe speciation, trace metal chemistry and C, S and N isotope analyses to provide a thorough characterization of marine biogeochemical cycles as they responded to the GOE and set the stage for the demise of BIFs at ca. 1.8 Ga. Our data reveal an ocean that was both surprising similar to, and demonstrably different from, Archean and later Proterozoic oceans. Of particular interest, we find that ferruginous and euxinic conditions co-existed during this period and that sea water trace metal inventories fluctuated dramatically in conjunction with major carbon isotope excursions. By comparing our Paleoproterozoic contribution with recent biogeochemical studies of other Precambrian black shales we can begin to track first order changes in ocean chemistry without the major time gaps that have plagued previous attempts.

Ion microprobe, electron microprobe and cathodoluminescence data for Allende inclusions with emphasis on plagioclase chemistry

NASA Technical Reports Server (NTRS)

Hutcheon, I. D.; Steele, I. M.; Smith, J. V.; Clayton, R. N.

1978-01-01

Three Type B inclusions from the Allende meteorite have been analyzed. A grain-to-grain characterization of mineral chemistry and isotopic content was made possible by the use of a range of techniques, including luminescence and scanning electron microscopy and electron and ion microprobe analysis. Cathodoluminescence was used in fine-grained, optically opaque regions to distinguish between sub-micrometer phases, such as garnet and Si-rich material, subsequently identified by electron probe and scanning electron microscope analyses. Four types of luminescence patterns, due to twinning, primary sector zoning, alteration of boundaries and fractures, and shock effects, were identified in Allende plagioclase. Luminescence color exhibited a strong correlation with Mg content and provided a guide for an electron probe quantitative map of Mg and Na distributions. Ion microprobe studies of individual grains revealed large excesses of Mg-26.

Petrology of Impact-Melt Rocks at the Chicxulub Multiring Basin, Yucatan, Mexico

NASA Technical Reports Server (NTRS)

Schuraytz, Benjamin C.; Sharpton, Virgil L.; Marin, Luis E.

1994-01-01

Compositions and textures of melt rocks from the upper part of the Chicxulub structure are typical of melt rocks at other large terrestrial impact structures. Apart from variably elevated iridium concentrations (less than 1.5 to 13.5 +/- 0.9 ppb) indicating nonuniform dissemination of a meteoritic component, bulk rock and phenocryst compositions imply that these melt rocks were derived exclusively from continental crust and platform-sediment target lithologies. Modest differences in bulk chemistry among samples from wells located approximately 40 km apart suggest minor variations in relative contributions of these target lithologies to the melts. Subtle variations in the compositions of early-formed pyroxene and plagioclase also support minor primary differences in chemistry between the melts. Evidence for pervasive hydrothermal alteration of the porous mesostasis includes albite, K-feldspar, quartz, epidote, chlorite, and other phyllosilicates, as well as siderophile element-enriched sulfides, suggesting the possibility that Chicxulub, like Sudbury, may host important ore deposits.

Indoles as therapeutics of interest in medicinal chemistry: Bird's eye view.

PubMed

Chadha, Navriti; Silakari, Om

2017-07-07

Indoles constitute extensively explored heterocyclic ring systems with wide range of applications in pathophysiological conditions that is, cancer, microbial and viral infections, inflammation, depression, migraine, emesis, hypertension, etc. Presence of indole nucleus in amino acid tryptophan makes it prominent in phytoconstituents such as perfumes, neurotransmitters, auxins (plant hormones), indole alkaloids etc. The interesting molecular architecture of indole makes them suitable candidates for the drug development. This review article provides an overview of the chemistry, biology, and toxicology of indoles focusing on their application as drugs. Our effort is to corroborate the information available on the natural indole alkaloids, indole based FDA approved drugs and clinical trial candidates having diverse therapeutic implementations. This compiled information may serve as a benchmark for the alteration of existing ligands to design novel potent molecules with lesser side effects. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Motorization of China implies changes in Pacific air chemistry and primary production

NASA Astrophysics Data System (ADS)

Elliott, Scott; Blake, Donald R.; Duce, Robert A.; Lai, C. Aaron; McCreary, Iain; McNair, Laurie A.; Rowland, F. Sherwood; Russell, Armistead G.; Streit, Gerald E.; Turco, Richard P.

1997-11-01

The People's Republic of China, the world's most populous nation, is considering extensive development of its automotive transportation infrastructure. Upper limits to the associated pollution increases can be defined through scenarios with Western style vehicles and vehicle-to-person ratios. Here we construct estimates of fundamental changes to chemistry of the Pacific ocean/atmosphere system through simple budgeting procedures. Regional increases in tropospheric ozone could reach tens of parts per billion. Observations/experiments suggest that enhanced nitrogen oxides will react with sea salt aerosols to yield chlorine atoms in the marine boundary layer. Nitrate deposition onto the open sea surface would support several percent of exported North Pacific carbon production. Transport of biologically active iron to surface waters may follow from increases in mineral dust and acid sulfate aerosols. Altered plankton ecodynamics will feed back into climate processes through sea to air flux of reduced sulfur gases and through carbon dioxide drawdown.

Macro-/micro-environment-sensitive chemosensing and biological imaging.

PubMed

Yang, Zhigang; Cao, Jianfang; He, Yanxia; Yang, Jung Ho; Kim, Taeyoung; Peng, Xiaojun; Kim, Jong Seung

2014-07-07

Environment-related parameters, including viscosity, polarity, temperature, hypoxia, and pH, play pivotal roles in controlling the physical or chemical behaviors of local molecules. In particular, in a biological environment, such factors predominantly determine the biological properties of the local environment or reflect corresponding status alterations. Abnormal changes in these factors would cause cellular malfunction or become a hallmark of the occurrence of severe diseases. Therefore, in recent years, they have increasingly attracted research interest from the fields of chemistry and biological chemistry. With the emergence of fluorescence sensing and imaging technology, several fluorescent chemosensors have been designed to respond to such parameters and to further map their distributions and variations in vitro/in vivo. In this work, we have reviewed a number of various environment-responsive chemosensors related to fluorescent recognition of viscosity, polarity, temperature, hypoxia, and pH that have been reported thus far.

Low-Temperature Alteration of the Seafloor: Impacts on Ocean Chemistry

NASA Astrophysics Data System (ADS)

Coogan, Laurence A.; Gillis, Kathryn M.

2018-05-01

Over 50% of Earth is covered by oceanic crust, the uppermost portion of which is a high-permeability layer of basaltic lavas through which seawater continuously circulates. Fluid flow is driven by heat lost from the oceanic lithosphere; the global fluid flux is dependent on plate creation rates and the thickness and distribution of overlying sediment, which acts as a low-permeability layer impeding seawater access to the crust. Fluid-rock reactions in the crust, and global chemical fluxes, depend on the average temperature in the aquifer, the fluid flux, and the composition of seawater. The average temperature in the aquifer depends largely on bottom water temperature and, to a lesser extent, on the average seafloor sediment thickness. Feedbacks between off-axis chemical fluxes and their controls may play an important role in modulating ocean chemistry and planetary climate on long timescales, but more work is needed to quantify these feedbacks.

Biological Chemistry and Functionality of Protein Sulfenic Acids and Related Thiol Modifications

PubMed Central

Devarie-Baez, Nelmi O.; Silva Lopez, Elsa I.; Furdui, Cristina M.

2016-01-01

Selective modification of proteins at cysteine residues by reactive oxygen, nitrogen or sulfur species formed under physiological and pathological states is emerging as a critical regulator of protein activity impacting cellular function. This review focuses primarily on protein sulfenylation (-SOH), a metastable reversible modification connecting reduced cysteine thiols to many products of cysteine oxidation. An overview is first provided on the chemistry principles underlining synthesis, stability and reactivity of sulfenic acids in model compounds and proteins, followed by a brief description of analytical methods currently employed to characterize these oxidative species. The following chapters present a selection of redox-regulated proteins for which the -SOH formation was experimentally confirmed and linked to protein function. These chapters are organized based on the participation of these proteins in the regulation of signaling, metabolism and epigenetics. The last chapter discusses the therapeutic implications of altered redox microenvironment and protein oxidation in disease. PMID:26340608

Workshop on Parent-Body and Nebular Modification of Chondritic Materials

NASA Technical Reports Server (NTRS)

Zolensky, M. E. (Editor); Krot, A. N. (Editor); Scott, E. R. D. (Editor)

1997-01-01

Topics considered include: thermal Metamorphosed Antarctic CM and CI Carbonaceous Chondrites in Japanese Collections, and Transformation Processes of Phyllosilicates; use of Oxygen Isotopes to Constrain the Nebular and Asteroidal Modification of Chondritic Materials; effect of Revised Nebular Water Distribution on Enstatite Chondrite Formation; interstellar Hydroxyls in Meteoritic Chondrules: Implications for the Origin of Water in the Inner Solar System; theoretical Models and Experimental Studies of Gas-Grain Chemistry in the Solar Nebula; chemical Alteration of Chondrules on Parent Bodies; thermal Quenching of Silicate Grains in Protostellar Sources; an Experimental Study of Magnetite Formation in the Solar Nebula; the Kaidun Meteorite: Evidence for Pre- and Postaccretionary Aqueous Alteration; a Transmission Electron Microscope Study of the Matrix Mineralogy of the Leoville CV3 (Reduced-Group) Carbonaceous Chondrite: Nebular and Parent-Body Features; rubidium-Strontium Isotopic Systematic of Chondrules from the Antarctic CV Chondrites Yamato 86751 and Yamato 86009: Additional Evidence for Late Parent-Body Modification; oxygen-Fugacity Indicators in Carbonaceous Chondrites: Parent-Body Alteration or High-Temperature Nebular Oxidation; thermodynamic Modeling of Aqueous Alteration in CV Chondrites; asteroidal Modification of C and O Chondrites: Myths and Models; oxygen Fugacity in the Solar Nebular; and the History of Metal and Sulfides in Chondrites.

Chromite alteration processes within Vourinos ophiolite

NASA Astrophysics Data System (ADS)

Grieco, Giovanni; Merlini, Anna

2012-09-01

The renewed interest in chromite ore deposits is directly related to the increase in Cr price ruled by international market trends. Chromite, an accessory mineral in peridotites, is considered to be a petrogenetic indicator because its composition reflects the degree of partial melting that the mantle experienced while producing the chromium spinel-bearing rock (Burkhard in Geochim Cosmochim Acta 57:1297-1306, 1993). However, the understanding of chromite alteration and metamorphic modification is still controversial (e.g. Evans and Frost in Geochim Cosmochim Acta 39:959-972, 1975; Burkhard in Geochim Cosmochim Acta 57:1297-1306, 1993; Oze et al. in Am J Sci 304:67-101, 2004). Metamorphic alteration leads to major changes in chromite chemistry and to the growth of secondary phases such as ferritchromite and chlorite. In this study, we investigate the Vourinos complex chromitites (from the mines of Rizo, Aetoraches, Xerolivado and Potamia) with respect to textural and chemical analyses in order to highlight the most important trend of alteration related to chromite transformation. The present study has been partially funded by the Aliakmon project in collaboration between the Public Power Corporation of Greece and Institute of Geology and Mineral Exploration of Kozani.

Using Workflows to Explore and Optimise Named Entity Recognition for Chemistry

PubMed Central

Kolluru, BalaKrishna; Hawizy, Lezan; Murray-Rust, Peter; Tsujii, Junichi; Ananiadou, Sophia

2011-01-01

Chemistry text mining tools should be interoperable and adaptable regardless of system-level implementation, installation or even programming issues. We aim to abstract the functionality of these tools from the underlying implementation via reconfigurable workflows for automatically identifying chemical names. To achieve this, we refactored an established named entity recogniser (in the chemistry domain), OSCAR and studied the impact of each component on the net performance. We developed two reconfigurable workflows from OSCAR using an interoperable text mining framework, U-Compare. These workflows can be altered using the drag-&-drop mechanism of the graphical user interface of U-Compare. These workflows also provide a platform to study the relationship between text mining components such as tokenisation and named entity recognition (using maximum entropy Markov model (MEMM) and pattern recognition based classifiers). Results indicate that, for chemistry in particular, eliminating noise generated by tokenisation techniques lead to a slightly better performance than others, in terms of named entity recognition (NER) accuracy. Poor tokenisation translates into poorer input to the classifier components which in turn leads to an increase in Type I or Type II errors, thus, lowering the overall performance. On the Sciborg corpus, the workflow based system, which uses a new tokeniser whilst retaining the same MEMM component, increases the F-score from 82.35% to 84.44%. On the PubMed corpus, it recorded an F-score of 84.84% as against 84.23% by OSCAR. PMID:21633495

Structure-to-property relationships in fuel cell catalyst supports: Correlation of surface chemistry and morphology with oxidation resistance of carbon blacks

NASA Astrophysics Data System (ADS)

Artyushkova, Kateryna; Pylypenko, Svitlana; Dowlapalli, Madhu; Atanassov, Plamen

2012-09-01

Linking durability of carbon blacks, expressed as their oxidation resistance, used in PEMFCs as catalyst supports, with their chemistry and morphology is an important task towards designing carbon blacks with desired properties. Structure-to-property relationship between surface chemistry determined by X-ray photoelectron spectroscopy (XPS), morphological structure determined by digital image processing of scanning electron microscopy (SEM) images, physical properties, and electrochemical corrosion behavior determined in an air-breathing gas-diffusion electrode is studied for several un-altered and several modified carbon blacks. We are showing that surface chemistry, graphitic content and certain physical characteristics such as Brunauer-Emmett-Teller (BET) surface area and pore volume, determined by nitrogen adsorptions are not sufficient to explain high corrosion instability of types of carbon blacks. Inclusion of morphological characteristics, such as roughness, texture and shape parameters provide for more inclusive description and therefore more complete structure-to-property correlations of corrosion behavior of carbon blacks. This paper presents the first direct statistically-derived structure-to-property relationship, developed by multivariate analysis (MVA) that links chemical and physical structural properties of the carbon blacks to their critical properties as supports for PEMFC catalysts. We have found that balance between electrocatalytic activity and high resistance towards oxidation and corrosion is achieved by balance between amount of graphitic content and surface oxide coverage, smaller overall roughness and, finally, larger amount of big elongated and loose, and, hypothetically, more hydrophobic pores.

Using workflows to explore and optimise named entity recognition for chemistry.

PubMed

Kolluru, Balakrishna; Hawizy, Lezan; Murray-Rust, Peter; Tsujii, Junichi; Ananiadou, Sophia

2011-01-01

Chemistry text mining tools should be interoperable and adaptable regardless of system-level implementation, installation or even programming issues. We aim to abstract the functionality of these tools from the underlying implementation via reconfigurable workflows for automatically identifying chemical names. To achieve this, we refactored an established named entity recogniser (in the chemistry domain), OSCAR and studied the impact of each component on the net performance. We developed two reconfigurable workflows from OSCAR using an interoperable text mining framework, U-Compare. These workflows can be altered using the drag-&-drop mechanism of the graphical user interface of U-Compare. These workflows also provide a platform to study the relationship between text mining components such as tokenisation and named entity recognition (using maximum entropy Markov model (MEMM) and pattern recognition based classifiers). Results indicate that, for chemistry in particular, eliminating noise generated by tokenisation techniques lead to a slightly better performance than others, in terms of named entity recognition (NER) accuracy. Poor tokenisation translates into poorer input to the classifier components which in turn leads to an increase in Type I or Type II errors, thus, lowering the overall performance. On the Sciborg corpus, the workflow based system, which uses a new tokeniser whilst retaining the same MEMM component, increases the F-score from 82.35% to 84.44%. On the PubMed corpus, it recorded an F-score of 84.84% as against 84.23% by OSCAR.

Species and tissue type regulate long-term decomposition of brackish marsh plants grown under elevated CO2 conditions

NASA Astrophysics Data System (ADS)

Jones, Joshua A.; Cherry, Julia A.; McKee, Karen L.

2016-02-01

Organic matter accumulation, the net effect of plant production and decomposition, contributes to vertical soil accretion in coastal wetlands, thereby playing a key role in whether they keep pace with sea-level rise. Any factor that affects decomposition may affect wetland accretion, including atmospheric CO2 concentrations. Higher CO2 can influence decomposition rates by altering plant tissue chemistry or by causing shifts in plant species composition or biomass partitioning. A combined greenhouse-field experiment examined how elevated CO2 affected plant tissue chemistry and subsequent decomposition of above- and belowground tissues of two common brackish marsh species, Schoenoplectus americanus (C3) and Spartina patens (C4). Both species were grown in monoculture and in mixture under ambient (350-385 μL L-1) or elevated (ambient + 300 μL L-1) atmospheric CO2 conditions, with all other growth conditions held constant, for one growing season. Above- and belowground tissues produced under these treatments were decomposed under ambient field conditions in a brackish marsh in the Mississippi River Delta, USA. Elevated CO2 significantly reduced nitrogen content of S. americanus, but not sufficiently to affect subsequent decomposition. Instead, long-term decomposition (percent mass remaining after 280 d) was controlled by species composition and tissue type. Shoots of S. patens had more mass remaining (41 ± 2%) than those of S. americanus (12 ± 2%). Belowground material decomposed more slowly than that placed aboveground (62 ± 1% vs. 23 ± 3% mass remaining), but rates belowground did not differ between species. Increases in atmospheric CO2 concentration will likely have a greater effect on overall decomposition in this brackish marsh community through shifts in species dominance or biomass allocation than through effects on tissue chemistry. Consequent changes in organic matter accumulation may alter marsh capacity to accommodate sea-level rise through vertical accretion.

Short-term impacts of Hurricanes Irma and Maria on tropical stream chemistry as measured by in-situ sensors

NASA Astrophysics Data System (ADS)

McDowell, W. H.; Potter, J.; López-Lloreda, C.

2017-12-01

High intensity hurricanes have been shown to alter topical forest productivity and stream chemistry for years to decades in the montane rain forest of Puerto Rico, but much less is known about the immediate ecosystem response to these extreme events. Here we report the short-term impacts of Hurricanes Irma and Maria on the chemistry of Quebrada Sonadora immediately before and after the storms. We place the results from our 15-minute sensor record in the context of long-term weekly sampling that spans 34 years and includes two earlier major hurricanes (Hugo and Geoges). As expected, turbidity during Maria was the highest in our sensor record (> 1000 NTU). Contrary to our expectations, we found that solute-flow behavior changed with the advent of the storms. Specific conductance showed a dilution response to flow before the storms, but then changed to an enrichment response during and after Maria. This switch in system behavior is likely due to the deposition of marine aerosols during the hurricane. Nitrate concentrations showed very little response to discharge prior to the recent hurricanes, but large increase in concentration occurred at high flow both during and after the hurricanes. Baseflow nitrate concentrations decreased immediately after Irma to below the long-term background concentrations, which we attribute to the immobilization of N on organic debris choking the stream channel. Within three weeks of Hurricane Maria, baseflow nitrate concentrations began to rise. This is likely due to mineralization of N from decomposing canopy vegetation on the forest floor, and reduced N uptake by hurricane-damaged vegetation. The high frequency sensors are providing new insights into the response of this ecosystem in the days and weeks following two major disturbance events. The flipping of nitrate response to storms, from source limited to transport limited, suggests that these two severe hurricanes have fundamentally altered the nitrogen cycle at the site in ways that would not be evident without sensors.

Characterization of the surface properties of epoxy-type models used for multiphase flow studies in fractured media and creation of a new model

NASA Astrophysics Data System (ADS)

Bergslien, Elisa; Fountain, John; Giese, Rossman

2004-05-01

Epoxy models have been used as analogs for fractured rock surfaces in many laboratory investigations of multiphase flow processes. However, there is no agreement on how well or poorly such an analog replicates the surface chemistry of geologic materials, nor is there a satisfactory analysis of the surface properties of epoxy. This paper addresses the issue of accurately characterizing the surface chemistry of a typical epoxy used in laboratory multiphase flow studies and comparing that surface to a polystyrene surface and a radio frequency glow discharge treated polystyrene surface. Surface properties were determined using direct contact angle measurements of polar and apolar liquids on flat test samples. The epoxy was determined to have surface properties as follows: γ = 62.3, γLW = 39, γAB = 23.3, γ⊕ = 0, and γ? = 23.3 mJ/m2, where γ is the total surface tension of the solid, γLW is the Lifshitz-van der Waals (LW) surface tension component, γAB is the Lewis acid base (AB) surface tension component, γ? is the electron-donor (negative) parameter, and γ⊕ is the electron-acceptor (positive) parameter. Values of γ? < 27.9 mJ/m2 indicate a hydrophobic surface, which means that epoxy is not a good analog for most geologic materials. This study also explores the use of radio frequency glow discharge plasma to add hydroxyl functionality to polymer surfaces producing a material with alterable surface properties and the same optical and casting properties as epoxy. Using this method, the degree of alteration of the surface chemistry of polymer fracture models can be controlled, allowing the creation of models with a variety of different wettabilities. The resultant models were found to be durable, long lasting, and a potentially very useful alternative to the more typical epoxy models.

Species and tissue type regulate long-term decomposition of brackish marsh plants grown under elevated CO2 conditions

USGS Publications Warehouse

Jones, Joshua A; Cherry, Julia A; Mckee, Karen L.

2016-01-01

Organic matter accumulation, the net effect of plant production and decomposition, contributes to vertical soil accretion in coastal wetlands, thereby playing a key role in whether they keep pace with sea-level rise. Any factor that affects decomposition may affect wetland accretion, including atmospheric CO2 concentrations. Higher CO2 can influence decomposition rates by altering plant tissue chemistry or by causing shifts in plant species composition or biomass partitioning. A combined greenhouse-field experiment examined how elevated CO2 affected plant tissue chemistry and subsequent decomposition of above- and belowground tissues of two common brackish marsh species, Schoenoplectus americanus (C3) and Spartina patens (C4). Both species were grown in monoculture and in mixture under ambient (350-385 μL L-1) or elevated (ambient + 300 μL L-1) atmospheric CO2 conditions, with all other growth conditions held constant, for one growing season. Above- and belowground tissues produced under these treatments were decomposed under ambient field conditions in a brackish marsh in the Mississippi River Delta, USA. Elevated CO2 significantly reduced nitrogen content of S. americanus, but not sufficiently to affect subsequent decomposition. Instead, long-term decomposition (percent mass remaining after 280 d) was controlled by species composition and tissue type. Shoots of S. patens had more mass remaining (41 ± 2%) than those of S. americanus (12 ± 2 %). Belowground material decomposed more slowly than that placed aboveground (62 ± 1% vs. 23 ± 3% mass remaining), but rates belowground did not differ between species. Increases in atmospheric CO2concentration will likely have a greater effect on overall decomposition in this brackish marsh community through shifts in species dominance or biomass allocation than through effects on tissue chemistry. Consequent changes in organic matter accumulation may alter marsh capacity to accommodate sea-level rise through vertical accretion.

Xenobiology: State-of-the-Art, Ethics, and Philosophy of New-to-Nature Organisms.

PubMed

Schmidt, Markus; Pei, Lei; Budisa, Nediljko

The basic chemical constitution of all living organisms in the context of carbon-based chemistry consists of a limited number of small molecules and polymers. Until the twenty-first century, biology was mainly an analytical science and has now reached a point where it merges with engineering science, paving the way for synthetic biology. One of the objectives of synthetic biology is to try to change the chemical compositions of living cells, that is, to create an artificial biological diversity, which in turn fosters a new sub-field of synthetic biology, xenobiology. In particular, the genetic code in living systems is based on highly standardized chemistry composed of the same "letters" or nucleotides as informational polymers (DNA, RNA) and the 20 amino acids which serve as basic building blocks for proteins. The universality of the genetic code enables not only vertical gene transfer within the same species but also horizontal gene transfer across biological taxa, which require a high degree of standardization and interconnectivity. Although some minor alterations of the standard genetic code are found in nature (e.g., proteins containing non-conical amino acids exist in nature, and some organisms use alternated coding systems), all structurally deep chemistry changes within living systems are generally lethal, making the creation of artificial biological system an extremely difficult challenge.In this context, one of the great challenges for bioscience is the development of a strategy for expanding the standard basic chemical repertoire of living cells. Attempts to alter the meaning of the genetic information stored in DNA as an informational polymer by changing the chemistry of the polymer (i.e., xeno-nucleic acids) or by changes in the genetic code have already yielded successful results. In the future this should enable the partial or full redirection of the biological information flow to generate "new" version(s) of the genetic code derived from the "old" biological world.In addition to the scientific challenges, the attempt to increase biochemical diversity also raises important ethical and philosophical issues. Although promotors of this branch of synthetic biology highlight the many potential applications to come (e.g., novel tools for diagnostics and fighting infection diseases), such developments could also bring risks affecting social, political, and other structures of nearly all societies.

Molybdenite in the Montezuma District of central Colorado

USGS Publications Warehouse

Neuerburg, George J.; Botinelly, Theodore; Watterson, John R.

1974-01-01

The Montezuma mining district, in the Colorado mineral belt, is defined by an assemblage of porphyry, ore, and altered rocks that originated in the venting of a Tertiary batholith through weak structures in Precambrian rocks. The ore consists of silver-lead-zinc veins clustered on the propylitic fringe of a geometrically complex system of altered rocks, which is centered on the intersection of the Oligocene Montezuma stock with the Montezuma shear zone of Precambrian ancestry. Alteration chemistry conforms to the standard porphyry-metal model but is developed around several small intrusives strung out along the shear zone and is expressed as a mottled pattern, rather than as the usual thick concentric zones centered on one large plug. The distribution of trace amounts of molybdenite is consistent with the postulate of molybdenite deposits in the district, but the mottled alteration pattern may signify small and scattered, possibly very deep, deposits. Disseminated molybdenite is essentially coextensive with altered rock and increases slightly in quantity toward the inner alteration zones. Two groups of molybdenite veins, associated with phyllic and potassic alteration, represent possible diffuse halos of molybdenite deposits. One group of veins resembles the Climax and Henderson deposits but was seen only in a small and isolated area of outcrops. The second group of molybdenite veins is in a bismuth-rich part of the Montezuma stock and underlies an area of bismuth veins; this group records the passage of contact metasomatic ore fluids. Another bismuth-rich area is in the southeast corner of the stock in a region of bismuth veins and may indicate a third group of molybdenite veins.

Role of Nuclear Matrix in Estrogen Regulated Gene Expression in Human Breast Cancer Cells

DTIC Science & Technology

1998-08-01

reticular pattern evenly distributed throughout the nucleus, excluding the nucleolus (Figure 4A). This is not so for T47D cells where a composite pattern...acetylation is required to maintain the unfolded nucleosome structure associated with transcribing DNA. Journal of Biological Chemistry 273:14516...nuclear matrix include ER, YY1, AML-1, Spl, Oct1, mutant p53, and Rb [25,28,31,34-40]. Appendix A, part 4 reviews alterations in nuclear matrix composition

Chromite from the Blue Ridge province of North Carolina.

USGS Publications Warehouse

Lipin, B.R.

1984-01-01

Chromite is found as ubiquitous accessory grains and occasional segregations within dunite bodies. Results of analysis of chromite textures and chemistry and estimation of equilibration T of olivine-chromite pairs are cited as evidence that the dunites are metamorphic rocks rather than primary mantle peridotites. They are considered to be disrupted fragments of ophiolites that were emplaced before or during the peak of Ordovician metamorphism which was responsible for dehydration of serpentine-bearing rocks and alteration of chromite compositions and textures.-M.S.

Analyzing Cell Wall Elasticity After Hormone Treatment: An Example Using Tobacco BY-2 Cells and Auxin.

PubMed

Braybrook, Siobhan A

2017-01-01

Atomic force microscopy, and related nano-indentation techniques, is a valuable tool for analyzing the elastic properties of plant cell walls as they relate to changes in cell wall chemistry, changes in development, and response to hormones. Within this chapter I will describe a method for analyzing the effect of the phytohormone auxin on the cell wall elasticity of tobacco BY-2 cells. This general method may be easily altered for different experimental systems and hormones of interest.

Effects of inhalation of Freon 113 on laboratory animals

NASA Technical Reports Server (NTRS)

Carter, V. L.; Chikos, P. M.; Macewen, J. D.; Back, K. C.

1970-01-01

Four monkeys, 8 dogs, 40 mice, and 50 rats were exposed continuously to 2000 ppm Freon 113 in a Thomas Dome for 14 days. This exposure produced no mortalities nor adverse symptomology. There were no significant alterations in hematological values, clinical chemistries, electroencephalographic findings, body weights, or organ to body weight ratios. The effect of 2% Freon 113 on nicotinic transmission through the stellate ganglion of the spinal dog was also evaluated. The exposure induced a reduction in nicotinic transmission comparable to 2% halothane.

Impact of pore-water freshening on clays and the compressibility of hydrate-bearing reservoirs during production

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

Jang, Junbong; Cao, Shuang; Waite, William

Gas production efficiency from natural hydrate-bearing sediments depends in part on geotechnical properties of fine-grained materials, which are ubiquitous even in sandy hydrate-bearing sediments. The responses of fine-grained material to pore fluid chemistry changes due to freshening during hydrate dissociation could alter critical sediment characteristics during gas production activities. We investigate the electrical sensitivity of fine grains to pore fluid freshening and the implications of freshening on sediment compression and recompression parameters.

Magmatic-vapor expansion and the formation of high-sulfidation gold deposits: Structural controls on hydrothermal alteration and ore mineralization

USGS Publications Warehouse

Berger, Byron R.; Henley, Richard W.

2011-01-01

High-sulfidation copper–gold lode deposits such as Chinkuashih, Taiwan, Lepanto, Philippines, and Goldfield, Nevada, formed within 1500 m of the paleosurface in volcanic terranes. All underwent an early stage of extensive advanced argillic silica–alunite alteration followed by an abrupt change to spatially much more restricted stages of fracture-controlled sulfide–sulfosalt mineral assemblages and gold–silver mineralization. The alteration as well as ore mineralization stages of these deposits were controlled by the dynamics and history of syn-hydrothermal faulting.At the Sulfate Stage, aggressive advanced argillic alteration and silicification were consequent on the in situ formation of acidic condensate from magmatic vapor as it expanded through secondary fracture networks alongside active faults. The reduction of permeability at this stage due to alteration decreased fluid flow to the surface, and progressively developed a barrier between magmatic-vapor expansion constrained by the active faults and peripheral hydrothermal activity dominated by hot-water flow. In conjunction with the increased rock strength resulting from alteration, subsequent fault-slip inversion in response to an increase in compressional stress generated new, highly permeable fractures localized by the embrittled, altered rock. The new fractures focused magmatic-vapor expansion with much lower heat loss so that condensation occurred. Sulfide Stage sulfosalt, sulfide, and gold–silver deposition then resulted from destabilization of vapor phase metal species due to vapor decompression through the new fracture array. The switch from sulfate to sulfide assemblages is, therefore, a logical consequence of changes in structural permeability due to the coupling of alteration and fracture dynamics rather than to changes in the chemistry of the fluid phase at its magmatic source.

Chemistry-Climate Interactions in the GISS GCM. Part 1; Tropospheric Chemistry Model Description and Evaluation

NASA Technical Reports Server (NTRS)

Shindell, Drew T.; Grenfell, J. Lee; Rind, David; Price, Colin; Grewe, Volker; Hansen, James E. (Technical Monitor)

2001-01-01

A tropospheric chemistry module has been developed for use within the Goddard Institute for Space Studies (GISS) general circulation model (GCM) to study interactions between chemistry and climate change. The model uses a simplified chemistry scheme based on CO-NOx-CH4 chemistry, and also includes a parameterization for emissions of isoprene, the most important non-methane hydrocarbon. The model reproduces present day annual cycles and mean distributions of key trace gases fairly well, based on extensive comparisons with available observations. Examining the simulated change between present day and pre-industrial conditions, we find that the model has a similar response to that seen in other simulations. It shows a 45% increase in the global tropospheric ozone burden, within the 25% - 57% range seen in other studies. Annual average zonal mean ozone increases by more than 125% at Northern Hemisphere middle latitudes near the surface. Comparison of model runs that allow the calculated ozone to interact with the GCM's radiation and meteorology with those that do not shows only minor differences for ozone. The common usage of ozone fields that are not calculated interactively seems to be adequate to simulate both the present day and the pre-industrial ozone distributions. However, use of coupled chemistry does alter the change in tropospheric oxidation capacity, enlarging the overall decrease in OH concentrations from the pre-industrial to the present by about 10% (-5.3% global annual average in uncoupled mode, -5.9% in coupled mode). This indicates that there may be systematic biases in the simulation of the pre-industrial to present day decrease in the oxidation capacity of the troposphere (though a 10% difference is well within the total uncertainty). Global annual average radiative forcing from pre-industrial to present day ozone change is 0.32 W/sq m. The forcing seems to be increased by about 10% when the chemistry is coupled to the GCM. Forcing values greater than 0.8 W/sq m are seen over large areas of the United States, Southern Europe, North Africa, the Middle East, Central Asia, and the Arctic. Radiative forcing is greater than 1.5 W/sq m over parts of these areas during Northern summer Though there are local differences, the radiative forcing is overall in good agreement with the results of other modeling studies in both its magnitude and spatial distribution, demonstrating that the simplified chemistry is adequate for climate studies.

Influence of isoprene chemical mechanism on modelled changes in tropospheric ozone due to climate and land use over the 21st century

NASA Astrophysics Data System (ADS)

Squire, O. J.; Archibald, A. T.; Griffiths, P. T.; Jenkin, M. E.; Smith, D.; Pyle, J. A.

2015-05-01

Isoprene is a~precursor to tropospheric ozone, a key pollutant and greenhouse gas. Anthropogenic activity over the coming century is likely to cause large changes in atmospheric CO2 levels, climate and land use, all of which will alter the global vegetation distribution leading to changes in isoprene emissions. Previous studies have used global chemistry-climate models to assess how possible changes in climate and land use could affect isoprene emissions and hence tropospheric ozone. The chemistry of isoprene oxidation, which can alter the concentration of ozone, is highly complex, therefore it must be parameterised in these models. In this work, we compare the effect of four different reduced isoprene chemical mechanisms, all currently used in Earth system models, on tropospheric ozone. Using a box model we compare ozone in these reduced schemes to that in a more explicit scheme (the Master Chemical Mechanism) over a range of NOx and isoprene emissions, through the use of O3 isopleths. We find that there is some variability, especially at high isoprene emissions, caused by differences in isoprene-derived NOx reservoir species. A global model is then used to examine how the different reduced schemes respond to potential future changes in climate, isoprene emissions, anthropogenic emissions and land use change. We find that, particularly in isoprene-rich regions, the response of the schemes varies considerably. The wide-ranging response is due to differences in the model descriptions of the peroxy radical chemistry, particularly their relative rates of reaction towards NO, leading to ozone formation, or HO2, leading to termination. Also important is the yield of isoprene nitrates and peroxyacyl nitrate precursors from isoprene oxidation. Those schemes that produce less of these NOx reservoir species, tend to produce more ozone locally and less away from the source region. We also note changes in other key oxidants such as NO3 and OH (due to the inclusion of additional isoprene-derived HOx recycling pathways). These have implications for secondary organic aerosol formation, as does the inclusion of an epoxide formation pathway in one of the mechanisms. By combining the emissions and O3 data from all of the global model integrations, we are able to construct isopleth plots comparable to those from the box model analysis. We find that the global and box model isopleths show good qualitative agreement, suggesting that comparing chemical mechanisms with a box model in this framework is a useful tool for assessing mechanistic performance in complex global models. We conclude that as the choice of reduced isoprene mechanism may alter both the magnitude and sign of the ozone response, how isoprene chemistry is parameterised in perturbation experiments such as these is a crucially important consideration. More measurements and laboratory studies are needed to validate these reduced mechanisms especially under high-volatile-organic-compound, low-NOx conditions.

Impact of diagenetic alteration on sea urchin (Echinodermata) magnesium isotope signatures: Comparison of experimental and fossil data

NASA Astrophysics Data System (ADS)

Riechelmann, Sylvia; Mavromatis, Vasileios; Buhl, Dieter; Dietzel, Martin; Hoffmann, René; Jöns, Niels; Eisenhauer, Anton; Immenhauser, Adrian

2017-04-01

Due to their thermodynamically instable high-Mg calcite mineralogy, the skeletal elements of echinoderms are often regarded as unreliable archives of Phanerozoic marine climate dynamics. Nevertheless, traditional and non-traditional isotope and elemental proxy data from echinoderms have been used to reconstruct global changes in palaeoseawater composition (Sandberg-cycles). Recently, these data and the interpretation have been controversially discussed in context with ancient seawater properties. This paper tests the sensitivity of echinoderm skeletal hardparts, specifically sea urchin spines to diagenetic alteration based on magnesium isotope data. We apply a dual approach by: (i) performing hydrothermal alteration experiments using meteoric, marine, and burial reactive fluids; and (ii) comparing these data with fossil sea urchin hardparts. The degree of alteration of experimentally altered and fossil sea urchin hardparts is assessed by a combination of optical (fluorescence, cathodoluminescence (CL), scanning electron microscopy (SEM)) and geochemical tools (elemental distribution, carbon, oxygen and magnesium isotopes). Although initial fluid chemistry of the experiments did not allow the detection of diagenetic overprint by elemental distribution (Fe, Mn) and cathodoluminescence, other tools such as fluorescence, SEM, delta18O, Mg concentration and delta26Mg display alteration effects, which respond to differential fluid temperature, chemistry, and experiment duration time. At experiments run under meteoric conditions with no Mg in the initial fluid, the solid is enriched in the heavier Mg isotopomer due to preferential dissolution of the lighter isotope. In contrast, initial burial and marine fluids have medium to high Mg concentrations. There, the Mg concentration and the delta26Mg values of the altered sea urchin spines increase. Fossil sea urchin hardparts display partly very strong diagenetic overprint as observed by their elemental distribution, cathodoluminescence, delta18O, Mg elemental concentration and delta26Mg. The absence of luminescence might indicate both well-preserved sea urchin spines, but also the secondary enrichment of quenching elements such as iron along diagenetic pathways. The relation between Mg concentration and delta26Mg of the experimentally altered sea urchin spines is in agreement with observations from fossil spines, which also display a 26Mg-enrichment of the solid phase. There, it seems that with increasing degree of alteration, an increase in Mg concentration and delta26Mg occurs. Hence, the experiments performed in this study seem to reflect diagenetic processes under natural conditions. However, the patterns observed are complicated by the interplay of kinetic and thermodynamic processes and the presence of variable amounts of water soluble and water insoluble organic matter within these biominerals. Due to (i) a natural inter- and intra-species variability of the Mg concentration and Mg isotopic composition throughout the echinoderm skeleton and (ii) the fractionation of Mg isotopes during the transformation of ACC as a precursor phase to calcite, the use of delta26Mg values of sea urchin hardparts as a proxy for past seawater delta26Mg is deemed unsuitable. In general, the data shown here are considered significant for those aiming to reconstruct palaeoenvironmental parameters based on echinoderm archives.

Developing the Surface Chemistry of Transparent Butyl Rubber for Impermeable Stretchable Electronics.

PubMed

Vohra, Akhil; Carmichael, R Stephen; Carmichael, Tricia Breen

2016-10-11

Transparent butyl rubber is a new elastomer that has the potential to revolutionize stretchable electronics due to its intrinsically low gas permeability. Encapsulating organic electronic materials and devices with transparent butyl rubber protects them from problematic degradation due to oxygen and moisture, preventing premature device failure and enabling the fabrication of stretchable organic electronic devices with practical lifetimes. Here, we report a methodology to alter the surface chemistry of transparent butyl rubber to advance this material from acting as a simple device encapsulant to functioning as a substrate primed for direct device fabrication on its surface. We demonstrate a combination of plasma and chemical treatment to deposit a hydrophilic silicate layer on the transparent butyl rubber surface to create a new layered composite that combines Si-OH surface chemistry with the favorable gas-barrier properties of bulk transparent butyl rubber. We demonstrate that these surface Si-OH groups react with organosilanes to form self-assembled monolayers necessary for the deposition of electronic materials, and furthermore demonstrate the fabrication of stretchable gold wires using nanotransfer printing of gold films onto transparent butyl rubber modified with a thiol-terminated self-assembled monolayer. The surface modification of transparent butyl rubber establishes this material as an important new elastomer for stretchable electronics and opens the way to robust, stretchable devices.

Effects of Precursor Concentration and Acidic Sulfate in Aqueous Glyoxal−OH Radical Oxidation and Implications for Secondary Organic Aerosol

PubMed Central

2009-01-01

Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30−3000 μM) and the presence of acidic sulfate (0−840 μM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 μM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA. PMID:19924930

The weathering of organic carbon and pyrite sulfur in Earth's crust and its importance for regulating atmospheric composition, seawater chemistry, and stable isotope records

NASA Astrophysics Data System (ADS)

Reinhard, C. T.; Planavsky, N.; Bolton, E. W.

2016-12-01

Earth's crust stores extremely large reservoirs of organic carbon and pyrite sulfur, and transient or secular changes in the sizes of these reservoirs have the capacity to dramatically alter atmospheric composition, climate, seawater acid-base chemistry, and the propagation of isotopic signals into the geologic record. This talk will present and discuss new quantitative approaches toward better understanding the factors that control organic carbon and pyrite sulfur weathering under a wide range of Earth surface conditions, as well as their downstream effects on seawater chemistry, stability of atmospheric pO2, and conventional interpretations of stable carbon isotope mass balance during pivotal events in Earth's biogeochemical evolution. In particular, we will focus on (1) development of a weathering-driven scaling between atmospheric pO2 and geologic carbon isotope signals that explains the relative stability of marine δ13C through time and provides a mechanism for protracted negative δ13C excursions during transient increases in atmospheric pO2; (2) experimental and theoretical approaches aimed at better understanding the role of pyrite sulfur weathering in stabilizing atmospheric pO2; and (3) the importance of redox balance in the sedimentary rock cycle for controlling the marine carbonate system and atmospheric pCO2.

Modifying the visual appearance of metal nanoparticle composites by infrared laser annealing

NASA Astrophysics Data System (ADS)

Halabica, Andrej; Indrobo, J. C.; Magruder, R. H., III; Haglund, R. F., Jr.; Epp, J. M.; Rashkeev, S.; Boatner, L. A.; Pennycook, S. J.; Pantelides, S. T.

2007-03-01

It has long been known that noble-metal nanoparticles in insulators can alter their visual appearance. Many metal nanoparticle composites can be created by ion implantation and subsequent annealing to initiate phase separation, nucleation and growth of nanoparticles. The size and size distribution of the nanoparticles - and therefore the color of the composite - are determined by the chemistry and thermodynamics of the annealing process. In this paper we report that we can also alter the color of gold- and silver-implanted silica and alumina by tunable infrared laser irradiation. Essentially a variant of rapid thermal annealing, this laser treatment can shift the plasmon band of the nanoparticles by tens of nm, resulting in significantly altered visual appearance. The amount of energy delivered to the implanted layer, and the subsequent color variation, can be adjusted by changing the wavelength and fluence of the laser. This makes it possible, as we will show, to write or pattern the composite material with 200 μm linewidths. This work is partially supported by DOE (DE-AC05-00OR22725), NSF (DMR-0513048), and by Alcoa Inc.

Plant growth, biomass partitioning and soil carbon formation in response to altered lignin biosynthesis in Populus tremuloides.

PubMed

Hancock, Jessica E; Loya, Wendy M; Giardina, Christian P; Li, Laigeng; Chiang, Vincent L; Pregitzer, Kurt S

2007-01-01

We conducted a glasshouse mesocosm study that combined (13)C isotope techniques with wild-type and transgenic aspen (Populus tremuloides) in order to examine how altered lignin biosynthesis affects plant production and soil carbon formation. Our transgenic aspen lines expressed low stem lignin concentration but normal cellulose concentration, low lignin stem concentration with high cellulose concentration or an increased stem syringyl to guaiacyl lignin ratio. Large differences in stem lignin concentration observed across lines were not observed in leaves or fine roots. Nonetheless, low lignin lines accumulated 15-17% less root C and 33-43% less new soil C than the control line. Compared with the control line, transformed aspen expressing high syringyl lignin accumulated 30% less total plant C - a result of greatly reduced total leaf area - and 70% less new soil C. These findings suggest that altered stem lignin biosynthesis in Populus may have little effect on the chemistry of fine roots or leaves, but can still have large effects on plant growth, biomass partitioning and soil C formation.

HRTEM and EFTEM Studies of Phyllosilicate-Organic Matter Associations in Matrix and Dark Inclusions in the EET92042 CR2 Carbonaceous Chondrite

NASA Technical Reports Server (NTRS)

Abreu, Neyda M.; Brearley, Adrian J.

2005-01-01

Based on petrologic and isotopic observations, the CR chondrites represent one of the most primitive carbonaceous chondrite groups. The organic matter in CR chondrite matrices is considered to be among the most ancient carbonaceous matter known, potentially providing a link between organic matter in the interstellar medium and our solar system [1]. However, the organic chemistry of CR chondrites may be complicated by the fact that these meteorites have undergone moderate secondary alteration, which potentially overprints primordial features [2]. Although the general effects of this alteration have been documented [2], the details of the fine-grained mineralogy and alteration styles of CR matrices are not fully understood. Here we present TEM observations of matrix in EET 92042, a CR chondrite that contains particularly primitive insoluble organic matter [1]. Preliminary studies [3] determined that EET 92042 matrix is heterogeneous in terms of mineralogy, texture, and petrographic fabric on the micron scale. EET 92042 contains magnetite-rich regions, foliated matrix and dark inclusions (DIs). Some chondrules show fine-grained rims, similar to those described by [4].

Adverse effects of ocean acidification on early development of squid (Doryteuthis pealeii).

PubMed

Kaplan, Maxwell B; Mooney, T Aran; McCorkle, Daniel C; Cohen, Anne L

2013-01-01

Anthropogenic carbon dioxide (CO2) is being absorbed into the ocean, altering seawater chemistry, with potentially negative impacts on a wide range of marine organisms. The early life stages of invertebrates with internal and external aragonite structures may be particularly vulnerable to this ocean acidification. Impacts to cephalopods, which form aragonite cuttlebones and statoliths, are of concern because of the central role they play in many ocean ecosystems and because of their importance to global fisheries. Atlantic longfin squid (Doryteuthis pealeii), an ecologically and economically valuable taxon, were reared from eggs to hatchlings (paralarvae) under ambient and elevated CO2 concentrations in replicated experimental trials. Animals raised under elevated pCO2 demonstrated significant developmental changes including increased time to hatching and shorter mantle lengths, although differences were small. Aragonite statoliths, critical for balance and detecting movement, had significantly reduced surface area and were abnormally shaped with increased porosity and altered crystal structure in elevated pCO2-reared paralarvae. These developmental and physiological effects could alter squid paralarvae behavior and survival in the wild, directly and indirectly impacting marine food webs and commercial fisheries.

Adverse Effects of Ocean Acidification on Early Development of Squid (Doryteuthis pealeii)

PubMed Central

Kaplan, Maxwell B.; Mooney, T. Aran; McCorkle, Daniel C.; Cohen, Anne L.

2013-01-01

Anthropogenic carbon dioxide (CO2) is being absorbed into the ocean, altering seawater chemistry, with potentially negative impacts on a wide range of marine organisms. The early life stages of invertebrates with internal and external aragonite structures may be particularly vulnerable to this ocean acidification. Impacts to cephalopods, which form aragonite cuttlebones and statoliths, are of concern because of the central role they play in many ocean ecosystems and because of their importance to global fisheries. Atlantic longfin squid (Doryteuthis pealeii), an ecologically and economically valuable taxon, were reared from eggs to hatchlings (paralarvae) under ambient and elevated CO2 concentrations in replicated experimental trials. Animals raised under elevated pCO2 demonstrated significant developmental changes including increased time to hatching and shorter mantle lengths, although differences were small. Aragonite statoliths, critical for balance and detecting movement, had significantly reduced surface area and were abnormally shaped with increased porosity and altered crystal structure in elevated pCO2-reared paralarvae. These developmental and physiological effects could alter squid paralarvae behavior and survival in the wild, directly and indirectly impacting marine food webs and commercial fisheries. PMID:23741298

Polyhedral Serpentine Grains in CM Chondrites

NASA Technical Reports Server (NTRS)

Zega, Thomas J.; Garvie, Laurence A. J.; Dodony, Istvan; Stroud, Rhonda M.; Buseck, Peter R.

2005-01-01

CM chondrites are primitive rocks that experienced aqueous alteration in the early solar system. Their matrices and fine-grained rims (FGRs) sustained the effects of alteration, and the minerals within them hold clues to the aqueous reactions. Sheet silicates are an important product of alteration, and those of the serpentine group are abundant in the CM2 chondrites. Here we expand on our previous efforts to characterize the structure and chemistry of serpentines in CM chondrites and report results on a polyhedral form that is structurally similar to polygonal serpentine. Polygonal serpentine consists of tetrahedral (T) sheets joined to M(2+)-centered octahedral (O) sheets (where (M2+) is primarily Mg(2+) and Fe(2+)), which give rise to a 1:1 (TO) layered structure with a 0.7-nm layer periodicity. The structure is similar to chrysotile in that it consists of concentric lizardite layers wrapped around the fiber axis. However, unlike the rolled-up chrysotile, the tetrahedral sheets of the lizardite layers are periodically inverted and kinked, producing sectors. The relative angles between sectors result in 15- and 30-sided polygons in terrestrial samples.

Ocean Acidification Refugia of the Florida Reef Tract

NASA Astrophysics Data System (ADS)

Manzello, D.; Enochs, I.; Melo, N.; Gledhill, D. K.; Johns, E. M.

2012-12-01

Ocean acidification (OA) is expected to reduce the calcification rates of marine organisms, yet we have little understanding of how OA will manifest within dynamic, real-world systems. Natural CO2, alkalinity, and salinity gradients can significantly alter local carbonate chemistry, and thereby create a range of susceptibility for different ecosystems to OA. As such, there is a need to characterize this natural variability of seawater carbonate chemistry, especially within coastal ecosystems. Since 2009, carbonate chemistry data have been collected on the Florida Reef Tract (FRT). During periods of heightened productivity, there is a net uptake of total CO2 (TCO2) which increases aragonite saturation state (Ωarag) values on inshore patch reefs of the upper FRT. These waters can exhibit greater Ωarag than what has been modeled for the tropical surface ocean during preindustrial times, with mean (± std. error) Ωarag-values in spring = 4.69 (± 0.101). Conversely, Ωarag-values on offshore reefs generally represent oceanic carbonate chemistries consistent with present day tropical surface ocean conditions. This gradient is opposite from what has been reported for other reef environments. We hypothesize this pattern is caused by the photosynthetic uptake of TCO2 mainly by seagrasses and, to a lesser extent, macroalgae in the inshore waters of the FRT. These inshore reef habitats are therefore potential acidification refugia that are defined not only in a spatial sense, but also in time; coinciding with seasonal productivity dynamics. Coral reefs located within or immediately downstream of seagrass beds may find refuge from OA.

Ocean Acidification Refugia of the Florida Reef Tract

PubMed Central

Manzello, Derek P.; Enochs, Ian C.; Melo, Nelson; Gledhill, Dwight K.; Johns, Elizabeth M.

2012-01-01

Ocean acidification (OA) is expected to reduce the calcification rates of marine organisms, yet we have little understanding of how OA will manifest within dynamic, real-world systems. Natural CO2, alkalinity, and salinity gradients can significantly alter local carbonate chemistry, and thereby create a range of susceptibility for different ecosystems to OA. As such, there is a need to characterize this natural variability of seawater carbonate chemistry, especially within coastal ecosystems. Since 2009, carbonate chemistry data have been collected on the Florida Reef Tract (FRT). During periods of heightened productivity, there is a net uptake of total CO2 (TCO2) which increases aragonite saturation state (Ωarag) values on inshore patch reefs of the upper FRT. These waters can exhibit greater Ωarag than what has been modeled for the tropical surface ocean during preindustrial times, with mean (± std. error) Ωarag-values in spring = 4.69 (±0.101). Conversely, Ωarag-values on offshore reefs generally represent oceanic carbonate chemistries consistent with present day tropical surface ocean conditions. This gradient is opposite from what has been reported for other reef environments. We hypothesize this pattern is caused by the photosynthetic uptake of TCO2 mainly by seagrasses and, to a lesser extent, macroalgae in the inshore waters of the FRT. These inshore reef habitats are therefore potential acidification refugia that are defined not only in a spatial sense, but also in time; coinciding with seasonal productivity dynamics. Coral reefs located within or immediately downstream of seagrass beds may find refuge from OA. PMID:22848575

Ocean acidification refugia of the Florida Reef Tract.

PubMed

Manzello, Derek P; Enochs, Ian C; Melo, Nelson; Gledhill, Dwight K; Johns, Elizabeth M

2012-01-01

Ocean acidification (OA) is expected to reduce the calcification rates of marine organisms, yet we have little understanding of how OA will manifest within dynamic, real-world systems. Natural CO(2), alkalinity, and salinity gradients can significantly alter local carbonate chemistry, and thereby create a range of susceptibility for different ecosystems to OA. As such, there is a need to characterize this natural variability of seawater carbonate chemistry, especially within coastal ecosystems. Since 2009, carbonate chemistry data have been collected on the Florida Reef Tract (FRT). During periods of heightened productivity, there is a net uptake of total CO(2) (TCO(2)) which increases aragonite saturation state (Ω(arag)) values on inshore patch reefs of the upper FRT. These waters can exhibit greater Ω(arag) than what has been modeled for the tropical surface ocean during preindustrial times, with mean (± std. error) Ω(arag)-values in spring = 4.69 (±0.101). Conversely, Ω(arag)-values on offshore reefs generally represent oceanic carbonate chemistries consistent with present day tropical surface ocean conditions. This gradient is opposite from what has been reported for other reef environments. We hypothesize this pattern is caused by the photosynthetic uptake of TCO(2) mainly by seagrasses and, to a lesser extent, macroalgae in the inshore waters of the FRT. These inshore reef habitats are therefore potential acidification refugia that are defined not only in a spatial sense, but also in time; coinciding with seasonal productivity dynamics. Coral reefs located within or immediately downstream of seagrass beds may find refuge from OA.

The effect of dissolution of volcanic glass on the water chemistry in a tuffaceous aquifer, Rainier Mesa, Nevada

USGS Publications Warehouse

White, Art F.; Claassen, H.C.; Benson, Larry V.

1980-01-01

Geochemistry of ground water associated with the Tertiary tuffs within Rainier Mesa, southern Nevada, was investigated to determine the relative importance of glass dissolution in controlling water chemistry. Water samples were obtained both from interstitial pores in core sections and from free-flowing fractures. Cation com- positions showed that calcium and magnesium decreased as a function of depth in the mesa, as sodium increased. The maximum effect occurs within alteration zones containing clinoptilolite and montmorillonite, suggesting these minerals effectively remove bivalent cations from the system. Comparisons are made between compositions of ground waters found within Rainier Mesa that apparently have not reacted with secondary minerals and compositions of waters produced by experimental dissolution of vitric and crystalline tufts which comprise the principal aquifers in the area. The two tuff phases have the same bulk chemistry but produce aqueous solutions of different chemistry. Rapid parabolic dissolution of sodium and silica from, and the retention of, potassium within the vitric phase verify previous predictions concerning water compositions associated with vitric volcanic rocks. Parabolic dissolution of the crystalline phase results in solutions high in calcium and magnesium and low in silica. Extrapolation of the parabolic dissolution mechanism for the vitric tuff to long times successfully reproduces, at com- parable pH, cation ratios existing in Rainier Mesa ground water. Comparison of mass- transfer rates of the vitric and crystalline tuffs indicates that the apparent higher glass-surface to aqueous-volume ratio associated with the vitric rocks may account for dominance of the glass reaction.

Influence of isoprene chemical mechanism on modelled changes in tropospheric ozone due to climate and land use over the 21st century

NASA Astrophysics Data System (ADS)

Squire, O. J.; Archibald, A. T.; Griffiths, P. T.; Jenkin, M. E.; Pyle, J. A.

2014-09-01

Isoprene is a precursor to tropospheric ozone, a key pollutant and greenhouse gas. Anthropogenic activity over the coming century is likely to cause large changes in atmospheric CO2 levels, climate and land use, all of which will alter the global vegetation distribution leading to changes in isoprene emissions. Previous studies have used global chemistry-climate models to assess how possible changes in climate and land use could affect isoprene emissions and hence tropospheric ozone. The chemistry of isoprene oxidation, which can alter the concentration of ozone, is highly complex, therefore it must be parameterised in these models. In this work we compare the effect of four different reduced isoprene chemical mechanisms, all currently used in Earth-system models, on tropospheric ozone. Using a box model we compare ozone in these reduced schemes to that in a more explicit scheme (the MCM) over a range of NOx and isoprene emissions, through the use of O3 isopleths. We find that there is some variability, especially at high isoprene emissions, caused by differences in isoprene-derived NOx reservoir species. A global model is then used to examine how the different reduced schemes respond to potential future changes in climate, isoprene emissions, anthropogenic emissions and land use change. We find that, particularly in isoprene rich regions, the response of the schemes varies considerably. The wide ranging response is due to differences in the types of peroxy radicals produced by isoprene oxidation, and their relative rates of reaction towards NO, leading to ozone formation, or HO2, leading to termination. Also important is the yield of isoprene-nitrates and peroxyacyl nitrate precursors from isoprene oxidation. Those schemes that produce less of these NOx reservoir species, tend to produce more ozone locally and less away from the source region. Additionally, by combining the emissions and O3 data from all of the global model integrations, we are able to construct isopleth plots comparable to those from the box model analysis. We find that the global and box model isopleths show good qualitative agreement, suggesting that comparing chemical mechanisms with a box model in this framework is a useful tool for assessing mechanistic performance in complex global models. We conclude that as the choice of reduced isoprene mechanism may alter both the magnitude and sign of the ozone response, how isoprene chemistry is parameterised in perturbation experiments such as these is a crucially important consideration. More measurements are needed to validate these reduced mechanisms especially in high-VOC, low-NOx environments.

LA-ICP-MS analysis of isolated phosphatic grains indicates selective rare earth element enrichment during reworking and transport processes

NASA Astrophysics Data System (ADS)

Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

2016-04-01

Rare earth elements (REE) are a commonly used proxy to reconstruct water chemistry and oxygen saturation during the formation history of authigenic and biogenic phosphates in marine environments. In the modern ocean REE exhibit a distinct pattern with enrichment of heavy REE and strong depletion in Cerium. Studies of ancient phosphates and carbonates, however, showed that this 'modern' pattern is only rarely present in the geological past. Consequently, the wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry had to have been radically different in the earth's past. A wealth of studies has already shown that both early and late diagenesis can strongly affect REE signatures in phosphates and severely alter primary marine signals. However, no previous research was conducted on how alteration processes occurring prior to final deposition affect marine phosphates. Herein we present a dataset of multiple LA-ICP-MS measurements of REE signatures in isolated phosphate and carbonate grains deposited in a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene "Monterey event". The phosphates are represented by authigenic, biogenic and detrital grains emplaced in bioclastic grain- to packstones dominated by bryozoan and echinoderm fragments, as well as abundant benthic and planktic foraminifers. The results of 39 grain specific LA-ICP-MS measurements in three discrete rock samples reveals four markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Considering grain shape and REE patterns together indicate that authigenic, detrital and biogenic phosphates have distinct REE patterns irrespective of the sample. Our results show that the observed REE patterns in phosphates only broadly reflect water chemistry under certain well constrained circumstances of primary authigenesis. Are these conditions not met, REE patterns are more likely to reflect complex enrichment processes that likely already started to occur during reworking over geologically relatively short time frames. Similarities in the REE patterns of clearly detrital and biogenic phosphate further suggest that the often observed 'hat-shaped' pattern in biogenic phosphates can easily result from increased middle REE (Neodymium to Holmium) scavenging during taphonomic processes prior to final deposition. Finally, cluster analysis coupled with sedimentological considerations proved a valuable tool for the characterization of REE patterns of phosphates in terms of their formation conditions and depositional history, such as the distinction of phosphates formed in situ from reworked and transported phosphate grains.

Hydrated mineral stratigraphy of Ius Chasma, Valles Marineris

USGS Publications Warehouse

Roach, L.H.; Mustard, J.F.; Swayze, G.; Milliken, R.E.; Bishop, J.L.; Murchie, S.L.; Lichtenberg, K.

2010-01-01

New high-resolution spectral and morphologic imaging of deposits on walls and floor of Ius Chasma extend previous geomorphic mapping, and permit a new interpretation of aqueous processes that occurred during the development of Valles Marineris. We identify hydrated mineralogy based on visible-near infrared (VNIR) absorptions. We map the extents of these units with CRISM spectral data as well as morphologies in CTX and HiRISE imagery. Three cross-sections across Ius Chasma illustrate the interpreted mineral stratigraphy. Multiple episodes formed and transported hydrated minerals within Ius Chasma. Polyhydrated sulfate and kieserite are found within a closed basin at the lowest elevations in the chasma. They may have been precipitates in a closed basin or diagenetically altered after deposition. Fluvial or aeolian processes then deposited layered Fe/Mg smectite and hydrated silicate on the chasma floor, postdating the sulfates. The smectite apparently was weathered out of Noachian-age wallrock and transported to the depositional sites. The overlying hydrated silicate is interpreted to be an acid-leached phyllosilicate transformed from the underlying smectite unit, or a smectite/jarosite mixture. The finely layered smectite and massive hydrated silicate units have an erosional unconformity between them, that marks a change in surface water chemistry. Landslides transported large blocks of wallrock, some altered to contain Fe/Mg smectite, to the chasma floor. After the last episode of normal faulting and subsequent landslides, opal was transported short distances into the chasma from a few m-thick light-toned layer near the top of the wallrock, by sapping channels in Louros Valles. Alternatively, the material was transported into the chasma and then altered to opal. The superposition of different types of hydrated minerals and the different fluvial morphologies of the units containing them indicate sequential, distinct aqueous environments, characterized by alkaline, then circum-neutral, and finally very acidic surface or groundwater chemistry. ?? 2009 Elsevier Inc. All rights reserved.

Warming and elevated CO 2 alter the suberin chemistry in roots of photosynthetically divergent grass species

DOE PAGES

Suseela, Vidya; Tharayil, Nishanth; Pendall, Elise; ...

2017-09-01

A majority of soil carbon (C) is either directly or indirectly derived from fine roots, yet roots remain the least understood component of the terrestrial carbon cycle. The decomposability of fine roots and their potential to contribute to soil C is partly regulated by their tissue chemical composition. Roots rely heavily on heteropolymers such as suberins, lignins and tannins to adapt to various environmental pressures and to maximize their resource uptake functions. Since the chemical construction of roots is partly shaped by their immediate biotic/abiotic soil environments, global changes that perturb soil resource availability and plant growth could potentially altermore » root chemistry, and hence the decomposability of roots. However, the effect of global change on the quantity and composition of root heteropolymers are seldom investigated. We examined the effects of elevated CO 2 and warming on the quantity and composition of suberin in roots of Bouteloua gracilis (C4) and Hesperostipa comata (C3) grass species at the Prairie Heating and CO 2 Enrichment (PHACE) experiment at Wyoming, USA. Roots of B. gracilis exposed to elevated CO 2 and warming had higher abundances of suberin and lignin than those exposed to ambient climate treatments. In addition to changes in their abundance, roots exposed to warming and elevated CO 2 had higher ω-hydroxy acids compared to plants grown under ambient conditions. The suberin content and composition in roots of H. comata was less responsive to climate treatments. In H. comata, α,ω-dioic acids increased with the main effect of elevated CO 2, whereas the total quantity of suberin exhibited an increasing trend with the main effect of warming and elevated CO 2. The increase in suberin content and altered composition could lower root decomposition rates with implications for root-derived soil carbon under global change. Our study also suggests that the climate change induced alterations in species composition will further mediate potential suberin contributions to soil carbon pools.« less

Warming and elevated CO 2 alter the suberin chemistry in roots of photosynthetically divergent grass species

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

Suseela, Vidya; Tharayil, Nishanth; Pendall, Elise

A majority of soil carbon (C) is either directly or indirectly derived from fine roots, yet roots remain the least understood component of the terrestrial carbon cycle. The decomposability of fine roots and their potential to contribute to soil C is partly regulated by their tissue chemical composition. Roots rely heavily on heteropolymers such as suberins, lignins and tannins to adapt to various environmental pressures and to maximize their resource uptake functions. Since the chemical construction of roots is partly shaped by their immediate biotic/abiotic soil environments, global changes that perturb soil resource availability and plant growth could potentially altermore » root chemistry, and hence the decomposability of roots. However, the effect of global change on the quantity and composition of root heteropolymers are seldom investigated. We examined the effects of elevated CO 2 and warming on the quantity and composition of suberin in roots of Bouteloua gracilis (C4) and Hesperostipa comata (C3) grass species at the Prairie Heating and CO 2 Enrichment (PHACE) experiment at Wyoming, USA. Roots of B. gracilis exposed to elevated CO 2 and warming had higher abundances of suberin and lignin than those exposed to ambient climate treatments. In addition to changes in their abundance, roots exposed to warming and elevated CO 2 had higher ω-hydroxy acids compared to plants grown under ambient conditions. The suberin content and composition in roots of H. comata was less responsive to climate treatments. In H. comata, α,ω-dioic acids increased with the main effect of elevated CO 2, whereas the total quantity of suberin exhibited an increasing trend with the main effect of warming and elevated CO 2. The increase in suberin content and altered composition could lower root decomposition rates with implications for root-derived soil carbon under global change. Our study also suggests that the climate change induced alterations in species composition will further mediate potential suberin contributions to soil carbon pools.« less

Microbial Life Driving Low-Temperature Basalt Alteration in the Subsurface: Decoupling Abiotic Processes from Biologically-Mediated Rock Alteration

NASA Astrophysics Data System (ADS)

Moore, R.; Lecoeuvre, A.; Stephant, S.; Dupraz, S.; Ranchou-Peyruse, M.; Ranchou-Peyruse, A.; Gérard, E.; Ménez, B.

2017-12-01

Microorganisms are involved with specific rock alteration processes in the deep subsurface. It is a challenge to link any contribution microbial life may have on rock alteration with specific functions or phyla because many alteration features and secondary minerals produced by metabolic processes can also produce abiotically. Here, two flow-through experiments were designed to mimic the circulation of a CO2-rich fluid through crystalline basalt. In order to identify microbially-mediated alteration and be able to link it with specific metabolisms represented in the subsurface, a relatively fresh crystalline basalt substrate was subsampled, sterilized and used as the substrate for both experiments. In one experiment, the substrate was left sterile, and in the other it was inoculated with an enrichment culture derived from the same aquifer as the rock substrate. Initial results show that the inoculum contained Proteobacteria and Firmicutes, which have diverse metabolic potentials. Fluid and rock analyses before, during, and after the experiments show that mineralogy, fluid chemistry, and dissolution processes differ between the sterile and inoculated systems. In the inoculated experiment iron-rich orthopyroxenes were preferentially dissolved while in the sterile system clinopyroxenes and plagioclases both exhibited a higher degree of dissolution. Additionally, the patterns of CO2 consumption and production over the duration of both experiments is different. This suggest that in a low-temperature basalt system with microorganisms CO2 is either consumed to produce biomass, or that carbonates are produced and then subsequently preserved. This suite of results combined with molecular ecology analyses can be used to conclude that in low-temperature basalts microorganisms play an intrinsic role in rock alteration.

Diagenetic susceptibility of carbonate archives - an experimental approach

NASA Astrophysics Data System (ADS)

Pederson, C.; Purgstaller, B.; Mavromatis, V.; Dietzel, M.; Jöns, N.; Buhl, D.; Neuser, R. D.; Breitenbach, S. F. M.; Hoffmann, R.; Kwiecien, O.; Riechelmann, S.; Immenhauser, A.

2017-12-01

Carbonate sediments and biominerals can record environmental conditions during both deposition and subsequent diagenesis, making them important archives of within the geologic record. Therefore, the alteration processes of these paleoenvironmental proxies are important to understand if one is to deduce environmental conditions based on their petrographic and geochemical signature. This study uses an experimental approach in order to best indicate the controls and effects of the diagenesis of various carbonate archives. Samples are hydrothermally altered at known conditions including pore water chemistry (meteoric and brine fluids), and temperature (100-200°C), and are directly compared to an unaltered subsample (same specimen) for petrographic and geochemical alteration, allowing for reduced heterogeneity, and a quantitative and systematic approach to determine the type, extent, and controls of diagenesis. Initial results indicate little-no alteration at the lower temperature experiments (100°C), and almost complete alteration observed at higher temperatures (175-200°C), while intermediate temperature ranges (130-160°C) prove promising for the evaluation of both diagenetic mechanisms, as well as rate limiting factors controlling alteration. Initial results indicate partial recrystallization of the bivalve A. Islandica, as well as other carbonates (corals, bivalves, gastropods, ammonites, and speleothems), with a visually distinct recrystallization front for select specimens. Results indicate that the diagenetic pathway preferentially follows organic distribution, and internal structures within the organo-sediments and minerals, possibly formed during initial formation. Alteration also suggests preferential movement of intercrystalline organics in some sample types, where they appear to be pushed away from the diagenetic front, causing concentration of the water insoluble organics, and the production of visually darker areas surrounding diagenetic fluid pathways.

Characterization of alteration textures in Cretaceous oceanic crust (pillow lava) from the N-Atlantic (DSDP Hole 418A) by spatially-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Fliegel, Daniel; Knowles, Emily; Wirth, Richard; Templeton, Alexis; Staudigel, Hubert; Muehlenbachs, Karlis; Furnes, Harald

2012-11-01

The habit, mineralogy, crystallography, and Fe speciation of tubular and granular alteration textures in basaltic glass recovered from DSDP Hole 418A, which have previously been associated with biologically mediated alteration, were investigated using an integrated suite of microscopic and spectroscopic approaches in order to shine light on their formation and mineralization history. Two different analytical approaches were used: (1) micro scale investigations with conventional petrographic optical microcopy and microscale X-ray fluorescence mapping and X-ray absorption spectroscopy, and (2) nano scale analyses with FIB (focused ion beam milling) to prepare cross-sections for TEM (transmission electron microscopy), EELS (electron energy loss spectroscopy), and STXM (scanning transmission electron microscopy) analyses. The integrated data show that tubular and granular textures are similar in chemical, mineralogical and structural habit. Both granular and tubular alteration textures show a marked transition from ferrous iron in the glass matrix to ferric iron in the textures. Granular and tubular textures are filled with sheet silicates of similar chemistry, and both exhibit thin amorphous alteration rims ∼10-20 nm wide. The alteration rims are typically depleted in Ca and Fe. Ca is enriched at the contact between the secondary mineralization and the alteration rims, whereas Fe is enriched throughout the alteration features and is mainly present as FeIII in contrast to FeII in the host glass. Carbon is enriched only in a few areas, and could possibly be of organic origin but is not bound in carbonate. The mineralization of the features follows the sequence: dissolution of the glass; formation of a leached amorphous rim; mineralizing the cavities by smectide type clays and subsequently congruent growing of the texture diameter by diffusing of the elements through the alteration layer. None of the features could be linked solely to a biogenic origin and hence the biogenicity of the textures can neither be refuted nor supported by this micro- and nano-scale data set.

Tuning Wettability and Adhesion of Structured Surfaces

NASA Astrophysics Data System (ADS)

Badge, Ila

Structured surfaces with feature size ranging from a few micrometers down to nanometers are of great interest in the applications such as design of anti-wetting surfaces, tissue engineering, microfluidics, filtration, microelectronic devices, anti-reflective coatings and reversible adhesives. A specific surface property demands particular roughness geometry along with suitable surface chemistry. Plasma Enhanced Chemical Vapor Deposition (PECVD) is a technique that offers control over surface chemistry without significantly affecting the roughness and thus, provides a flexibility to alter surface chemistry selectively for a given structured surface. In this study, we have used PECVD to fine tune wetting and adhesion properties. The research presented focuses on material design aspects as well as the fundamental understanding of wetting and adhesion phenomena of structured surfaces. In order to study the effect of surface roughness and surface chemistry on the surface wettability independently, we developed a model surface by combination of colloidal lithography and PECVD. A systematically controlled hierarchical roughness using spherical colloidal particles and surface chemistry allowed for quantitative prediction of contact angles corresponding to metastable and stable wetting states. A well-defined roughness and chemical composition of the surface enabled establishing a correlation between theory predictions and experimental measurements. We developed an extremely robust superhydrophobic surface based on Carbon-Nanotubes (CNT) mats. The surface of CNTs forming a nano-porous mesh was modified using PECVD to deposit a layer of hydrophobic coating (PCNT). The PCNT surface thus formed is superhydrophobic with almost zero contact angle hysteresis. We demonstrated that the PCNT surface is not wetted under steam condensation even after prolonged exposure and also continues to retain its superhydrophobicity after multiple frosting-defrosting cycles. The anti-wetting behavior of PCNT surface is consistent with our model predictions, derived based on thermodynamic theory of wetting. The surface of gecko feet is a very unique natural structured surface. The hierarchical surface structure of a Gecko toe pad is responsible for its reversible adhesive properties and superhydrophobicity. van der Waals interactions is known to be the key mechanism behind Gecko adhesion. However, we found that the wettability, thus the surface chemistry plays a significant role in Gecko adhesion mechanism, especially in the case of underwater adhesion. We used PECVD process to deposit a layer of coating with known chemistry on the surface of sheds of gecko toes to study the effect that wettability of the toe surface has on its adhesion. In summary, we demonstrated that PECVD can be effectively used as means of surface chemistry control for tunable structure-property relationship of three types of structured surfaces; each having unique surface features.

Tuning cell adhesive properties via layer-by-layer assembly of chitosan and alginate

PubMed Central

Silva, Joana M.; García, José R.; Reis, Rui L.; García, Andrés J.; Mano, João F.

2017-01-01

Understanding the mechanisms controlling cell-multilayer film interactions is crucial to the successful engineering of these coatings for biotechnological and biomedical applications. Herein, we present a strategy to tune the cell adhesive properties of multilayers based on marine polysaccharides with and without cross-linking and/or coating with extracellular matrix proteins. Chemical cross-linking of multilayers improved mechanical properties of the coatings but also elicited changes in surface chemistry that alter the adhesion of human umbilical vein endothelial cells. We evaluated a strategy to decouple the mechanical and chemical properties of these films, enabling the transition from cell-adhesive to cell-resistant multilayers. Addition of chitosan/alginate multilayers on top of cross-linked films decreased endothelial cell adhesion, spreading, and proliferation to similar levels as uncross-linked films. Our findings highlight the key role of surface chemistry in cell-multilayer film interactions, and these engineered nanocoatings represent a tunable model of cell adhesive and non-adhesive multilayered films. PMID:28126597

Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

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

Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.

Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. The chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of themore » interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO3 biomineralization.« less

Chemistry and petrography of calcite in the KTB pilot borehole, Bavarian Oberpfalz, Germany

USGS Publications Warehouse

Komor, S.C.

1995-01-01

The KTB pilot borehole in northeast Bavaria, Germany, penetrates 4000 m of gneiss, amphibolite, and subordinate calc-silicate, lamprophyre and metagabbro. There are three types of calcite in the drilled section: 1) metamorphic calcite in calc-silicate and marble; 2) crack-filling calcite in all lithologies; and 3) replacement calcite in altered minerals. Crack-filling and replacement calcite postdate metamorphic calcite. Multiple calcite generations in individual cracks suggest that different generations of water repeatedly flowed through the same cracks. Crack-filling mineral assemblages that include calcite originally formed at temperatures of 150-350??C. Presently, crack-filling calcite is in chemical and isotopic equilibrium with saline to brackish water in the borehole at temperatures of ???120??C. The saline to brackish water contains a significant proportion of meteoric water. Re-equilibration of crack-filling calcite to lower temperatures means that calcite chemistry tells us little about water-rock interactions in the crystal section of temperatures higher than ~120??C. -from Author

Picoliter DNA Sequencing Chemistry on an Electrowetting-based Digital Microfluidic Platform

PubMed Central

Ferguson Welch, Erin R.; Lin, Yan-You; Madison, Andrew; Fair, R.B.

2011-01-01

The results of investigations into performing DNA sequencing chemistry on a picoliter-scale electrowetting digital microfluidic platform are reported. Pyrosequencing utilizes pyrophosphate produced during nucleotide base addition to initiate a process ending with detection through a chemiluminescence reaction using firefly luciferase. The intensity of light produced during the reaction can be quantified to determine the number of bases added to the DNA strand. The logic-based control and discrete fluid droplets of a digital microfluidic device lend themselves well to the pyrosequencing process. Bead-bound DNA is magnetically held in a single location, and wash or reagent droplets added or split from it to circumvent product dilution. Here we discuss the dispensing, control, and magnetic manipulation of the paramagnetic beads used to hold target DNA. We also demonstrate and characterize the picoliter-scale reaction of luciferase with adenosine triphosphate to represent the detection steps of pyrosequencing and all necessary alterations for working on this scale. PMID:21298802

A preliminary sensitivity analysis of the coupled diffusion and chemistry model. [effect of SST operations on ambient ozone in lower stratosphere

NASA Technical Reports Server (NTRS)

Hilst, G. R.; Contiliano, R. M.

1973-01-01

The sensitivity of the coupled chemistry/diffusion model's outputs to a wide range of variation of the model's independent variables has been investigated. It is shown that the efficiency with which the now catalytic cycle destroys ambient O3 is extremely sensitive to the amount of NO emitted and to the relative rates of turbulent diffusion and chemical reactions. For representative conditions in the stratosphere, a tenfold variation of either the turbulence intensity or the reaction rate constant or the source strength can vary the efficiency from 1% to 50%. If the duration of Phase 3 is a significant fraction of the total residence time of the plume, then these efficiency variations can alter O3 depletion rates by more than a factor of two. These results, therefore, point toward those variables which must be accurately defined or measured if one is to adequately predict the effect of SST operations on the ambient inventory of O3 in the lower stratosphere.

Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

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

Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.

2016-10-28

Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. The chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of themore » interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO3 biomineralization.« less

Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

DOE PAGES

Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.; ...

2016-10-28

Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. Here, the chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side ofmore » the interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO 3 biomineralization.« less

Greenhouse conditions induce mineralogical changes and dolomite accumulation in coralline algae on tropical reefs

PubMed Central

Diaz-Pulido, Guillermo; Nash, Merinda C.; Anthony, Kenneth R.N.; Bender, Dorothea; Opdyke, Bradley N.; Reyes-Nivia, Catalina; Troitzsch, Ulrike

2014-01-01

Human-induced ocean acidification and warming alter seawater carbonate chemistry reducing the calcification of reef-building crustose coralline algae (CCA), which has implications for reef stability. However, due to the presence of multiple carbonate minerals with different solubilities in seawater, the algal mineralogical responses to changes in carbonate chemistry are poorly understood. Here we demonstrate a 200% increase in dolomite concentration in living CCA under greenhouse conditions of high pCO2 (1,225 μatm) and warming (30 °C). Aragonite, in contrast, increases with lower pCO2 (296 μatm) and low temperature (28 °C). Mineral changes in the surface pigmented skeleton are minor and dolomite and aragonite formation largely occurs in the white crust beneath. Dissolution of high-Mg-calcite and particularly the erosive activities of endolithic algae living inside skeletons play key roles in concentrating dolomite in greenhouse treatments. As oceans acidify and warm in the future, the relative abundance of dolomite in CCA will increase. PMID:24518160

Daily and seasonal variability of pH, dissolved oxygen, temperature, and specific conductance in the Colorado River between the forebay of Glen Canyon, Dam and Lees Ferry, northeastern Arizona, 1998-99

USGS Publications Warehouse

Flynn, Marilyn E.; Hart, Robert J.; Marzolf, G. Richard; Bowser, Carl J.

2001-01-01

The productivity of the trout fishery in the tailwater reach of the Colorado River downstream from Glen Canyon Dam depends on the productivity of lower trophic levels. Photosynthesis and respiration are basic biological processes that control productivity and alter pH and oxygen concentration. During 1998?99, data were collected to aid in the documentation of short- and long-term trends in these basic ecosystem processes in the Glen Canyon reach. Dissolved-oxygen, temperature, and specific-conductance profile data were collected monthly in the forebay of Glen Canyon Dam to document the status of water chemistry in the reservoir. In addition, pH, dissolved-oxygen, temperature, and specific-conductance data were collected at five sites in the Colorado River tailwater of Glen Canyon Dam to document the daily, seasonal, and longitudinal range of variation in water chemistry that could occur annually within the Glen Canyon reach.

Celebrating wobble decoding: Half a century and still much is new.

PubMed

Agris, Paul F; Eruysal, Emily R; Narendran, Amithi; Väre, Ville Y P; Vangaveti, Sweta; Ranganathan, Srivathsan V

2017-08-16

A simple post-transcriptional modification of tRNA, deamination of adenosine to inosine at the first, or wobble, position of the anticodon, inspired Francis Crick's Wobble Hypothesis 50 years ago. Many more naturally-occurring modifications have been elucidated and continue to be discovered. The post-transcriptional modifications of tRNA's anticodon domain are the most diverse and chemically complex of any RNA modifications. Their contribution with regards to chemistry, structure and dynamics reveal individual and combined effects on tRNA function in recognition of cognate and wobble codons. As forecast by the Modified Wobble Hypothesis 25 years ago, some individual modifications at tRNA's wobble position have evolved to restrict codon recognition whereas others expand the tRNA's ability to read as many as four synonymous codons. Here, we review tRNA wobble codon recognition using specific examples of simple and complex modification chemistries that alter tRNA function. Understanding natural modifications has inspired evolutionary insights and possible innovation in protein synthesis.

Microtopographic and depth controls on active layer chemistry in Arctic polygonal ground

DOE PAGES

Newman, Brent D.; Throckmorton, Heather M.; Graham, David E.; ...

2015-03-24

Polygonal ground is a signature characteristic of Arctic lowlands, and carbon release from permafrost thaw can alter feedbacks to Arctic ecosystems and climate. This study describes the first comprehensive spatial examination of active layer biogeochemistry that extends across high- and low-centered, ice wedge polygons, their features, and with depth. Water chemistry measurements of 54 analytes were made on surface and active layer pore waters collected near Barrow, Alaska, USA. Significant differences were observed between high- and low-centered polygons suggesting that polygon types may be useful for landscape-scale geochemical classification. However, differences were found for polygon features (centers and troughs) formore » analytes that were not significant for polygon type, suggesting that finer-scale features affect biogeochemistry differently from polygon types. Depth variations were also significant, demonstrating important multidimensional aspects of polygonal ground biogeochemistry. These results have major implications for understanding how polygonal ground ecosystems function, and how they may respond to future change.« less

Principal components - Petrology and chemistry of polyphase units in chondritic porous interplanetary dust particles

NASA Astrophysics Data System (ADS)

Rietmeijer, Frans J. M.

1997-03-01

Chondritic porous (CP) interplanetary dust particles (IDPs) can be described as 'cosmic sediments'. It should be possible to recognize in these IDPs the 4500 Myrs old solar nebula dusts. The studies of unaltered chondritic IDPs show that their matrices are a mixture of three different principal components (PCs) that also describe variable C/Si ratios of chondritic IDPs. Among others, PCs include polyphase units (PUs) that are amorphous to holocrystalline, both ultrafine- and coarse-grained, ferromagnesiosilica(te) materials with minor Al and Ca. The properties of PCs and their alteration products define the physical and chemical processes that produced and altered these components. PCs are also cornerstones of IDP classification. For example, the bulk composition of ultrafine-grained PCs can be reconstructed using the 'butterfly method' and also allows an evaluation of the metamorphic signatures, (e.g., dynamic pyrometamorphism), in chondritic IDPs.

Effect of ionic liquid on activity, stability, and structure of enzymes: a review.

PubMed

Naushad, Mu; Alothman, Zied Abdullah; Khan, Abbul Bashar; Ali, Maroof

2012-11-01

Ionic liquids have shown their potential as a solvent media for many enzymatic reactions as well as protein preservation, because of their unusual characteristics. It is also observed that change in cation or anion alters the physiochemical properties of the ionic liquids, which in turn influence the enzymatic reactions by altering the structure, activity, enatioselectivity, and stability of the enzymes. Thus, it is utmost need of the researchers to have full understanding of these influences created by ionic liquids before choosing or developing an ionic liquid to serve as solvent media for enzymatic reaction or protein preservation. So, in the present review, we try to shed light on effects of ionic liquids chemistry on structure, stability, and activity of enzymes, which will be helpful for the researchers in various biocatalytic applications. Copyright © 2012. Published by Elsevier B.V.

The Martian Soil as a Geochemical Sink for Hydrothermally Altered Crustal Rocks and Mobile Elements: Implications of Early MER Results

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Nelson, M. J.; Shearer, C. K.; Draper, D. S.

2005-01-01

Hydrothermal and aqueous alteration can explain some of the exciting results from the MER team s analyses of the martian soil, including the major elements, mobile elements, and the nickel enrichment. Published results from the five lander missions lead to the following conclusions: 1) The soil appears to be globally mixed and basaltic with only small local variations in chemistry. Relative to martian basaltic meteorites and Gusev rocks the soils are depleted in the fluid-mobile element calcium, but only slightly enriched to somewhat depleted in iron oxide. 2) The presence of olivine in the soils based on M ssbauer data argues that the soil is only partly weathered and is more akin to a lunar regolith than a terrestrial soil. 3) The presence of bromine along with sulfur and chlorine in the soils is consistent with addition of a mobile element component to the soil.

Personalizing Biomaterials for Precision Nanomedicine Considering the Local Tissue Microenvironment.

PubMed

Oliva, Nuria; Unterman, Shimon; Zhang, Yi; Conde, João; Song, Hyun Seok; Artzi, Natalie

2015-08-05

New advances in (nano)biomaterial design coupled with the detailed study of tissue-biomaterial interactions can open a new chapter in personalized medicine, where biomaterials are chosen and designed to match specific tissue types and disease states. The notion of a "one size fits all" biomaterial no longer exists, as growing evidence points to the value of customizing material design to enhance (pre)clinical performance. The complex microenvironment in vivo at different tissue sites exhibits diverse cell types, tissue chemistry, tissue morphology, and mechanical stresses that are further altered by local pathology. This complex and dynamic environment may alter the implanted material's properties and in turn affect its in vivo performance. It is crucial, therefore, to carefully study tissue context and optimize biomaterials considering the implantation conditions. This practice would enable attaining predictable material performance and enhance clinical outcomes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Imaging natural materials with a quasi-microscope. [spectrophotometry of granular materials

NASA Technical Reports Server (NTRS)

Bragg, S.; Arvidson, R.

1977-01-01

A Viking lander camera with auxilliary optics mounted inside the dust post was evaluated to determine its capability for imaging the inorganic properties of granular materials. During mission operations, prepared samples would be delivered to a plate positioned within the camera's field of view and depth of focus. The auxiliary optics would then allow soil samples to be imaged with an 11 pm pixel size in the broad band (high resolution, black and white) mode, and a 33 pm pixel size in the multispectral mode. The equipment will be used to characterize: (1) the size distribution of grains produced by igneous (intrusive and extrusive) processes or by shock metamorphism, (2) the size distribution resulting from crushing, chemical alteration, or by hydraulic or aerodynamic sorting; (3) the shape and degree of grain roundness and surface texture induced by mechanical and chemical alteration; and (4) the mineralogy and chemistry of grains.

Impacts on water quality and biota from natural acid rock drainage in Colorado's Lake Creek watershed

USGS Publications Warehouse

Bird, D.A.; Sares, Matthew A.; Policky, Greg A.; Schmidt, Travis S.; Church, Stan E.

2006-01-01

Colorado's Lake Creek watershed hosts natural acid rock drainage that significantly impacts surface water, streambed sediment, and aquatic life. The source of the ARD is a group of iron-rich springs that emerge from intensely hydrothermally altered, unexploited, low-grade porphyry copper mineralization in the Grizzly Peak Caldera. Source water chemistry includes pH of 2.5 and dissolved metal concentrations of up to 277 mg/L aluminum, 498 mg/L iron, and 10 mg/L copper. From the hydrothermally altered area downstream for 27 kilometers to Twin Lakes Reservoir, metal concentrations in streambed sediment are elevated and the watershed experiences locally severe adverse impacts to aquatic life due to the acidic, metal-laden water. The water and sediment quality of Twin Lakes Reservoir is sufficiently improved that the reservoir supports a trout fishery, and remnants of upstream ARD are negligible.

Rational approaches for engineering novel functionalities in carbon-carbon bond forming enzymes

PubMed Central

Baker, Perrin; Seah, Stephen Y. K.

2012-01-01

Enzymes that catalyze carbon-carbon bond formation can be exploited as biocatalyst for synthetic organic chemistry. However, natural enzymes frequently do not possess the required properties or specificities to catalyze industrially useful transformations. This mini-review describes recent work using knowledge-guided site-specific mutagenesis of key active site residues to alter substrate specificity, stereospecificity and reaction specificity of these enzymes. In addition, examples of de novo designed enzymes that catalyze C-C bond reactions not found in nature will be discussed. PMID:24688644

Oncogene-Induced Changes in Mammary Cell Fate and EMT in Breast Tumorigenesis

DTIC Science & Technology

2015-04-01

have worked on the project? Name: Lauren Walheim Project Role: Chemistry pre-medicine undergraduate student Researcher Identifier (e.g. ORCID ID...Distribution Unlimited The views, opinions and/or findings contained in this report are those of the author( s ) and should not be construed as an...Examine if IGF1R alters mammary cell fate in vivo and the effect this has on mammary tumorigenesis (months 13-30) ...…………………………………………….......11 2a

Overview of Stabilizing Ligands for Biocompatible Quantum Dot Nanocrystals

PubMed Central

Zhang, Yanjie; Clapp, Aaron

2011-01-01

Luminescent colloidal quantum dots (QDs) possess numerous advantages as fluorophores in biological applications. However, a principal challenge is how to retain the desirable optical properties of quantum dots in aqueous media while maintaining biocompatibility. Because QD photophysical properties are directly related to surface states, it is critical to control the surface chemistry that renders QDs biocompatible while maintaining electronic passivation. For more than a decade, investigators have used diverse strategies for altering the QD surface. This review summarizes the most successful approaches for preparing biocompatible QDs using various chemical ligands. PMID:22247651

Solute-specific patterns and drivers of urban stream chemistry revealed by long-term monitoring in Baltimore, Maryland

NASA Astrophysics Data System (ADS)

Reisinger, A. J.; Woytowitz, E.; Majcher, E.; Rosi, E. J.; Groffman, P.

2017-12-01

Urban streams receive a myriad of chemical inputs from the surrounding landscape due to altered lithology (asphalt, concrete), leaky sewage infrastructure, and other human activities (road salt, fertilizer, industrial wastes, wastewater effluent), potentially leading to multiple chemical stressors occurring simultaneously. To evaluate potential drivers of water chemistry change, we used approximately 20 years of weekly water chemistry monitoring data from streams in the Baltimore Ecosystem Study (BES) to quantify trends of annual loads and flow-weighted concentrations for multiple solutes of interest, including nitrate (NO3-), phosphate (PO43-), total nitrogen (TN), total phosphorus (TP), chloride (Cl-), and sulfate (SO42-) and subsequently examined various gray and green infrastructure characteristics at the watershed scale. For example, we quantified annual volume and duration of reported sanitary sewer overflows (SSO) and cumulative storage volume and area of various best management practices (BMPs). Site- and solute-specific trends differed, but across our monitoring network we found evidence for decreasing annual export for multiple solutes. Additionally, we found that changes in gray- and green-infrastructure characteristics were related to changes in water quality at our most downstream (most urban) monitoring site. For example, annual NO3- loads increased with longer cumulative SSO duration, whereas annual PO43- and TP loads decreased with a cumulative BMP area in the watershed. Further, we used same long-term water chemistry data and multivariate analyses to investigate whether urban streams have unique water chemistry fingerprints representing the multiple chemical stressors at a given site, which could provide insight into sources and impacts of water-quality impairment. These analyses and results illustrate the major role gray and green infrastructure play in influencing water quality in urban environments, and illustrate that focusing on a variety of chemical stressors is necessary to gain a broader understanding of the issues affecting urban water quality.

The NOx dependence of bromine chemistry in the Arctic atmospheric boundary layer

NASA Astrophysics Data System (ADS)

Custard, K. D.; Thompson, C. R.; Pratt, K. A.; Shepson, P. B.; Liao, J.; Huey, L. G.; Orlando, J. J.; Weinheimer, A. J.; Apel, E.; Hall, S. R.; Flocke, F.; Mauldin, L.; Hornbrook, R. S.; Pöhler, D.; S., General; Zielcke, J.; Simpson, W. R.; Platt, U.; Fried, A.; Weibring, P.; Sive, B. C.; Ullmann, K.; Cantrell, C.; Knapp, D. J.; Montzka, D. D.

2015-09-01

Arctic boundary layer nitrogen oxides (NOx = NO2 + NO) are naturally produced in and released from the sunlit snowpack and range between 10 to 100 pptv in the remote background surface layer air. These nitrogen oxides have significant effects on the partitioning and cycling of reactive radicals such as halogens and HOx (OH + HO2). However, little is known about the impacts of local anthropogenic NOx emission sources on gas-phase halogen chemistry in the Arctic, and this is important because these emissions can induce large variability in ambient NOx and thus local chemistry. In this study, a zero-dimensional photochemical kinetics model was used to investigate the influence of NOx on the unique springtime halogen and HOx chemistry in the Arctic. Trace gas measurements obtained during the 2009 OASIS (Ocean - Atmosphere - Sea Ice - Snowpack) field campaign at Barrow, AK were used to constrain many model inputs. We find that elevated NOx significantly impedes gas-phase halogen radical-based depletion of ozone, through the production of a variety of reservoir species, including HNO3, HO2NO2, peroxyacetyl nitrate (PAN), BrNO2, ClNO2 and reductions in BrO and HOBr. The effective removal of BrO by anthropogenic NOx was directly observed from measurements conducted near Prudhoe Bay, AK during the 2012 Bromine, Ozone, and Mercury Experiment (BROMEX). Thus, while changes in snow-covered sea ice attributable to climate change may alter the availability of molecular halogens for ozone and Hg depletion, predicting the impact of climate change on polar atmospheric chemistry is complex and must take into account the simultaneous impact of changes in the distribution and intensity of anthropogenic combustion sources. This is especially true for the Arctic, where NOx emissions are expected to increase because of increasing oil and gas extraction and shipping activities.

Hydrothermal Alteration of the Mt Unzen Conduit (Shimabara/Japan)

NASA Astrophysics Data System (ADS)

Yilmaz, T. I.; Mayer, K.; Hess, K. U.; Janots, E.; Gilg, H. A.; Dingwell, D. B.

2016-12-01

Investigations were carried out on hydrothermally altered coherent dacitic dykes samples from (USDP-4) drill core at Mt Unzen stratovolcano (Shimabara/Japan). XRF, XRD, EMPA, and C-O-isotope analysis led to insights concerning chemistry, mineralogy, and intensity of alteration as well as the origin of carbonate-precipitating fluids. Additionally a textural characterization of the occurring replacement features in the magma conduit zone was performed. The occurrence of the main secondary phases such as chlorite, pyrite, carbonates, and R1 (Reichweite parameter) illite-smectite indicate a weak to moderate propylitic to phyllic hydrothermal alteration. The dacitic samples of the dykes show different hydrothermal alteration features: (i) carbonate pseudomorphs after hornblende as well as core and zonal textures due to replacement of plagioclase by R1 illite-smectite, (ii) colloform banded fracture fillings and fillings in dissolution vugs, and (iii) chlorite and R1 illite-smectite in the groundmass. Carbonates in fractures comprise iron-rich dolomite solid solutions ("ankerite") and calcite. Isotopic values of d13Cvpdb = -4.59 ± 0.6‰ and d18Ovpdb = -21.73 ± 0.5‰ indicate a hydrothermal-magmatic origin for the carbonate formation. The chlorite-carbonate-pyrite index (CCPI) and the Ishikawa alteration index (AI), applied to the investigated samples show significant differences (CCPI=52.7-57.8; AI=36.1-40.6) indicating their different degree of alteration. According to Nakada et al., 2005, the C13 to C16 dykes represent the feeder dyke from the latest eruption (1991-1995) whereas C8 represents an earlier dyke feeder dyke from an older eruption. Weakest conduit alteration, which was obtained in samples C16-1-5 and C13-2-5, correlates with the alteration degree of the pristine dome rocks. Highest CCPI value was determined for sample C14-1-5 and the highest AI value was determined for sample C15-2-6. The degrees of alteration do not indicate highest alteration of the samples C8-1-2 and C8-2-1 from the older dykes.

Plant litter chemistry alters the content and composition of organic carbon associated with soil mineral and aggregate fractions in invaded ecosystems.

PubMed

Tamura, Mioko; Suseela, Vidya; Simpson, Myrna; Powell, Brian; Tharayil, Nishanth

2017-10-01

Through the input of disproportionate quantities of chemically distinct litter, invasive plants may potentially influence the fate of organic matter associated with soil mineral and aggregate fractions in some of the ecosystems they invade. Although context dependent, these native ecosystems subjected to prolonged invasion by exotic plants may be instrumental in distinguishing the role of plant-microbe-mineral interactions from the broader edaphic and climatic influences on the formation of soil organic matter (SOM). We hypothesized that the soils subjected to prolonged invasion by an exotic plant that input recalcitrant litter (Japanese knotweed, Polygonum cuspidatum) would have a greater proportion of plant-derived carbon (C) in the aggregate fractions, as compared with that in adjacent soil inhabited by native vegetation that input labile litter, whereas the soils under an invader that input labile litter (kudzu, Pueraria lobata) would have a greater proportion of microbial-derived C in the silt-clay fraction, as compared with that in adjacent soils that receive recalcitrant litter. At the knotweed site, the higher C content in soils under P. cuspidatum, compared with noninvaded soils inhabited by grasses and forbs, was limited to the macroaggregate fraction, which was abundant in plant biomarkers. The noninvaded soils at this site had a higher abundance of lignins in mineral and microaggregate fractions and suberin in the macroaggregate fraction, partly because of the greater root density of the native species, which might have had an overriding influence on the chemistry of the above-ground litter input. At the kudzu site, soils under P. lobata had lower C content across all size fractions at a 0-5 cm soil depth despite receiving similar amounts of Pinus litter. Contrary to our prediction, the noninvaded soils receiving recalcitrant Pinus litter had a similar abundance of plant biomarkers across both mineral and aggregate fractions, potentially because of the higher surface area of soil minerals at this site. The plant biomarkers were lower in the aggregate fractions of the P. lobata-invaded soils, compared with noninvaded pine stands, potentially suggesting a microbial co-metabolism of pine-derived compounds. These results highlight the complex interactions among litter chemistry, soil biota, and minerals in mediating soil C storage in unmanaged ecosystems; these interactions are particularly important under global changes that may alter plant species composition and hence the quantity and chemistry of litter inputs in terrestrial ecosystems. © 2017 John Wiley & Sons Ltd.

Carbon petrology in cometary dust

NASA Technical Reports Server (NTRS)

Rietmeijer, Frans J. M.

1992-01-01

Chondritic porous (CP) interplanetary dust particles (IDP's) are collected in the Earth's stratosphere. There exists an extensive database on major and minor element chemistry, stable isotopes, noble gas abundances and mineralogy of many CP IDP's, as well as infrared and Raman spectroscopic properties. For details on the mineralogy, chemistry and physical properties of IDP's, I refer to the reviews by Mackinnon and Rietmeijer (1987), Bradley et al. (1988) and Sandford (1987). Texture, mineralogy (Mackinnon and Rietmeijer, 1987) and chemistry (Schramm et al., 1989; Flynn and Sutton, 1991) support the notion that CP IDP's are a unique group of ultrafine-grained extraterrestiral materials that are distinct from any known meteorite class. Their fluffy, or porous, morphology suggests that CP IDP's probably endured minimal alteration by protoplanetary processes since their formation. It is generally accepted that CP IDP's are solid debris from short-period comets. The evidence is mostly circumstantial but this notion gained significant support based on the comet Halley dust data (Brownlee, 1990). In this paper, I will accept that CP IDP's are indeed cometary dust. The C/Si ratio in CP IDP's is 3.3 times higher than in CI carbonaceous chondrites (Schramm et al. 1989). The intraparticle carbon distribution is heteorogeneous (Rietmeijer and McKay, 1986). Carbon occurs both in oxidized and reduced forms. Analytical electron microscope (AEM) and Raman spectroscopic analyses have shown the presence of several carbon forms in CP IDP's but the data are scattered in the literature. Carbons in cometary CP IDP's are among the most pristine Solar System carbons available for laboratory study. Similar to a recently developed petrological model for the diversity of layer silicates in CP IDP's (Zolensky, 1991) that is useful to constrain in situ aqueous alteration in comets (Rietmeijer and Mackinnon, 1987a), I here present the first effort to develop a petrological concept of carbons in CP IDP's. This concept is useful to constrain comet evolution. I also present the philosophical constraint facing Earth Scientists in studies of protoplanets that require a new approach to cometary dust studies.

Droplet Deformation in an Extensional Flow: The Role of Surfactant Physical Chemistry

NASA Technical Reports Server (NTRS)

Stebe, Kathleen J.

1996-01-01

Surfactant-induced Marangoni effects strongly alter the stresses exerted along fluid particle interfaces. In low gravity processes, these stresses can dictate the system behavior. The dependence of Marangoni effects on surfactant physical chemistry is not understood, severely impacting our ability to predict and control fluid particle flows. A droplet in an extensional flow allows the controlled study of stretching and deforming interfaces. The deformations of the drop allow both Marangoni stresses, which resist tangential shear, and Marangoni elasticities, which resist surface dilatation, to develop. This flow presents an ideal model system for studying these effects. Prior surfactant-related work in this flow considered a linear dependence of the surface tension on the surface concentration, valid only at dilute surface concentrations, or a non-linear framework at concentrations sufficiently dilute that the linear approximation was valid. The linear framework becomes inadequate for several reasons. The finite dimensions of surfactant molecules must be taken into account with a model that includes surfaces saturation. Nonideal interactions between adsorbed surfactant molecules alter the partitioning of surfactant between the bulk and the interface, the dynamics of surfactant adsorptive/desorptive exchange, and the sensitivity of the surface tension to adsorbed surfactant. For example, cohesion between hydrocarbon chains favors strong adsorption. Cohesion also slows the rate of desorption from interfaces, and decreases the sensitivity of the surface tension to adsorbed surfactant. Strong cohesive interactions result in first order surface phase changes with a plateau in the surface tension vs surface concentration. Within this surface concentration range, the surface tension is decoupled from surface concentration gradients. We are engaged in the study of the role of surfactant physical chemistry in determining the Marangoni stresses on a drop in an extensional flow in a numerical and experimental program. Using surfactants whose dynamics and equilibrium behavior have been characterized in our laboratory, drop deformation will be studied in ground-based experiment. In an accompanying numerical study, predictive drop deformations will be determined based on the isotherm and equation of state determined in our laboratory. This work will improve our abilities to predict and control all fluid particle flows.

Short-term Dynamics of Photopriming Increase Carbon Loss During Litter Decomposition

NASA Astrophysics Data System (ADS)

Lin, Y.; King, J. Y.; Karlen, S. D.; Ralph, J.

2017-12-01

Solar radiation plays a key role in carbon (C) cycling by increasing the decomposition rates of plant litter through photodegradation. This process is particularly important in drylands where solar radiation is high and microbial activity may be limited by water availability. One mechanism of photodegradation may be the facilitation of microbial decomposition of litter by altering litter chemistry and consequently degradability, termed photopriming. However, it remains unclear to what extent photopriming contributes to litter decomposition. We evaluated photopriming by ultraviolet (UV) radiation through two laboratory experiments. In one experiment, we found that four months of UV exposure increased mass loss by 3-4% compared to dark treatment in two of three litter species commonly found in California oak savanna; however, UV exposure did not alter litter degradability as measured by microbial respiration in an incubation study. UV exposure had limited effects on lignin and other cell wall structures, but one month of microbial decomposition in the dark significantly reduced lignin β-aryl ether inter-unit linkages and acetylated xylans, which interestingly was the same pattern seen in litter exposed to UV radiation under field conditions and may account for the significant effects of UV exposure on litter mass loss observed in situ. These results indicate that microbial decomposition, not abiotic photodegradation, was ultimately responsible for changes in litter chemistry observed in the field. In a separate experiment, litter of a common grass was incubated for 128 days under either alternating UV radiation and dark conditions at two-day intervals or continuous darkness. During the second half of the experiment, alternating UV exposure increased CO2 production by 35% compared to continuous darkness, suggesting that UV exposure induces subtle but important changes in litter chemistry that facilitate microbial decomposition on a temporal scale of days. Together the results point to microbial facilitation as the primary mechanism of photodegradation and suggest that photopriming is governed by short-term dynamics at the litter-microbe interface. The C cycling associated with these short-term dynamics may be especially sensitive to anticipated increases in drought conditions in drylands.

Urban and Suburban Influences on Water Chemistry in Washington DC: Impervious Surfaces and Urban Stream Syndrome

NASA Astrophysics Data System (ADS)

MacAvoy, S. E.; Petersen, E.

2015-12-01

Among the challenges facing urban rivers are water stormwater runoff problems and changing water chemistry, not only from air and water pollution sources, but also from altered geology with the development of "urban karst". Seventy five percent of the Anacostia River in Washington, D.C. is urban or impervious. The Anacostia River experiences environmental challenges similar to those of other urban industrial rivers (heavy metal, PCB and PAH contamination). It also has Ca/Sr ratios above 200, and Na concentrations higher than Ca, and elevated ionic strength, all associated with extended chemical interaction with concrete. While these chemical characteristics have been documented in the urban areas within DC, they have not been examined in the largely suburban/mixed development tributaries of the Anacostia. Here we examine the base-flow geochemistry of the Anacostia River and its suburban tributaries (6 locations) over a year (November 2014- August 2015), concentrating on the following water chemistry variables: pH, hardness, SAR, alkalinity, Ca, Mg, Na, K, Fe, Mn, Zn, Al, Ba, Ni, total P, S, Sr, NO3-, NH4+, PO43-. NO3- and NH4+ were generally lowest in at all sites in January, but rose to between 0.5 and 2.4 mg/L in June, with highest NO3- concentrations in suburban areas. Na and Cl concentrations were 5x higher in suburban areas than urban areas during the winter months. Ca/Sr concentration ratios, were between 120 and 200 for suburban sites but increased as the sites became more urban (to a high of 240 for the most urban site). These trends have been observed in other urban streams, and correlate with percent impervious area. The data follow patterns expected for "urban stream syndrome" and dissolution of concrete. Suburban areas, with their relatively small streams, show greater winter salting effects than more urban areas down stream. Suburban areas also show higher NO3- (and occasionally higher NH4+) than urban areas except in winter. The data presented here demonstrates that the geochemistry of highly urbanized systems may be significantly altered and should be better understood in order to assess urban impacts on water quality.

Transformations of DOM in forested catchments: the pathways of DOM from litter and soil to river export

NASA Astrophysics Data System (ADS)

Lajtha, K.; Yano, Y.; Crow, S.; Kaushal, S.

2006-12-01

Although the quality and quantity of DOM ultimately derives from plant detritus and soils in watersheds, three is substantial alteration of DOM as it passes from litter through the terrestrial landscape. As DOM is generated from plant and microbial detritus and processing, different fractions may be lost via respiration, form quasi-stable soil organic matter, or be temporarily sorbed to soil minerals. We followed the fate of DOC and DON from forested plots with experimentally altered detritus loads to determine the relative roles of original plant litter chemistry and soil transformations. Our study site was the DIRT (Detrital Input and Removal Treatment) plots at the H.J. Andrews Experimental Forest in Oregon, where treatments include detrital additions (wood vs. needle litter), litter exclusion, and root exclusions. Fractionation of detritus leachate solutions demonstrated significant differences in DOC chemistry from different detrital sources. Root leachates produced high quantities of hydrophilic neutral DOC, a fraction rich in labile sugars and polysaccharides; young wood extracts produced higher quantities of weak hydrophobic acids and hydrophobic neutrals (longer chain hydrocarbons); older wood had lower quantities of most labile constituents but was rich in strong hydrophobic acids. Although laboratory extracts of different litter types showed differences in DOM chemistry, soil solutions collected just below the forest floor from the differing detrital treatments were remarkably uniform and poor in labile constituents, suggesting microbial equalization of DOM leachate in the field. DOM quality and concentrations changed significantly with passage through soil profiles. DOC concentrations decreased through the soil profile in all plots to a greater degree than did dissolved organic nitrogen (DON), most likely due to preferential sorption of high C:N hydrophobic dissolved organic matter (DOM) in upper horizons. Percent hydrophobic DOM decreased significantly with depth, and the remaining hydrophilic DOM had a much lower and narrower C:N ratio than hydrophobic DOM. We also hypothesize that protein-reactive polyphenols, or tannins, may contribute to the decreased lability of N-rich DOM in soil solutions and thus significantly influence the quality of DOM delivered to streams.

Biogenic acidification reduces sea urchin gonad growth and increases susceptibility of aquaculture to ocean acidification.

PubMed

Mos, Benjamin; Byrne, Maria; Dworjanyn, Symon A

2016-02-01

Decreasing oceanic pH (ocean acidification) has emphasised the influence of carbonate chemistry on growth of calcifying marine organisms. However, calcifiers can also change carbonate chemistry of surrounding seawater through respiration and calcification, a potential limitation for aquaculture. This study examined how seawater exchange rate and stocking density of the sea urchin Tripneustes gratilla that were reproductively mature affected carbonate system parameters of their culture water, which in turn influenced growth, gonad production and gonad condition. Growth, relative spine length, gonad production and consumption rates were reduced by up to 67% by increased density (9-43 individuals.m(-2)) and reduced exchange rates (3.0-0.3 exchanges.hr(-1)), but survival and food conversion efficiency were unaffected. Analysis of the influence of seawater parameters indicated that reduced pH and calcite saturation state (ΩCa) were the primary factors limiting gonad production and growth. Uptake of bicarbonate and release of respiratory CO2 by T. gratilla changed the carbonate chemistry of surrounding water. Importantly total alkalinity (AT) was reduced, likely due to calcification by the urchins. Low AT limits the capacity of culture water to buffer against acidification. Direct management to counter biogenic acidification will be required to maintain productivity and reproductive output of marine calcifiers, especially as the ocean carbonate system is altered by climate driven ocean acidification. Copyright © 2015 Elsevier Ltd. All rights reserved.

Heterogeneity, pore pressure, and injectate chemistry: Control measures for geologic carbon storage

DOE PAGES

Dewers, Thomas; Eichhubl, Peter; Ganis, Ben; ...

2017-11-28

Desirable outcomes for geologic carbon storage include maximizing storage efficiency, preserving injectivity, and avoiding unwanted consequences such as caprock or wellbore leakage or induced seismicity during and post injection. Here, to achieve these outcomes, three control measures are evident including pore pressure, injectate chemistry, and knowledge and prudent use of geologic heterogeneity. Field, experimental, and modeling examples are presented that demonstrate controllable GCS via these three measures. Observed changes in reservoir response accompanying CO 2 injection at the Cranfield (Mississippi, USA) site, along with lab testing, show potential for use of injectate chemistry as a means to alter fracture permeabilitymore » (with concomitant improvements for sweep and storage efficiency). Further control of reservoir sweep attends brine extraction from reservoirs, with benefit for pressure control, mitigation of reservoir and wellbore damage, and water use. State-of-the-art validated models predict the extent of damage and deformation associated with pore pressure hazards in reservoirs, timing and location of networks of fractures, and development of localized leakage pathways. Experimentally validated geomechanics models show where wellbore failure is likely to occur during injection, and efficiency of repair methods. Use of heterogeneity as a control measure includes where best to inject, and where to avoid attempts at storage. Lastly, an example is use of waste zones or leaky seals to both reduce pore pressure hazards and enhance residual CO 2 trapping.« less

Heterogeneity, pore pressure, and injectate chemistry: Control measures for geologic carbon storage

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

Dewers, Thomas; Eichhubl, Peter; Ganis, Ben

Desirable outcomes for geologic carbon storage include maximizing storage efficiency, preserving injectivity, and avoiding unwanted consequences such as caprock or wellbore leakage or induced seismicity during and post injection. Here, to achieve these outcomes, three control measures are evident including pore pressure, injectate chemistry, and knowledge and prudent use of geologic heterogeneity. Field, experimental, and modeling examples are presented that demonstrate controllable GCS via these three measures. Observed changes in reservoir response accompanying CO 2 injection at the Cranfield (Mississippi, USA) site, along with lab testing, show potential for use of injectate chemistry as a means to alter fracture permeabilitymore » (with concomitant improvements for sweep and storage efficiency). Further control of reservoir sweep attends brine extraction from reservoirs, with benefit for pressure control, mitigation of reservoir and wellbore damage, and water use. State-of-the-art validated models predict the extent of damage and deformation associated with pore pressure hazards in reservoirs, timing and location of networks of fractures, and development of localized leakage pathways. Experimentally validated geomechanics models show where wellbore failure is likely to occur during injection, and efficiency of repair methods. Use of heterogeneity as a control measure includes where best to inject, and where to avoid attempts at storage. Lastly, an example is use of waste zones or leaky seals to both reduce pore pressure hazards and enhance residual CO 2 trapping.« less

Macroevolution of plant defenses against herbivores in the evening primroses.

PubMed

Johnson, Marc T J; Ives, Anthony R; Ahern, Jeffrey; Salminen, Juha-Pekka

2014-07-01

Plant species vary greatly in defenses against herbivores, but existing theory has struggled to explain this variation. Here, we test how phylogenetic relatedness, tradeoffs, trait syndromes, and sexual reproduction affect the macroevolution of defense. To examine the macroevolution of defenses, we studied 26 Oenothera (Onagraceae) species, combining chemistry, comparative phylogenetics and experimental assays of resistance against generalist and specialist herbivores. We detected dozens of phenolic metabolites within leaves, including ellagitannins (ETs), flavonoids, and caffeic acid derivatives (CAs). The concentration and composition of phenolics exhibited low to moderate phylogenetic signal. There were clear negative correlations between multiple traits, supporting the prediction of allocation tradeoffs. There were also positively covarying suites of traits, but these suites did not strongly predict resistance to herbivores and thus did not act as defensive syndromes. By contrast, specific metabolites did correlate with the performance of generalist and specialist herbivores. Finally, that repeated losses of sex in Oenothera was associated with the evolution of increased flavonoid diversity and altered phenolic composition. These results show that secondary chemistry has evolved rapidly during the diversification of Oenothera. This evolution has been marked by allocation tradeoffs between traits, some of which are related to herbivore performance. The repeated loss of sex appears also to have constrained the evolution of plant secondary chemistry, which may help to explain variation in defense among plants. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

Inhibition of bacterial and leukocyte adhesion under shear stress conditions by material surface chemistry.

PubMed

Patel, Jasmine D; Ebert, Michael; Stokes, Ken; Ward, Robert; Anderson, James M

2003-01-01

Biomaterial-centered infections, initiated by bacterial adhesion, persist due to a compromised host immune response. Altering implant materials with surface modifying endgroups (SMEs) may enhance their biocompatibility by reducing bacterial and inflammatory cell adhesion. A rotating disc model, which generates shear stress within physiological ranges, was used to characterize adhesion of leukocytes and Staphylococcus epidermidis on polycarbonate-urethanes and polyetherurethanes modified with SMEs (polyethylene oxide, fluorocarbon and dimethylsiloxane) under dynamic flow conditions. Bacterial adhesion in the absence of serum was found to be mediated by shear stress and surface chemistry, with reduced adhesion exhibited on materials modified with polydimethylsiloxane and polyethylene oxide SMEs. In contrast, bacterial adhesion was enhanced on materials modified with fluorocarbon SMEs. In the presence of serum, bacterial adhesion was primarily neither material nor shear dependent. However, bacterial adhesion in serum was significantly reduced to < or = 10% compared to adhesion in serum-free media. Leukocyte adhesion in serum exhibited a shear dependency with increased adhesion occurring in regions exposed to lower shear-stress levels of < or = 7 dyne/cm2. Additionally, polydimethylsiloxane and polyethylene oxide SMEs reduced leukocyte adhesion on polyether-urethanes. In conclusion, these results suggest that surface chemistry and shear stress can mediate bacterial and cellular adhesion. Furthermore, materials modified with polyethylene oxide SMEs are capable of inhibiting bacterial adhesion, consequently minimizing the probability of biomaterial-centered infections.

The response of Antarctic sea ice algae to changes in pH and CO2.

PubMed

McMinn, Andrew; Müller, Marius N; Martin, Andrew; Ryan, Ken G

2014-01-01

Ocean acidification substantially alters ocean carbon chemistry and hence pH but the effects on sea ice formation and the CO2 concentration in the enclosed brine channels are unknown. Microbial communities inhabiting sea ice ecosystems currently contribute 10-50% of the annual primary production of polar seas, supporting overwintering zooplankton species, especially Antarctic krill, and seeding spring phytoplankton blooms. Ocean acidification is occurring in all surface waters but the strongest effects will be experienced in polar ecosystems with significant effects on all trophic levels. Brine algae collected from McMurdo Sound (Antarctica) sea ice was incubated in situ under various carbonate chemistry conditions. The carbon chemistry was manipulated with acid, bicarbonate and bases to produce a pCO2 and pH range from 238 to 6066 µatm and 7.19 to 8.66, respectively. Elevated pCO2 positively affected the growth rate of the brine algal community, dominated by the unique ice dinoflagellate, Polarella glacialis. Growth rates were significantly reduced when pH dropped below 7.6. However, when the pH was held constant and the pCO2 increased, growth rates of the brine algae increased by more than 20% and showed no decline at pCO2 values more than five times current ambient levels. We suggest that projected increases in seawater pCO2, associated with OA, will not adversely impact brine algal communities.

Clathrin to Lipid Raft-Endocytosis via Controlled Surface Chemistry and Efficient Perinuclear Targeting of Nanoparticle.

PubMed

Chakraborty, Atanu; Jana, Nikhil R

2015-09-17

Nanoparticle interacts with live cells depending on their surface chemistry, enters into cell via endocytosis, and is commonly trafficked to an endosome/lysozome that restricts subcellular targeting options. Here we show that nanoparticle surface chemistry can be tuned to alter their cell uptake mechanism and subcellular trafficking. Quantum dot based nanoprobes of 20-30 nm hydrodynamic diameters have been synthesized with tunable surface charge (between +15 mV to -25 mV) and lipophilicity to influence their cellular uptake processes and subcellular trafficking. It is observed that cationic nanoprobe electrostatically interacts with cell membrane and enters into cell via clathrin-mediated endocytosis. At lower surface charge (between +10 mV to -10 mV), the electrostatic interaction with cell membrane becomes weaker, and additional lipid raft endocytosis is initiated. If a lipophilic functional group is introduced on a weakly anionic nanoparticle surface, the uptake mechanism shifts to predominant lipid raft-mediated endocytosis. In particular, the zwitterionic-lipophilic nanoprobe has the unique advantage as it weakly interacts with anionic cell membrane, migrates toward lipid rafts for interaction through lipophilic functional group, and induces lipid raft-mediated endocytosis. While predominate or partial clathrin-mediated entry traffics most of the nanoprobes to lysozome, predominate lipid raft-mediated entry traffics them to perinuclear region, particularly to the Golgi apparatus. This finding would guide in designing appropriate nanoprobe for subcellular targeting and delivery.

Molecular Mechanisms and Regulation of Urinary Acidification

PubMed Central

Kurtz, Ira

2015-01-01

The H+ concentration in human blood is kept within very narrow limits, ~ 40 nM, despite the fact that dietary metabolism generates acid and base loads that are added to the systemic circulation throughout the life of mammals. One of the primary functions of the kidney is to maintain the constancy of systemic acid-base chemistry. The kidney has evolved the capacity to regulate blood acidity by performing three key functions: 1) reabsorb HCO3− that is filtered through the glomeruli to prevent its excretion in the urine; 2) generate a sufficient quantity of new HCO3− to compensate for the loss of HCO3− resulting from dietary metabolic H+ loads and loss of HCO3− in the urea cycle; and 3) excrete HCO3− (or metabolizable organic anions) following a systemic base load. The ability of the kidney to perform these functions requires that various cell types throughout the nephron respond to changes in acid-base chemistry by modulating specific ion transport and/or metabolic processes in a coordinated fashion such that the urine and renal vein chemistry is altered appropriately. The purpose of the article is to provide the interested reader with a broad review of a field that began historically ~ 60 years ago with whole animal studies, and has evolved to where we are currently addressing questions related to kidney acid-base regulation at the single protein structure/function level. PMID:25428859

Effects of lead shot ingestion on delta-aminolevulinic acid dehydratase activity, hemoglobin concentration, and serum chemistry in bald eagles

USGS Publications Warehouse

Hoffman, D.J.; Pattee, O.H.; Wiemeyer, Stanley N.; Mulhern, B.

1981-01-01

Lead shot ingestion by bald eagles (Haliaeetus leucocephalus) is considered to be widespread and has been implicated in the death of eagles in nature. It was recently demonstrated under experimental conditions that ingestion of as few as 10 lead shot resulted in death within 12 to 20 days. In the present study hematological responses to lead toxicity including red blood cell ALAD activity, hemoglobin concentration and 23 different blood serum chemistries were examined in five captive bald eagles that were unsuitable for rehabilitation and release. Eagles were dosed by force-feeding with 10 lead shot; they were redosed if regurgitation occurred. Red blood cell ALAD activity was inhibited by nearly 80% within 24 hours when mean blood lead concentration had increased to 0.8 parts per million (ppm). By the end of 1 week there was a significant decrease (20-25%) in hematocrit and hemoglobin, and the mean blood lead concentration was over 3 ppm. Within as little as 1-2 weeks after dosing, significant elevations in serum creatinine and serum alanine aminotransferase occurred, as well as a significant decrease in the ratio of serum aspartic aminotransferase to serum alanine aminotransferase. The mean blood lead concentration was over 5 ppm by the end of 2 weeks. These changes in serum chemistry may be indicative of kidney and liver alterations.

Sense codon emancipation for proteome-wide incorporation of noncanonical amino acids: rare isoleucine codon AUA as a target for genetic code expansion

PubMed Central

Bohlke, Nina; Budisa, Nediljko

2014-01-01

One of the major challenges in contemporary synthetic biology is to find a route to engineer synthetic organisms with altered chemical constitution. In terms of core reaction types, nature uses an astonishingly limited repertoire of chemistries when compared with the exceptionally rich and diverse methods of organic chemistry. In this context, the most promising route to change and expand the fundamental chemistry of life is the inclusion of amino acid building blocks beyond the canonical 20 (i.e. expanding the genetic code). This strategy would allow the transfer of numerous chemical functionalities and reactions from the synthetic laboratory into the cellular environment. Due to limitations in terms of both efficiency and practical applicability, state-of-the-art nonsense suppression- or frameshift suppression-based methods are less suitable for such engineering. Consequently, we set out to achieve this goal by sense codon emancipation, that is, liberation from its natural decoding function – a prerequisite for the reassignment of degenerate sense codons to a new 21st amino acid. We have achieved this by redesigning of several features of the post-transcriptional modification machinery which are directly involved in the decoding process. In particular, we report first steps towards the reassignment of 5797 AUA isoleucine codons in Escherichia coli using efficient tools for tRNA nucleotide modification pathway engineering. PMID:24433543

Impact of natural organic matter and increased water hardness on DGT prediction of copper bioaccumulation by yellow lampmussel (Lampsilis cariosa) and fathead minnow (Pimephales promelas).

PubMed

Philipps, Rebecca R; Xu, Xiaoyu; Mills, Gary L; Bringolf, Robert B

2018-06-01

We conducted an exposure experiment with Diffusive Gradients in Thin- Films (DGT), fathead minnow (Pimephales promelas), and yellow lampmussel (Lampsilis cariosa) to estimate bioavailability and bioaccumulation of Cu. We hypothesized that Cu concentrations measured by DGT can be used to predict Cu accumulation in aquatic animals and alterations of water chemistry can affect DGT's predict ability. Three water chemistries (control soft water, hard water, and addition of natural organic matter (NOM)) and three Cu concentrations (0, 30, and 60 μg/L) were selected, so nine Cu-water chemistry combinations were used. NOM addition treatments resulted in decreased concentrations of DGT-measured Cu and free Cu ion predicted by Biotic Ligand Model (BLM). Both hard water and NOM addition treatments had reduced concentrations of Cu ion and Cu-dissolved organic matter complexes compared to other treatments. DGT-measured Cu concentrations were linearly correlated to fish accumulated Cu, but not to mussel accumulated Cu. Concentrations of bioavailable Cu predicted by BLM, the species complexed with biotic ligands of aquatic organisms and, was highly correlated to DGT-measured Cu. In general, DGT-measured Cu fit Cu accumulations in fish, and this passive sampling technique is acceptable at predicting Cu concentrations in fish in waters with low NOM concentrations. Copyright © 2018 Elsevier Ltd. All rights reserved.

Simulated ocean acidification reveals winners and losers in coastal phytoplankton.

PubMed

Bach, Lennart T; Alvarez-Fernandez, Santiago; Hornick, Thomas; Stuhr, Annegret; Riebesell, Ulf

2017-01-01

The oceans absorb ~25% of the annual anthropogenic CO2 emissions. This causes a shift in the marine carbonate chemistry termed ocean acidification (OA). OA is expected to influence metabolic processes in phytoplankton species but it is unclear how the combination of individual physiological changes alters the structure of entire phytoplankton communities. To investigate this, we deployed ten pelagic mesocosms (volume ~50 m3) for 113 days at the west coast of Sweden and simulated OA (pCO2 = 760 μatm) in five of them while the other five served as controls (380 μatm). We found: (1) Bulk chlorophyll a concentration and 10 out of 16 investigated phytoplankton groups were significantly and mostly positively affected by elevated CO2 concentrations. However, CO2 effects on abundance or biomass were generally subtle and present only during certain succession stages. (2) Some of the CO2-affected phytoplankton groups seemed to respond directly to altered carbonate chemistry (e.g. diatoms) while others (e.g. Synechococcus) were more likely to be indirectly affected through CO2 sensitive competitors or grazers. (3) Picoeukaryotic phytoplankton (0.2-2 μm) showed the clearest and relatively strong positive CO2 responses during several succession stages. We attribute this not only to a CO2 fertilization of their photosynthetic apparatus but also to an increased nutrient competitiveness under acidified (i.e. low pH) conditions. The stimulating influence of high CO2/low pH on picoeukaryote abundance observed in this experiment is strikingly consistent with results from previous studies, suggesting that picoeukaryotes are among the winners in a future ocean.

Transgenic miR156 switchgrass in the field: growth, recalcitrance and rust susceptibility

DOE PAGES

Baxter, Holly L.; Mazarei, Mitra; Dumitrache, Alexandru; ...

2017-04-24

Sustainable utilization of lignocellulosic perennial grass feedstocks will be enabled by high biomass production and optimized cell wall chemistry for efficient conversion into biofuels. MicroRNAs are regulatory elements that modulate the expression of genes involved in various biological functions in plants, including growth and development. In greenhouse studies, overexpressing a microRNA (miR156) gene in switchgrass had dramatic effects on plant architecture and flowering, which appeared to be driven by transgene expression levels. High expressing lines were extremely dwarfed, whereas low and moderate-expressing lines had higher biomass yields, improved sugar release and delayed flowering. Four lines with moderate or low miR156more » overexpression from the prior greenhouse study were selected for a field experiment to assess the relationship between miR156 expression and biomass production over three years. We also analysed important bioenergy feedstock traits such as flowering, disease resistance, cell wall chemistry and biofuel production. Phenotypes of the transgenic lines were inconsistent between the greenhouse and the field as well as among different field growing seasons. One low expressing transgenic line consistently produced more biomass (25%–56%) than the control across all three seasons, which translated to the production of 30% more biofuel per plant during the final season. The other three transgenic lines produced less biomass than the control by the final season, and the two lines with moderate expression levels also exhibited altered disease susceptibilities. Results of this study emphasize the importance of performing multiyear field studies for plants with altered regulatory transgenes that target plant growth and development.« less

Fish Mercury Loads and Lake Productivity Are Not Impacted by Wildland Fire in Northern Minnesota

NASA Astrophysics Data System (ADS)

Riggs, C.; Kolka, R. K.; Nater, E. A.; Witt, E.; Wickman, T.; Woodruff, L. G.; Butcher, J.

2016-12-01

Wildland fire can significantly alter mercury (Hg) cycling on land and in adjacent aquatic environments. In addition to enhancing local atmospheric Hg deposition, fire can influence terrestrial movement of Hg and other elements into lakes via runoff from burned upland soil. However, the impact of fire on water quality and the accumulation of Hg in fish remains equivocal. We investigated the effects of fire - specifically a low severity prescribed fire and moderate severity wildfire - on young-of-the-year yellow perch (Perca flavescens) and lake chemistry in two small remote watersheds in the Boundary Waters Canoe Area Wilderness in northeastern Minnesota using a paired watershed approach (fire-impacted vs. control watershed). Prior to fire, surface soil in the two study watersheds contained significant loads of Hg, mainly from atmospheric deposition. We expected fire to increase transport and deposition of Hg from smoke and burned soil into the fire-impacted lake, leading to changes in lake productivity and fish Hg loads. In contrast to our prediction, and despite significant effects of the moderate severity wildfire fire on upland soil Hg stocks, fish Hg accumulation and lake productivity were not affected by fire. Instead, climate and lake water levels were the strongest predictors of lake chemistry and fish responses in our study lakes. Our results suggest that low to moderate severity wildland fire does not alter lake productivity nor Hg accumulation in young-of-the-year yellow perch in these small, shallow lakes in the northern deciduous and boreal forest region. The effect of a high severity fire remains to be tested.

Hyperbolic metamaterial nanostructures to tune charge-transfer dynamics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Kwang Jin; Xiao, Yiming; Woo, Jae Heun; Kim, Eun Sun; Kreher, David; Attias, André-Jean; Mathevet, Fabrice; Ribierre, Jean-Charles; Wu, Jeong Weon; André, Pascal

2016-09-01

Charge transfer (CT) is an essential phenomenon relevant to numerous fields including biology, physics and chemistry.1-5 Here, we demonstrate that multi-layered hyperbolic metamaterial (HMM) substrates alter organic semiconductor CT dynamics.6 With triphenylene:perylene diimide dyad supramolecular self-assemblies prepared on HMM substrates, we show that both charge separation (CS) and charge recombination (CR) characteristic times are increased by factors of 2.5 and 1.6, respectively, resulting in longer-lived CT states. We successfully rationalize the experimental data by extending Marcus theory framework with dipole image interactions tuning the driving force. The number of metal-dielectric pairs alters the HMM interfacial effective dielectric constant and becomes a solid analogue to solvent polarizability. Based on the experimental results and extended Marcus theory framework, we find that CS and CR processes are located in normal and inverted regions on Marcus parabola diagram, respectively. The model and further PH3T:PCBM data show that the phenomenon is general and that molecular and substrate engineering offer a wide range of kinetic tailoring opportunities. This work opens the path toward novel artificial substrates designed to control CT dynamics with potential applications in fields including optoelectronics, organic solar cells and chemistry. 1. Marcus, Rev. Mod. Phys., 1993, 65, 599. 2. Marcus, Phys. Chem. Chem. Phys., 2012, 14, 13729. 3. Lambert, et al., Nat. Phys., 2012, 9, 10. 4. C. Clavero, Nat. Photon., 2014, 8, 95. 5. A. Canaguier-Durand, et al., Angew. Chem. Int. Ed., 2013, 52, 10533. 6. K. J. Lee, et al., Submitted, 2015, arxiv.org/abs/1510.08574.

Role of platinum DNA damage-induced transcriptional inhibition in chemotherapy-induced neuronal atrophy and peripheral neurotoxicity.

PubMed

Yan, Fang; Liu, Johnson J; Ip, Virginia; Jamieson, Stephen M F; McKeage, Mark J

2015-12-01

Platinum-based anticancer drugs cause peripheral neurotoxicity by damaging sensory neurons within the dorsal root ganglia (DRG), but the mechanisms are incompletely understood. The roles of platinum DNA binding, transcription inhibition and altered cell size were investigated in primary cultures of rat DRG cells. Click chemistry quantitative fluorescence imaging of RNA-incorporated 5-ethynyluridine showed high, but wide ranging, global levels of transcription in individual neurons that correlated with their cell body size. Treatment with platinum drugs reduced neuronal transcription and cell body size to an extent that corresponded to the amount of preceding platinum DNA binding, but without any loss of neuronal cells. The effects of platinum drugs on neuronal transcription and cell body size were inhibited by blocking platinum DNA binding with sodium thiosulfate, and mimicked by treatment with a model transcriptional inhibitor, actinomycin D. In vivo oxaliplatin treatment depleted the total RNA content of DRG tissue concurrently with altering DRG neuronal size. These findings point to a mechanism of chemotherapy-induced peripheral neurotoxicity, whereby platinum DNA damage induces global transcriptional arrest leading in turn to neuronal atrophy. DRG neurons may be particularly vulnerable to this mechanism of toxicity because of their requirements for high basal levels of global transcriptional activity. Findings point to a new stepwise mechanism of chemotherapy-induced peripheral neurotoxicity, whereby platinum DNA damage induces global transcriptional arrest leading in turn to neuronal atrophy. Dorsal root ganglion neurons may be particularly vulnerable to this neurotoxicity because of their high global transcriptional outputs, demonstrated in this study by click chemistry quantitative fluorescence imaging. © 2015 International Society for Neurochemistry.

Simulated ocean acidification reveals winners and losers in coastal phytoplankton

PubMed Central

Alvarez-Fernandez, Santiago; Hornick, Thomas; Stuhr, Annegret; Riebesell, Ulf

2017-01-01

The oceans absorb ~25% of the annual anthropogenic CO2 emissions. This causes a shift in the marine carbonate chemistry termed ocean acidification (OA). OA is expected to influence metabolic processes in phytoplankton species but it is unclear how the combination of individual physiological changes alters the structure of entire phytoplankton communities. To investigate this, we deployed ten pelagic mesocosms (volume ~50 m3) for 113 days at the west coast of Sweden and simulated OA (pCO2 = 760 μatm) in five of them while the other five served as controls (380 μatm). We found: (1) Bulk chlorophyll a concentration and 10 out of 16 investigated phytoplankton groups were significantly and mostly positively affected by elevated CO2 concentrations. However, CO2 effects on abundance or biomass were generally subtle and present only during certain succession stages. (2) Some of the CO2-affected phytoplankton groups seemed to respond directly to altered carbonate chemistry (e.g. diatoms) while others (e.g. Synechococcus) were more likely to be indirectly affected through CO2 sensitive competitors or grazers. (3) Picoeukaryotic phytoplankton (0.2–2 μm) showed the clearest and relatively strong positive CO2 responses during several succession stages. We attribute this not only to a CO2 fertilization of their photosynthetic apparatus but also to an increased nutrient competitiveness under acidified (i.e. low pH) conditions. The stimulating influence of high CO2/low pH on picoeukaryote abundance observed in this experiment is strikingly consistent with results from previous studies, suggesting that picoeukaryotes are among the winners in a future ocean. PMID:29190760

Biological Behavior of Osteoblast Cell and Apatite Forming Ability of the Surface Modified Ti Alloys.

PubMed

Zhao, Jingming; Hwang, K H; Choi, W S; Shin, S J; Lee, J K

2016-02-01

Titanium as one kind of biomaterials comes in direct contact with the body, making evaluation of biocompatibility an important aspect to biomaterials development. Surface chemistry of titanium plays an important role in osseointegration. Different surface modification alters the surface chemistry and result in different biological response. In this study, three kinds of mixed acid solutions were used to treat Ti specimens to induce Ca-P formation. Following a strong mixed acid activation process, Ca-P coating successfully formed on the Ti surfaces in simulated body fluid. Strong mixed acid increased the roughness of the metal surface, because the porous and rough surface allows better adhesion between Ca-P coatings and substrates. After modification of titanium surface by mixed acidic solution and subsequently H2O2/HCL treatment evaluation of biocompatibility was conducted from hydroxyapatite formation by biomimetic process and cell viability on modified titanium surface. Nano-scale modification of titanium surfaces can alter cellular and tissue responses, which may benefit osseointegration and dental implant therapy. Results from this study indicated that surface treatment methods affect the surface morphology, type of TiO2 layer formed and subsequent apatite deposition and biological responses. The thermo scientific alamarblue cell viability assay reagent is used to quantitatively measure the viability of mammalian cell lines, bacteria and fungi by incorporating a rapid, sensitive and reliable fluorometric/colorimetric growth indicator, without any toxic and side effect to cell line. In addition, mixed acid treatment uses a lower temperature and shorter time period than widely used alkali treatment.

Transgenic miR156 switchgrass in the field: growth, recalcitrance and rust susceptibility

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

Baxter, Holly L.; Mazarei, Mitra; Dumitrache, Alexandru

Sustainable utilization of lignocellulosic perennial grass feedstocks will be enabled by high biomass production and optimized cell wall chemistry for efficient conversion into biofuels. MicroRNAs are regulatory elements that modulate the expression of genes involved in various biological functions in plants, including growth and development. In greenhouse studies, overexpressing a microRNA (miR156) gene in switchgrass had dramatic effects on plant architecture and flowering, which appeared to be driven by transgene expression levels. High expressing lines were extremely dwarfed, whereas low and moderate-expressing lines had higher biomass yields, improved sugar release and delayed flowering. Four lines with moderate or low miR156more » overexpression from the prior greenhouse study were selected for a field experiment to assess the relationship between miR156 expression and biomass production over three years. We also analysed important bioenergy feedstock traits such as flowering, disease resistance, cell wall chemistry and biofuel production. Phenotypes of the transgenic lines were inconsistent between the greenhouse and the field as well as among different field growing seasons. One low expressing transgenic line consistently produced more biomass (25%–56%) than the control across all three seasons, which translated to the production of 30% more biofuel per plant during the final season. The other three transgenic lines produced less biomass than the control by the final season, and the two lines with moderate expression levels also exhibited altered disease susceptibilities. Results of this study emphasize the importance of performing multiyear field studies for plants with altered regulatory transgenes that target plant growth and development.« less

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

PubMed

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

NASA Astrophysics Data System (ADS)

Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

2016-02-01

Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function.

Litter chemistry prevails over litter consumers in mediating effects of past steel industry activities on leaf litter decomposition.

PubMed

Lucisine, Pierre; Lecerf, Antoine; Danger, Michaël; Felten, Vincent; Aran, Delphine; Auclerc, Apolline; Gross, Elisabeth M; Huot, Hermine; Morel, Jean-Louis; Muller, Serge; Nahmani, Johanne; Maunoury-Danger, Florence

2015-12-15

Soil pollution has adverse effects on the performance and life history traits of microorganisms, plants, and animals, yet evidence indicates that even the most polluted sites can support structurally-complex and dynamic ecosystems. The present study aims at determining whether and how litter decomposition, one of the most important soil ecological processes leaf, is affected in a highly trace-metal polluted site. We postulated that past steel mill activities resulting in soil pollution and associated changes in soil characteristics would influence the rate of litter decomposition through two non-exclusive pathways: altered litter chemistry and responses of decomposers to lethal and sub-lethal toxic stress. We carried out a litter-bag experiment using Populus tremula L. leaf litter collected at, and allowed to decompose in, a trace metal polluted site and in three unpolluted sites used as controls. We designed a fully-factorial transplant experimental design to assess effects of litter origin and exposure site on the rate of litter decomposition. We further determined initial litter chemistry, fungal biomass, mesofauna abundance in litter bags, and the soil macrofauna community. Irrespective of the site of litter exposure, litter originating from the polluted site had a two-fold faster decomposition than litter from the unpolluted sites. Litter chemistry, notably the lignin content, seemed most important in explaining the degradation rate of the leaf litter. Abundance of meso and macro-detritivores was higher at the polluted site than at the unpolluted sites. However, litter decomposition proceeded at similar rates in polluted and unpolluted sites. Our results show that trace metal pollution and associated soil and litter changes do not necessarily weaken consumer control on litter decomposition through lethal and sub-lethal toxic stress. Copyright © 2015. Published by Elsevier B.V.

Searching for life in the Universe: unconventional methods for an unconventional problem.

PubMed

Nealson, K H; Tsapin, A; Storrie-Lombardi, M

2002-12-01

The search for life, on and off our planet, can be done by conventional methods with which we are all familiar. These methods are sensitive and specific, and are often capable of detecting even single cells. However, if the search broadens to include life that may be different (even subtly different) in composition, the methods and even the approach must be altered. Here we discuss the development of what we call non-earthcentric life detection--detecting life with methods that could detect life no matter what its form or composition. To develop these methods, we simply ask, can we define life in terms of its general properties and particularly those that can be measured and quantified? Taking such an approach we can search for life using physics and chemistry to ask questions about structure, chemical composition, thermodynamics, and kinetics. Structural complexity can be searched for using computer algorithms that recognize complex structures. Once identified, these structures can be examined for a variety of chemical traits, including elemental composition, chirality, and complex chemistry. A second approach involves defining our environment in terms of energy sources (i.e., reductants), and oxidants (e.g. what is available to eat and breathe), and then looking for areas in which such phenomena are inexplicably out of chemical equilibrium. These disequilibria, when found, can then be examined in detail for the presence of the structural and chemical complexity that presumably characterizes any living systems. By this approach, we move the search for life to one that should facilitate the detection of any earthly life it encountered, as well as any non-conventional life forms that have structure, complex chemistry, and live via some form of redox chemistry.

Toxic effects of multi-walled carbon nanotubes on bivalves: Comparison between functionalized and nonfunctionalized nanoparticles.

PubMed

De Marchi, Lucia; Neto, Victor; Pretti, Carlo; Figueira, Etelvina; Chiellini, Federica; Morelli, Andrea; Soares, Amadeu M V M; Freitas, Rosa

2018-05-01

Despite of the large array of available carbon nanotube (CNT) configurations that allow different industrial and scientific applications of these nanoparticles, their impacts on aquatic organisms, especially on invertebrate species, are still limited. To our knowledge, no information is available on how surface chemistry alteration (functionalization) of CNTs may impact the toxicity of these NPs to bivalve species after a chronic exposure. For this reason, the impacts induced by chronic exposure (28days) to unfunctionalized MWCNTs (Nf-MWCNTs) in comparison with functionalized MWCNTs (f-MWCNTs), were evaluated in R. philippinarum, by measuring alterations induced in clams' oxidative status, neurotoxicity and metabolic capacity. The results obtained revealed that exposure to both MWCNT materials altered energy-related responses, with higher metabolic capacity and lower glycogen, protein and lipid concentrations in clams exposed to these CNTs. Moreover, R. philippinarum exposed to Nf-MWCNTs and f-MWCNTs showed oxidative stress expressed in higher lipid peroxidation and lower ratio between reduced and oxidized glutathione, despite the activation of defense mechanisms (superoxide-dismutase, glutathione peroxidase and glutathione S-transferases) in exposed clams. Additionally, neurotoxicity was observed by inhibition of Cholinesterases activity in organisms exposed to both MWCNTs. Copyright © 2017 Elsevier B.V. All rights reserved.

Plant Species Rather Than Climate Greatly Alters the Temporal Pattern of Litter Chemical Composition During Long-Term Decomposition

NASA Astrophysics Data System (ADS)

Li, Yongfu; Chen, Na; Harmon, Mark E.; Li, Yuan; Cao, Xiaoyan; Chappell, Mark A.; Mao, Jingdong

2015-10-01

A feedback between decomposition and litter chemical composition occurs with decomposition altering composition that in turn influences the decomposition rate. Elucidating the temporal pattern of chemical composition is vital to understand this feedback, but the effects of plant species and climate on chemical changes remain poorly understood, especially over multiple years. In a 10-year decomposition experiment with litter of four species (Acer saccharum, Drypetes glauca, Pinus resinosa, and Thuja plicata) from four sites that range from the arctic to tropics, we determined the abundance of 11 litter chemical constituents that were grouped into waxes, carbohydrates, lignin/tannins, and proteins/peptides using advanced 13C solid-state NMR techniques. Decomposition generally led to an enrichment of waxes and a depletion of carbohydrates, whereas the changes of other chemical constituents were inconsistent. Inconsistent convergence in chemical compositions during decomposition was observed among different litter species across a range of site conditions, whereas one litter species converged under different climate conditions. Our data clearly demonstrate that plant species rather than climate greatly alters the temporal pattern of litter chemical composition, suggesting the decomposition-chemistry feedback varies among different plant species.

Plant Species Rather Than Climate Greatly Alters the Temporal Pattern of Litter Chemical Composition During Long-Term Decomposition

PubMed Central

Li, Yongfu; Chen, Na; Harmon, Mark E.; Li, Yuan; Cao, Xiaoyan; Chappell, Mark A.; Mao, Jingdong

2015-01-01

A feedback between decomposition and litter chemical composition occurs with decomposition altering composition that in turn influences the decomposition rate. Elucidating the temporal pattern of chemical composition is vital to understand this feedback, but the effects of plant species and climate on chemical changes remain poorly understood, especially over multiple years. In a 10-year decomposition experiment with litter of four species (Acer saccharum, Drypetes glauca, Pinus resinosa, and Thuja plicata) from four sites that range from the arctic to tropics, we determined the abundance of 11 litter chemical constituents that were grouped into waxes, carbohydrates, lignin/tannins, and proteins/peptides using advanced 13C solid-state NMR techniques. Decomposition generally led to an enrichment of waxes and a depletion of carbohydrates, whereas the changes of other chemical constituents were inconsistent. Inconsistent convergence in chemical compositions during decomposition was observed among different litter species across a range of site conditions, whereas one litter species converged under different climate conditions. Our data clearly demonstrate that plant species rather than climate greatly alters the temporal pattern of litter chemical composition, suggesting the decomposition-chemistry feedback varies among different plant species. PMID:26515033

Major and trace element chemistry of separated fragments from a hibonite-bearing Allende inclusion

NASA Technical Reports Server (NTRS)

Davis, A. M.; Grossman, L.; Allen, J. M.

1978-01-01

The major and trace elements of separated fragments and a bulk sample from CG-11, a hibonite-bearing inclusion in the Allende meteorite, were analyzed. Major element abundances were used to determine the minerology of separated fragments. The high degree of correlation between Eu/Sm ratios and Lu/Yb ratios for the samples studied indicates that their rare earth element (REE) distributions are governed by two components. One, Lu-, Eu-rich, is probably hibonite; the other, depleted in these elements, seems to be associated with the secondary alteration phases, grossular, nepheline and anorthite. The REE distribution in CG-11 precludes melting events after formation of the secondary alteration phases, but a melting event involving the primary minerals cannot be excluded. The enrichment of Lu with respect to other measured REE in hibonite can be explained by present REE condensation models. Two Hf-bearing components, most likely hibonite and perovskite, are necessary to account for variations in Sc/Hf ratios in the fragments studied. The lithophile volatiles Na, Mn, Fe, Zn, and probably Cr increase in the same order as the amount of secondary alteration minerals; the volatile siderophile elements Co and Au, however, do not.

Petrography and chemistry of tungsten-rich oxycalciobetafite in hydrothermal veins of the Adamello contact aureole, northern Italy

NASA Astrophysics Data System (ADS)

Lumpkin, Gregory R.; Gieré, Reto; Williams, C. Terry; McGlinn, Peter J.; Payne, Timothy E.

2017-09-01

Tungsten-rich oxycalciobetafite occurs in complex Ti-rich hydrothermal veins emplaced within dolomite marble in the contact aureole of the Adamello batholith, northern Italy, where it occurs as overgrowths on zirconolite. The betafite is weakly zoned and contains 29-34 wt% UO2. In terms of end-members, the betafite contains approximately 50 mol% CaUTi2O7 and is one of the closest known natural compositions to the pyrochlore phase proposed for use in titanate nuclear waste forms. Amorphization and volume expansion of the betafite caused cracks to form in the enclosing silicate mineral grains. Backscattered electron images reveal that betafite was subsequently altered along crystal rims, particularly near the cracks. Electron probe microanalyses reveal little difference in composition between altered and unaltered areas, except for lower totals, suggesting that alteration is primarily due to hydration. Zirconolite contains up to 18 wt% ThO2 and 24 wt% UO2, and exhibits strong compositional zoning, but no internal cracking due to differential (and anisotropic) volume expansion and no visible alteration. The available evidence demonstrates that both oxycalciobetafite and zirconolite retained actinides for approximately 40 million years after the final stage of vein formation. During this time, oxycalciobetafite and zirconolite accumulated a total alpha-decay dose of 3.0-3.6 × 1016 and 0.2-2.0 × 1016 α/mg, respectively.

High salt diet induces metabolic alterations in multiple biological processes of Dahl salt-sensitive rats.

PubMed

Wang, Yanjun; Liu, Xiangyang; Zhang, Chen; Wang, Zhengjun

2018-06-01

High salt induced renal disease is a condition resulting from the interactions of genetic and dietary factors causing multiple complications. To understand the metabolic alterations associated with renal disease, we comprehensively analyzed the metabonomic changes induced by high salt intake in Dahl salt-sensitive (SS) rats using GC-MS technology and biochemical analyses. Physiological features, serum chemistry, and histopathological data were obtained as complementary information. Our results showed that high salt (HS) intake for 16 weeks caused significant metabolic alterations in both the renal medulla and cortex involving a variety pathways involved in the metabolism of organic acids, amino acids, fatty acids, and purines. In addition, HS enhanced glycolysis (hexokinase, phosphofructokinase and pyruvate kinase) and amino acid metabolism and suppressed the TCA (citrate synthase and aconitase) cycle. Finally, HS intake caused up-regulation of the pentose phosphate pathway (glucose 6-phosphate dehydrogenase and 6-phosphogluconate dehydrogenase), the ratio of NADPH/NADP + , NADPH oxidase activity and ROS production, suggesting that increased oxidative stress was associated with an altered PPP pathway. The metabolic pathways identified may serve as potential targets for the treatment of renal damage. Our findings provide comprehensive biochemical details about the metabolic responses to a high salt diet, which may contribute to the understanding of renal disease and salt-induced hypertension in SS rats. Copyright © 2018. Published by Elsevier Inc.

14-Week toxicity and cell proliferation of methyleugenol administered by gavage to F344 rats and B6C3F1 mice.

PubMed

Abdo, K M; Cunningham, M L; Snell, M L; Herbert, R A; Travlos, G S; Eldridge, S R; Bucher, J R

2001-04-01

Methyleugenol, a food flavor and fragrance agent, was tested for toxicity in male and female F344/N rats and B6C3F1 mice. Groups of 10 males and 10 females per sex per species were administered 0, 10, 30, 100, 300 or 1000 mg methyleugenol/kg body weight in 0.5% aqueous methylcellulose by gavage, 5 days per week for 14 weeks. Additional groups of rats and mice of each sex were dosed similarly and used for hematology and clinical chemistry studies. Groups of 10 male and 10 female rats and mice received the vehicle by gavage on the same dosing schedule and served as vehicle controls. For serum gastrin, gastric pH and cell proliferation studies groups of 10 female rats were given 0, 37, 75 or 150 mg/kg, once daily 5 days per week for 30 or 90 days or 300 or 1000 mg/kg for 30 days; male mice were given 0, 9, 18.5, 37, 75, 150 or 300 mg/kg for 30 or 90 days. For the gastrin, pH and cell proliferation studies, groups of 10 female rats and 10 male mice were given the vehicle for 30 or 90 days and served as controls. Methyleugenol administration to rats induced erythrocyte microcytosis and thrombocytosis in male and female rats. It also caused an increase in serum alanine aminotransferase and sorbitol dehydrogenase activities and bile acid concentration, suggesting hepatocellular injury, cholestasis or altered hepatic function. Additionally, methyleugenol induced hypoproteinemia and hypoalbuminemia, evidenced by decreased total protein and albumin concentrations in both male and female rats, suggesting in inefficiency of dietary protein utilization due to methyleugenol-induced toxic effects on the liver and glandular stomach of rats and mice. The increase in gastrin and gastric pH of rats and mice given methyleugenol suggests that gastrin feedback was impaired and resulted in conditions not conducive to protein digestion. In rats, methyleugenol caused an increase in the incidences of hepatocyte cytologic alteration, cytomegaly, Kupffer cell pigmentation, mixed foci of cellular alteration and bile duct hyperplasia of the liver and atrophy and chronic inflammation of the mucosa of the glandular stomach. In mice, it caused an increase in the incidence of cytologic alteration, necrosis, bile duct hyperplasia and subacute inflammation of the liver and atrophy, degeneration, necrosis, edema, mitotic alteration, and cystic glands of the fundic region of the glandular stomach. The increased incidences of adrenal gland cortical hypertrophy and/or cytoplasmic alteration in the submandibular salivary glands, adrenal glands, testis and uterus of rats were considered secondary to the chemical-related effects observed in the liver and glandular stomach. Based on mortality, body weight gain, clinical chemistry and gross and microscopic evaluation of tissues of rats and mice, the no-observed-effect level (NOEL) of methyleugenol for both species was estimated at 10 mg/kg.

Lycopene loaded gelatin nanoparticles induces internucleosmal DNA fragmentation and apoptosis in human breast adenocarcinoma cells

NASA Astrophysics Data System (ADS)

Preetha, K. Mary Anne; Devasena, T.

2018-06-01

The complex disease, cancer is caused by genetic uncertainty and various molecular alterations. Due to the present ineffective diagnostic and prognostic classifications, the complete heterogeneity of a tumor is not revealed which in turn affects the selection of suitable treatment and patient outcome. Cancer nanotechnology is an emerging interdisciplinary research field that covers important aspects of chemistry, engineering, biology and medicine, leading to the advancement of cancer diagnosis and treatment. Hence the main aim of this study is to develop lycopene loaded gelatin nanoparticles and evaluate its in vitro anticancer activity using breast adenocarcinoma cells.

Remote analysis of biological invasion and biogeochemical change

PubMed Central

Asner, Gregory P.; Vitousek, Peter M.

2005-01-01

We used airborne imaging spectroscopy and photon transport modeling to determine how biological invasion altered the chemistry of forest canopies across a Hawaiian montane rain forest landscape. The nitrogen-fixing tree Myrica faya doubled canopy nitrogen concentrations and water content as it replaced native forest, whereas the understory herb Hedychium gardnerianum reduced nitrogen concentrations in the forest overstory and substantially increased aboveground water content. This remote sensing approach indicates the geographic extent, intensity, and biogeochemical impacts of two distinct invaders; its wider application could enhance the role of remote sensing in ecosystem analysis and management. PMID:15761055

McCrillisite, NaCs(Be,Li)Zr2(PO4)4.1-2H2O, a new mineral species from Mount Mica, Oxford County, Maine, and new data for gainesite

USGS Publications Warehouse

Foord, E.E.; Brownfield, M.E.; Lichte, F.E.; Davis, A.M.; Sutley, S.J.

1994-01-01

McCrillisite, a member of the gainesite group, occurs in the Mount Mica granitic pegmatite, South Paris, Oxford County, Maine. The mineral is a product of late-stage hydrothermal alteration and is associated with approximately 20 other silicate, oxide, carbonate, arsenite and phosphate minerals. Crystals occur in mm- to cm-sized cavities, and individuals are up to 1.2 mm in maximum dimension. The crystallography and mineral chemistry of McCrillisite are described. -from Authors

[Silymarin in pregnancy and during hormonal contraceptive treatment. Blood chemistry and ultrastructural findings in the experimental model].

PubMed

Martines, G; Piva, M; Copponi, V; Cagnetta, G

1979-01-01

Further systematic study of the relation between drugs and the ultrastructure of the liver is reported with regard to the experimental administration of silimarin to pregnant women and others on the pill. Marked signs of ultrastructural alteration of the REL and biliary cell pole were noted, matched, by evidence of throbophilia and changes in protein activity and lipid synthesis, are noted in these situations, but not when suitable doses of silimarine are taken with the pill. It is suggested that silimarin may prevent and correct liver damage during pregnancy and the administration of oestroprogestins.

The sensitivity of tropospheric chemistry to cloud interactions

NASA Technical Reports Server (NTRS)

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

1994-01-01

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

Hydrothermal alteration and diagenesis of terrestrial lacustrine pillow basalts: Coordination of hyperspectral imaging with laboratory measurements

USGS Publications Warehouse

Greenberger, Rebecca N; Mustard, John F; Cloutis, Edward A; Mann, Paul; Wilson, Janette H.; Flemming, Roberta L; Robertson, Kevin; Salvatore, Mark R; Edwards, Christopher

2015-01-01

The phases identified in the sample are albite, large iron oxides, and titanite throughout; calcite in vesicles; calcic clinopyroxene, aegirine, and Fe/Mg-bearing clay in the rind; and fine-grained hematite and pyroxenes in the interior. Using imaging spectroscopy, the chemistry and mineralogy results extend to the hand sample and larger outcrop. From all of the analyses, we suggest that the pillow basalts were altered initially after emplacement, either by heated lake water or magmatic fluids, at temperatures of at least 400-600°C, and the calcic clinopyroxenes and aegirine identified in the rind are a preserved record of that alteration. As the hydrothermal system cooled to slightly lower temperatures, clays formed in the rind, and, during this alteration, the sample oxidized to form hematite in the matrix of the interior and Fe3+ in the pyroxenes in the rind. During the waning stages of the hydrothermal system, calcite precipitated in vesicles within the rind. Later, diagenetic processes albitized the sample, with albite replacing plagioclase, lining vesicles, and accreting onto the exterior of the sample. This albitization or Na-metasomatism occurred when the lake within the Hartford Basin evaporated during a drier past climatic era, resulting in Na-rich brines. As Ca-rich plagioclase altered to albite, Ca was released into solution, eventually precipitating as calcite in previously-unfilled vesicles, dominantly in the interior of the pillow. Coordinated analyses of this sample permit identification of the alteration phases and help synthesize the aqueous history of pillow lavas of the Talcott formation. These results are also relevant to Mars, where volcanically-resurfaced open basin lakes have been found, and this Hartford Basin outcrop may be a valuable analog for any potential volcano-lacustrine interactions. The results can also help to inform the utility and optimization of potentially complementary, synergistic, and uniquely-suited techniques for characterization of hydrothermally-altered terrains.

Modeling the Evolution of the System IV Period of the Io Torus

NASA Astrophysics Data System (ADS)

Coffin, D. A.; Delamere, P. A.

2017-12-01

The response of the Io plasma torus to superthermal electron modulation and volcanic eruptions is studied using a physical chemistry and radial/azimuthal transport model (Copper et al., 2016). The model includes radial and azimuthal transport, latitudinally-averaged physical chemistry, and prescribed System III superthermal electron modulation following Steffl et al., [2008]. Volcanic eruptions are modelled as a temporal Gaussian enhancement (e.g., 2x) of the neutral source rate and hot electron fraction (e.g., <1%). However, we adopt an alternative approach for the Steffl et al., [2008] System IV electron modulation. Radially-dependent subcorotation is prescribed, consistent with observations [Brown, 1994; Thomas et al., 2001], as well as a hot electron modulation proportional to the radial flux tube content gradient. Coupling hot electron modulation to radial transport and subcorotation, we seek to analyze magnetosphere-ionosphere coupling. We find that the model produces a radially-independent periodicity and that eruptions can alter the modeled period, consistent with multi-epoch observations of a variable System IV. This periodicity remains consistent with the prescribed subcorotation period at L = 6.3.

Simulating Aerosol Optical Properties With the Aerosol Simulation Program (ASP): Closure Studies Using ARCTAS Data

NASA Astrophysics Data System (ADS)

Alvarado, M. J.; Macintyre, H. L.; Bian, H.; Chin, M.; Wang, C.

2012-12-01

The scattering and absorption of ultraviolet and visible radiation by aerosols can significantly alter actinic fluxes and photolysis rates. Accurate modeling of aerosol optical properties is thus essential to simulating atmospheric chemistry, air quality, and climate. Here we evaluate the aerosol optical property predictions of the Aerosol Simulation Program (ASP) with in situ data on aerosol scattering and absorption gathered during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. The model simulations are initialized with in situ data on the aerosol size distribution and composition. We perform a set of sensitivity studies (e.g., internal vs. external mixture, core-in-shell versus Maxwell-Garnett, fraction of the organic carbon mass that is light-absorbing "brown carbon," etc.) to determine the model framework and parameters most consistent with the observations. We compare the ASP results to the aerosol optical property lookup tables in FAST-JX and suggest improvements that will better enable FAST-JX to simulate the impact of aerosols on photolysis rates and atmospheric chemistry.

Bifunctional Coupling Agents for Radiolabeling of Biomolecules and Target-Specific Delivery of Metallic Radionuclides

PubMed Central

Liu, Shuang

2008-01-01

Receptor-based radiopharmaceuticals are of great current interest in early molecular imaging and radiotherapy of cancers, and provide a unique tool for target-specific delivery of radionuclides to the diseased tissues. In general, a target-specific radiopharmaceutical can be divided into four parts: targeting biomolecule (BM), pharmacokinetic modifying (PKM) linker, bifunctional coupling or chelating agent (BFC), and radionuclide. The targeting biomolecule serves as a “carrier” for specific delivery of the radionuclide. PKM linkers are used to modify radiotracer excretion kinetics. BFC is needed for radiolabeling of biomolecules with a metallic radionuclide. Different radiometals have significant difference in their coordination chemistry, and require BFCs with different donor atoms and chelator frameworks. Since the radiometal chelate can have a significant impact on physical and biological properties of the target-specific radiopharmaceutical, its excretion kinetics can be altered by modifying the coordination environment with various chelators or coligand, if needed. This review will focus on the design of BFCs and their coordination chemistry with technetium, copper, gallium, indium, yttrium and lanthanide radiometals. PMID:18538888

Rapid in situ generation of two patterned chemoselective surface chemistries from a single hydroxy-terminated surface using controlled microfluidic oxidation.

PubMed

Pulsipher, Abigail; Westcott, Nathan P; Luo, Wei; Yousaf, Muhammad N

2009-06-10

In this work, we develop a new, rapid and inexpensive method to generate spatially controlled aldehyde and carboxylic acid surface groups by microfluidic oxidation of 11-hydroxyundecylphosphonic acid self-assembled monolayers (SAMs) on indium tin oxide (ITO) surfaces. SAMs are activated and patterned using a reversibly sealable, elastomeric polydimethylsiloxane cassette, fabricated with preformed micropatterns by soft lithography. By flowing the mild oxidant pyridinium chlorochromate through the microchannels, only selected areas of the SAM are chemically altered. This microfluidic oxidation strategy allows for ligand immobilization by two chemistries originating from a single SAM composition. ITO is robust, conductive, and transparent, making it an ideal platform for studying interfacial interactions. We display spatial control over the immobilization of a variety of ligands on ITO and characterize the resulting oxime and amide linkages by electrochemistry, X-ray photoelectron spectroscopy, contact angle, fluorescence microscopy, and atomic force microscopy. This general method may be used with many other materials to rapidly generate patterned and tailored surfaces for studies ranging from molecular electronics to biospecific cell-based assays and biomolecular microarrays.

Interferences from blood collection tube components on clinical chemistry assays

PubMed Central

Bowen, Raffick A.R.; Remaley, Alan T.

2014-01-01

Improper design or use of blood collection devices can adversely affect the accuracy of laboratory test results. Vascular access devices, such as catheters and needles, exert shear forces during blood flow, which creates a predisposition to cell lysis. Components from blood collection tubes, such as stoppers, lubricants, surfactants, and separator gels, can leach into specimens and/or adsorb analytes from a specimen; special tube additives may also alter analyte stability. Because of these interactions with blood specimens, blood collection devices are a potential source of pre-analytical error in laboratory testing. Accurate laboratory testing requires an understanding of the complex interactions between collection devices and blood specimens. Manufacturers, vendors, and clinical laboratorians must consider the pre-analytical challenges in laboratory testing. Although other authors have described the effects of endogenous substances on clinical assay results, the effects/impact of blood collection tube additives and components have not been well systematically described or explained. This review aims to identify and describe blood collection tube additives and their components and the strategies used to minimize their effects on clinical chemistry assays. PMID:24627713

An interplay between plasticity and parental phenotype determines impacts of ocean acidification on a reef fish.

PubMed

Schunter, Celia; Welch, Megan J; Nilsson, Göran E; Rummer, Jodie L; Munday, Philip L; Ravasi, Timothy

2018-02-01

The impacts of ocean acidification will depend on the ability of marine organisms to tolerate, acclimate and eventually adapt to changes in ocean chemistry. Here, we use a unique transgenerational experiment to determine the molecular response of a coral reef fish to short-term, developmental and transgenerational exposure to elevated CO 2 , and to test how these responses are influenced by variations in tolerance to elevated CO 2 exhibited by the parents. Within-generation responses in gene expression to end-of-century predicted CO 2 levels indicate that a self-amplifying cycle in GABAergic neurotransmission is triggered, explaining previously reported neurological and behavioural impairments. Furthermore, epigenetic regulator genes exhibited a within-generation specific response, but with some divergence due to parental phenotype. Importantly, we find that altered gene expression for the majority of within-generation responses returns to baseline levels following parental exposure to elevated CO 2 conditions. Our results show that both parental variation in tolerance and cross-generation exposure to elevated CO 2 are crucial factors in determining the response of reef fish to changing ocean chemistry.

Influence of Surface Chemistry on the Release of an Antibacterial Drug from Nanostructured Porous Silicon.

PubMed

Wang, Mengjia; Hartman, Philip S; Loni, Armando; Canham, Leigh T; Bodiford, Nelli; Coffer, Jeffery L

2015-06-09

Nanostructured mesoporous silicon possesses important properties advantageous to drug loading and delivery. For controlled release of the antibacterial drug triclosan, and its associated activity versus Staphylococcus aureus, previous studies investigated the influence of porosity of the silicon matrix. In this work, we focus on the complementary issue of the influence of surface chemistry on such properties, with particular regard to drug loading and release kinetics that can be ideally adjusted by surface modification. Comparison between drug release from as-anodized, hydride-terminated hydrophobic porous silicon and the oxidized hydrophilic counterpart is complicated due to the rapid bioresorption of the former; hence, a hydrophobic interface with long-term biostability is desired, such as can be provided by a relatively long chain octyl moiety. To minimize possible thermal degradation of the surfaces or drug activity during loading of molten drug species, a solution loading method has been investigated. Such studies demonstrate that the ability of porous silicon to act as an effective carrier for sustained delivery of antibacterial agents can be sensitively altered by surface functionalization.

Chalk-calcite-microfluidic experiments: construction and flooding of microsystems with reactive fluids

NASA Astrophysics Data System (ADS)

Neuville, Amélie; Thuy Luu, Thi; Dysthe, Dag Kristian; Vinningland, Jan Ludvig; Hiorth, Aksel

2015-04-01

Direct in situ observation of the pore structure changes that occur when chalk is flooded with brines could resolve many of the open questions that remain about the interactions between mineralogical alterations and oil-liberating mechanisms. Experiments on core scale and field tests that have been carried out the last decade have clearly shown that water chemistry affects the final oil recovery. However, there is generally no consensus in the scientific community of why additional oil is released. In this work, our aim is to focus on in-situ observations of single phase flow and interactions at the pore scale. To do so, we create several types of custom-made microsystems with chalk and calcite crystals. We then do experiments with reacting fluids in these microsystems. During these experiments, we realize in-situ observations (geometrical characteristics, reaction rate) using microsopy techniques (white light vertical/phase shift interferometric microscopy, and classical microscopy), and show how they vary as function as the water chemistry. In simple systems made of calcite, we obtain reactive rates that are coherent with the litterature and with numerical simulations based on Lattice-Boltzmann methods.

Aerosolization and Atmospheric Transformation of Engineered Nanoparticles

NASA Astrophysics Data System (ADS)

Tiwari, Andrea J.

While research on the environmental impacts of engineered nanoparticles (ENPs) is growing, the potential for them to be chemically transformed in the atmosphere has been largely ignored. The overall objective of this work was to assess the atmospheric transformation of carbonaceous nanoparticles (CNPs). The research focuses on C60 fullerene because it is an important member of the carbonaceous nanoparticle (CNP) family and is used in a wide variety of applications. The first specific objective was to review the potential of atmospheric transformations to alter the environmental impacts of CNPs. We described atmospheric processes that were likely to physically or chemically alter aerosolized CNPs and demonstrated their relevance to CNP behavior and toxicity in the aqueous and terrestrial environment. In order to investigate the transformations of CNP aerosols under controlled conditions, we developed an aerosolization technique that produces nano-scale aerosols without using solvents, which can alter the surface chemistry of the aerosols. We demonstrated the technique with carbonaceous (C60) and metal oxide (TiO2, CeO2) nanoparticle powders. All resulting aerosols exhibited unimodal size distributions and mode particle diameters below 100 nm. We used the new aerosolization technique to investigate the reaction between aerosolized C60 and atmospherically realistic levels of ozone (O3) in terms of reaction products, reaction rate, and oxidative stress potential. We identified C60O, C60O2, and C60O3 as products of the C60-O3 reaction. We demonstrated that the oxidative stress potential of C 60 may be enhanced by exposure to O3. We found the pseudo-first order reaction rate to be 9 x 10-6 to 2 x 10 -5 s-1, which is several orders of magnitude lower than the rate for several PAH species under comparable conditions. This research has demonstrated that a thorough understanding of atmospheric chemistry of ENPs is critical for accurate prediction of their environmental impacts. It has also enabled future research in that vein by developing a novel technique to produce nanoscale aerosols from nanoparticle powders. Results of this research will help guide the formulation of appropriate environmental policy concerning the regulation of ENPs.

Smectite formation in the presence of sulfuric acid: Implications for acidic smectite formation on early Mars

NASA Astrophysics Data System (ADS)

Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

2018-01-01

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (∼200 °C). Smectites were analyzed by X-ray diffraction, Mössbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH ≤ 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH ∼3 and trioctahedral smectite saponite at final pH ∼4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Analysis of terrestrial and Martian volcanic compositions using thermal emission spectroscopy

NASA Astrophysics Data System (ADS)

Wyatt, Michael Bruce

2002-11-01

This dissertation comprises four separate parts that address the Mars Global Surveyor (MGS) Thermal Emission Spectrometer (TES) investigation objective of determining and mapping the composition and distribution of surface minerals and rocks on Mars from orbit. In Part 1, laboratory thermal infrared spectra (5 25 μm, at 2 cm-1 spectral sampling), deconvolved modal mineralogies, and derived mineral and bulk rock chemistries of basalt, basaltic andesite, andesite, and dacite were used to evaluate and revise volcanic rock classification schemes. Multiple steps of classification were required to distinguish volcanic rocks, reflecting the mineralogic diversity and continuum of compositions that exists in volcanic rock types. In Part 2, laboratory spectral data were convolved to TES 10 cm-1 sampling to ascertain whether adequate results for volcanic rock classification can be obtained with lower spectral resolution, comparable to that obtained from Mars orbit. Modeled spectra, modeled modal mineralogies, and derived bulk rock chemistries at low (10 cm-1) spectral sampling provide good matches to measured and high (2 cm-1) spectral sampling modeled values. These results demonstrate the feasibility of using similar techniques and classification schemes for the interpretation of terrestrial laboratory samples and TES-resolution data. In Part 3, new deconvolved mineral abundances from TES data and terrestrial basalts using a spectral end-member set representing minerals common in unaltered and low-temperature aqueously altered basalts were used to reclassify martian surface lithologies. The new formulations maintain the dominance of unaltered basalt in the southern highlands, but indicate the northern lowlands can be interpreted as weathered basalt. The coincidence between locations of altered basalt and a previously suggested northern ocean basin implies that lowland plains materials may be basalts altered under submarine conditions and/or weathered basaltic sediment transported into this depocenter. In Part 4, results from the previous parts are applied to examine the distribution of TES-derived surface compositions in the Oxia Palus region on Mars through high-spatial resolution mapping. Features of interest within Oxia Palus include volcanic/sedimentary materials in southern Acidalia Planitia, low-albedo crater floors and wind streaks in western Arabia Terra, and channel outflow deposits of the Mars Pathfinder (MP) landing site.

Analysis of spatiotemporal metabolomic dynamics for sensitively monitoring biological alterations in cisplatin-induced acute kidney injury.

PubMed

Irie, Miho; Hayakawa, Eisuke; Fujimura, Yoshinori; Honda, Youhei; Setoyama, Daiki; Wariishi, Hiroyuki; Hyodo, Fuminori; Miura, Daisuke

2018-01-29

Clinical application of the major anticancer drug, cisplatin, is limited by severe side effects, especially acute kidney injury (AKI) caused by nephrotoxicity. The detailed metabolic mechanism is still largely unknown. Here, we used an integrated technique combining mass spectrometry imaging (MSI) and liquid chromatography-mass spectrometry (LC-MS) to visualize the diverse spatiotemporal metabolic dynamics in the mouse kidney after cisplatin dosing. Biological responses to cisplatin was more sensitively detected within 24 h as a metabolic alteration, which is much earlier than possible with the conventional clinical chemistry method of blood urea nitrogen (BUN) measurement. Region-specific changes (e.g., medulla and cortex) in metabolites related to DNA damage and energy generation were observed over the 72-h exposure period. Therefore, this metabolomics approach may become a novel strategy for elucidating early renal responses to cisplatin, prior to the detection of kidney damage evaluated by conventional method. Copyright © 2018. Published by Elsevier Inc.

Providing Global Change Information for Decision-Making: Capturing and Presenting Provenance

NASA Technical Reports Server (NTRS)

Ma, Xiaogang; Fox, Peter; Tilmes, Curt; Jacobs, Katherine; Waple, Anne

2014-01-01

Global change information demands access to data sources and well-documented provenance to provide evidence needed to build confidence in scientific conclusions and, in specific applications, to ensure the information's suitability for use in decision-making. A new generation of Web technology, the Semantic Web, provides tools for that purpose. The topic of global change covers changes in the global environment (including alterations in climate, land productivity, oceans or other water resources, atmospheric composition and or chemistry, and ecological systems) that may alter the capacity of the Earth to sustain life and support human systems. Data and findings associated with global change research are of great public, government, and academic concern and are used in policy and decision-making, which makes the provenance of global change information especially important. In addition, since different types of decisions benefit from different types of information, understanding how to capture and present the provenance of global change information is becoming more of an imperative in adaptive planning.

25 years of neuroimaging in amyotrophic lateral sclerosis.

PubMed

Foerster, Bradley R; Welsh, Robert C; Feldman, Eva L

2013-09-01

Amyotrophic lateral sclerosis (ALS) is a fatal motor neuron disease for which a precise cause has not yet been identified. Standard CT or MRI evaluation does not demonstrate gross structural nervous system changes in ALS, so conventional neuroimaging techniques have provided little insight into the pathophysiology of this disease. Advanced neuroimaging techniques--such as structural MRI, diffusion tensor imaging and proton magnetic resonance spectroscopy--allow evaluation of alterations of the nervous system in ALS. These alterations include focal loss of grey and white matter and reductions in white matter tract integrity, as well as changes in neural networks and in the chemistry, metabolism and receptor distribution in the brain. Given their potential for investigation of both brain structure and function, advanced neuroimaging methods offer important opportunities to improve diagnosis, guide prognosis, and direct future treatment strategies in ALS. In this article, we review the contributions made by various advanced neuroimaging techniques to our understanding of the impact of ALS on different brain regions, and the potential role of such measures in biomarker development.

25 years of neuroimaging in amyotrophic lateral sclerosis

PubMed Central

Foerster, Bradley R.; Welsh, Robert C.; Feldman, Eva L.

2014-01-01

Amyotrophic lateral sclerosis (ALS) is a fatal motor neuron disease for which a precise cause has not yet been identified. Standard CT or MRI evaluation does not demonstrate gross structural nervous system changes in ALS, so conventional neuroimaging techniques have provided little insight into the pathophysiology of this disease. Advanced neuroimaging techniques—such as structural MRI, diffusion tensor imaging and proton magnetic resonance spectroscopy—allow evaluation of alterations of the nervous system in ALS. These alterations include focal loss of grey and white matter and reductions in white matter tract integrity, as well as changes in neural networks and in the chemistry, metabolism and receptor distribution in the brain. Given their potential for investigation of both brain structure and function, advanced neuroimaging methods offer important opportunities to improve diagnosis, guide prognosis, and direct future treatment strategies in ALS. In this article, we review the contributions made by various advanced neuroimaging techniques to our understanding of the impact of ALS on different brain regions, and the potential role of such measures in biomarker development. PMID:23917850

Tunable particles alter macrophage uptake based on combinatorial effects of physical properties

PubMed Central

Garapaty, Anusha

2017-01-01

Abstract The ability to tune phagocytosis of particle‐based therapeutics by macrophages can enhance their delivery to macrophages or reduce their phagocytic susceptibility for delivery to non‐phagocytic cells. Since phagocytosis is affected by the physical and chemical properties of particles, it is crucial to identify any interplay between physical properties of particles in altering phagocytic interactions. The combinatorial effect of physical properties size, shape and stiffness was investigated on Fc receptor mediated macrophage interactions by fabrication of layer‐by‐layer tunable particles of constant surface chemistry. Our results highlight how changing particle stiffness affects phagocytic interaction intricately when combined with varying size or shape. Increase in size plays a dominant role over reduction in stiffness in reducing internalization by macrophages for spherical particles. Internalization of rod‐shaped, but not spherical particles, was highly dependent on stiffness. These particles demonstrate the interplay between size, shape and stiffness in interactions of Fc‐functionalized particles with macrophages during phagocytosis. PMID:29313025

Physico-chemistry and geochemistry of Balengou clay deposit (West Cameroon) with inference to an argillic hydrothermal alteration

NASA Astrophysics Data System (ADS)

Tassongwa, Bernard; Eba, François; Njoya, Dayirou; Tchakounté, Jacqueline Numbem; Jeudong, Narcisse; Nkoumbou, Charles; Njopwouo, Daniel

2017-09-01

Field description and sampling along two pits, granulometry, Atterberg limits, mineralogical (XRD, FTIR, DSC & TGA) and geochemical analyses of the Balengou clays help to determine their characteristics and the genesis of the deposit. The mineralogical composition is comprised of halloysite-kaolinite, quartz, montmorillonite, hematite, anatase, feldspar, zircon, chromite, and apatite. Gibbsite and illite occur at the shallow and deep depth, respectively. Dikes of sand-poor clays contain also cristobalite and tridymite. Pairs of elements Rb-Ba, Rb-Sr, Nb-Ta, Ta-Zr, TiO2-Zr display good positive correlations (R2 > 0.85). REE patterns are highly fractionated (LaN up to 3312, LaN/YbN: 19-10) and are marked by deep Ce and Eu negative anomalies. Immobile element canonical ratios indicate that the protoliths were commendite/pantelerite, rhyolite and dacite, or their plutonic equivalents. Mineralogical and geochemical features lead to the suggestion that the clays derived from an advanced argillic hydrothermal alteration.

Mineralogical, crystallographic and redox features of the earliest stages of fluid alteration in CM chondrites

NASA Astrophysics Data System (ADS)

Pignatelli, Isabella; Marrocchi, Yves; Mugnaioli, Enrico; Bourdelle, Franck; Gounelle, Matthieu

2017-07-01

The CM chondrites represent the largest group of hydrated meteorites and span a wide range of conditions, from less altered (i.e., CM2) down to heavily altered (i.e., CM1). The Paris chondrite is considered the least altered CM and thus enables the earliest stages of aqueous alteration processes to be deciphered. Here, we report results from a nanoscale study of tochilinite/cronstedtite intergrowths (TCIs) in Paris-TCIs being the emblematic secondary mineral assemblages of CM chondrites, formed from the alteration of Fe-Ni metal beads (type-I TCIs) and anhydrous silicates (type-II TCIs). We combined high-resolution transmission electron microscopy, scanning transmission X-ray microscopy and electron diffraction tomography to characterize the crystal structure, crystal chemistry and redox state of TCIs. The data obtained are useful to reconstruct the alteration conditions of Paris and to compare them with those of other meteorites. Our results show that tochilinite in Paris is characterized by a high hydroxide layer content (n = 2.1-2.2) regardless of the silicate precursors. When examined alongside other CMs, it appears that the hydroxide layer and iron contents of tochilinites correlate with the degree of alteration experienced by the chondrites. The Fe3+/ΣFe ratios of TCIs are high: 8-15% in tochilinite, 33-60% in cronstedtite and 70-80% in hydroxides. These observations suggest that alteration of CM chondrites took place under oxidizing conditions that could have been induced by significant H2 release during serpentinization. Similar results were recently reported in CR chondrites (Le Guillou et al., 2015), suggesting that the process(es) controlling the redox state of the secondary mineral assemblages were quite similar in the CM and CR parent bodies despite the different alteration conditions. According to our mineralogical and crystallographic survey, the formation of TCIs in Paris occurred at temperatures lower than 100 °C, under neutral, slightly alkaline conditions that favored the formation of both tochilinite and cronstedtite. During the course of alteration, the reduction in sulfur activity and/or the decrease of temperature prevented tochilinite crystallization and favoured the formation of cronstedtite and iron hydroxides. We suggest that iron hydroxides probably formed as ferrihydrite and then progressively converted to goethite between 50° and 80 °C, a temperature range that is also favorable for cronstedtite formation. The presence of cronstedtite plays a key role in the reconstruction of the alteration history, demonstrating that the alteration of Paris took place by way of serpentinization processes similar to those described on the Earth.

Informing Rodent Behavior in Space: Gene Expression and Hyper-Emotionality Following Prenatal Stress

NASA Technical Reports Server (NTRS)

Moyer, E. L.; Talyansky, Y.; Baer, L. A.; Ronca, A. E.

2017-01-01

As space exploration pushes our boundaries further away from Earth and for longer durations, we will inevitably require the use of multi-generational studies to continue our expansion. Space is a stressful environment not only due to the deleterious effect of spaceflight on physiology, but also due to confinement, limited social interactions, inherently dangerous circumstances, and many other stresses of an unknown environment. Stress can alter the brain chemistry, and these alterations can affect behavior at all stages of development, but it is especially pronounced during the perinatal period and can have longstanding effects, even into adulthood, which manifest through augmented brain function and psychopathology. This study investigated the nexus of brain chemistry and brain function by observing behavior of adult rats whose mothers were exposed to unpredictable variable prenatal stress (UVPS) while they were in the womb. The UVPS consisted of strobe light, tube restraint, and white noise, and was administered at unpredictable times of the day and also varied in length, both of which were measures taken to prevent habituation to the stressor. The offspring rats were then allowed to reach adulthood and at 90 days were subjected to a series of behavioral tests including novel object, startle response, and an unknown intruder to quantify the adult rats stress response and anxiety. Here we report these results of the behavioral analysis and correlate adult behavioral measures with the expression of genes involved in the hypothalamic-pituitary-adrenal axis, which modulates the animals stress response. We hypothesized that hyper-expression of genes involved in the HPA axis would correlate with the observed anxiety-like behaviors associated with early stress.

On the in situ aqueous alteration of soils on Mars

USGS Publications Warehouse

Amundson, Ronald; Ewing, S.; Dietrich, W.; Sutter, B.; Owen, J.; Chadwick, O.; Nishiizumi, K.; Walvoord, Michelle Ann; McKay, C.

2008-01-01

Early (>3 Gy) wetter climate conditions on Mars have been proposed, and it is thus likely that pedogenic processes have occurred there at some point in the past. Soil and rock chemistry of the Martian landing sites were evaluated to test the hypothesis that in situ aqueous alteration and downward movement of solutes have been among the processes that have transformed these portions of the Mars regolith. A geochemical mass balance shows that Martian soils at three landing sites have lost significant quantities of major rock-forming elements and have gained elements that are likely present as soluble ions. The loss of elements is interpreted to have occurred during an earlier stage(s) of weathering that may have been accompanied by the downward transport of weathering products, and the salts are interpreted to be emplaced later in a drier Mars history. Chemical differences exist among the sites, indicating regional differences in soil composition. Shallow soil profile excavations at Gusev crater are consistent with late stage downward migration of salts, implying the presence of small amounts of liquid water even in relatively recent Martian history. While the mechanisms for chemical weathering and salt additions on Mars remain unclear, the soil chemistry appears to record a decline in leaching efficiency. A deep sedimentary exposure at Endurance crater contains complex depth profiles of SO4, Cl, and Br, trends generally consistent with downward aqueous transport accompanied by drying. While no model for the origin of Martian soils can be fully constrained with the currently available data, a pedogenic origin is consistent with observed Martian geology and geochemistry, and provides a testable hypothesis that can be evaluated with present and future data from the Mars surface. ?? 2008 Elsevier Ltd.

Molecular locks and keys: the role of small molecules in phytohormone research

PubMed Central

Fonseca, Sandra; Rosado, Abel; Vaughan-Hirsch, John; Bishopp, Anthony; Chini, Andrea

2014-01-01

Plant adaptation, growth and development rely on the integration of many environmental and endogenous signals that collectively determine the overall plant phenotypic plasticity. Plant signaling molecules, also known as phytohormones, are fundamental to this process. These molecules act at low concentrations and regulate multiple aspects of plant fitness and development via complex signaling networks. By its nature, phytohormone research lies at the interface between chemistry and biology. Classically, the scientific community has always used synthetic phytohormones and analogs to study hormone functions and responses. However, recent advances in synthetic and combinational chemistry, have allowed a new field, plant chemical biology, to emerge and this has provided a powerful tool with which to study phytohormone function. Plant chemical biology is helping to address some of the most enduring questions in phytohormone research such as: Are there still undiscovered plant hormones? How can we identify novel signaling molecules? How can plants activate specific hormone responses in a tissue-specific manner? How can we modulate hormone responses in one developmental context without inducing detrimental effects on other processes? The chemical genomics approaches rely on the identification of small molecules modulating different biological processes and have recently identified active forms of plant hormones and molecules regulating many aspects of hormone synthesis, transport and response. We envision that the field of chemical genomics will continue to provide novel molecules able to elucidate specific aspects of hormone-mediated mechanisms. In addition, compounds blocking specific responses could uncover how complex biological responses are regulated. As we gain information about such compounds we can design small alterations to the chemical structure to further alter specificity, enhance affinity or modulate the activity of these compounds. PMID:25566283

Hydrogeochemical and mineralogical effects of sustained CO2 contamination in a shallow sandy aquifer: A field-scale controlled release experiment

NASA Astrophysics Data System (ADS)

Cahill, Aaron G.; Marker, Pernille; Jakobsen, Rasmus

2014-02-01

A shallow aquifer CO2 contamination experiment was performed to investigate evolution of water chemistry and sediment alteration following leakage from geological storage by physically simulating a leak from a hypothetical storage site. In a carbonate-free aquifer, in western Denmark, a total of 1600 kg of gas phase CO2 was injected at 5 and 10 m depth over 72 days through four inclined injection wells into aeolian and glacial sands. Water chemistry was monitored for pH, EC, and dissolved element evolution through an extensive network of multilevel sampling points over 305 days. Sediment cores were taken pre and postinjection and analyzed to search for effects on mineralogy and sediment properties. Results showed the simulated leak to evolve in two distinct phases; an advective elevated ion pulse followed by increasing persistent acidification. Spatial and temporal differences in evolution of phases suggest separate chemical mechanisms and geochemical signatures. Dissolved element concentrations developed exhibiting four behaviors: (1) advective pulse (Ca, Mg, Na, Si, Ba, and Sr), (2) pH sensitive abundance dependent (Al and Zn), (3) decreasing (Mn and Fe), and (4) unaffected (K). Concentration behaviors were characterized by: (1) a maximal front moving with advective flow, (2) continual increase in close proximity to the injection plane, (3) removal from solution, and (4) no significant change. Only Al was observed to exceed WHO guidelines, however significantly so (10-fold excess). The data indicate that pH is controlled by equilibrium with gibbsite which is again coupled to cation exchange processes. Pre and postinjection sediment analysis indicated alteration of sediment composition and properties including depletion of reactive mineral species.

Above- and belowground linkages in Sphagnum peatland: climate warming affects plant-microbial interactions.

PubMed

Jassey, Vincent E J; Chiapusio, Geneviève; Binet, Philippe; Buttler, Alexandre; Laggoun-Défarge, Fatima; Delarue, Frédéric; Bernard, Nadine; Mitchell, Edward A D; Toussaint, Marie-Laure; Francez, André-Jean; Gilbert, Daniel

2013-03-01

Peatlands contain approximately one third of all soil organic carbon (SOC). Warming can alter above- and belowground linkages that regulate soil organic carbon dynamics and C-balance in peatlands. Here we examine the multiyear impact of in situ experimental warming on the microbial food web, vegetation, and their feedbacks with soil chemistry. We provide evidence of both positive and negative impacts of warming on specific microbial functional groups, leading to destabilization of the microbial food web. We observed a strong reduction (70%) in the biomass of top-predators (testate amoebae) in warmed plots. Such a loss caused a shortening of microbial food chains, which in turn stimulated microbial activity, leading to slight increases in levels of nutrients and labile C in water. We further show that warming altered the regulatory role of Sphagnum-polyphenols on microbial community structure with a potential inhibition of top predators. In addition, warming caused a decrease in Sphagnum cover and an increase in vascular plant cover. Using structural equation modelling, we show that changes in the microbial food web affected the relationships between plants, soil water chemistry, and microbial communities. These results suggest that warming will destabilize C and nutrient recycling of peatlands via changes in above- and belowground linkages, and therefore, the microbial food web associated with mosses will feedback positively to global warming by destabilizing the carbon cycle. This study confirms that microbial food webs thus constitute a key element in the functioning of peatland ecosystems. Their study can help understand how mosses, as ecosystem engineers, tightly regulate biogeochemical cycling and climate feedback in peatlands. © 2012 Blackwell Publishing Ltd.

Change in soil fungal community structure driven by a decline in ectomycorrhizal fungi following a mountain pine beetle (Dendroctonus ponderosae) outbreak.

PubMed

Pec, Gregory J; Karst, Justine; Taylor, D Lee; Cigan, Paul W; Erbilgin, Nadir; Cooke, Janice E K; Simard, Suzanne W; Cahill, James F

2017-01-01

Western North American landscapes are rapidly being transformed by forest die-off caused by mountain pine beetle (Dendroctonus ponderosae), with implications for plant and soil communities. The mechanisms that drive changes in soil community structure, particularly for the highly prevalent ectomycorrhizal fungi in pine forests, are complex and intertwined. Critical to enhancing understanding will be disentangling the relative importance of host tree mortality from changes in soil chemistry following tree death. Here, we used a recent bark beetle outbreak in lodgepole pine (Pinus contorta) forests of western Canada to test whether the effects of tree mortality altered the richness and composition of belowground fungal communities, including ectomycorrhizal and saprotrophic fungi. We also determined the effects of environmental factors (i.e. soil nutrients, moisture, and phenolics) and geographical distance, both of which can influence the richness and composition of soil fungi. The richness of both groups of soil fungi declined and the overall composition was altered by beetle-induced tree mortality. Soil nutrients, soil phenolics and geographical distance influenced the community structure of soil fungi; however, the relative importance of these factors differed between ectomycorrhizal and saprotrophic fungi. The independent effects of tree mortality, soil phenolics and geographical distance influenced the community composition of ectomycorrhizal fungi, while the community composition of saprotrophic fungi was weakly but significantly correlated with the geographical distance of plots. Taken together, our results indicate that both deterministic and stochastic processes structure soil fungal communities following landscape-scale insect outbreaks and reflect the independent roles tree mortality, soil chemistry and geographical distance play in regulating the community composition of soil fungi. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Seagrass habitat metabolism increases short-term extremes and long-term offset of CO2 under future ocean acidification.

PubMed

Pacella, Stephen R; Brown, Cheryl A; Waldbusser, George G; Labiosa, Rochelle G; Hales, Burke

2018-04-10

The role of rising atmospheric CO 2 in modulating estuarine carbonate system dynamics remains poorly characterized, likely due to myriad processes driving the complex chemistry in these habitats. We reconstructed the full carbonate system of an estuarine seagrass habitat for a summer period of 2.5 months utilizing a combination of time-series observations and mechanistic modeling, and quantified the roles of aerobic metabolism, mixing, and gas exchange in the observed dynamics. The anthropogenic CO 2 burden in the habitat was estimated for the years 1765-2100 to quantify changes in observed high-frequency carbonate chemistry dynamics. The addition of anthropogenic CO 2 alters the thermodynamic buffer factors (e.g., the Revelle factor) of the carbonate system, decreasing the seagrass habitat's ability to buffer natural carbonate system fluctuations. As a result, the most harmful carbonate system indices for many estuarine organisms [minimum pH T , minimum Ω arag , and maximum pCO 2(s.w.) ] change up to 1.8×, 2.3×, and 1.5× more rapidly than the medians for each parameter, respectively. In this system, the relative benefits of the seagrass habitat in locally mitigating ocean acidification increase with the higher atmospheric CO 2 levels predicted toward 2100. Presently, however, these mitigating effects are mixed due to intense diel cycling of CO 2 driven by aerobic metabolism. This study provides estimates of how high-frequency pH T , Ω arag , and pCO 2(s.w.) dynamics are altered by rising atmospheric CO 2 in an estuarine habitat, and highlights nonlinear responses of coastal carbonate parameters to ocean acidification relevant for water quality management.

Seagrass habitat metabolism increases short-term extremes and long-term offset of CO2 under future ocean acidification

NASA Astrophysics Data System (ADS)

Pacella, Stephen R.; Brown, Cheryl A.; Waldbusser, George G.; Labiosa, Rochelle G.; Hales, Burke

2018-04-01

The role of rising atmospheric CO2 in modulating estuarine carbonate system dynamics remains poorly characterized, likely due to myriad processes driving the complex chemistry in these habitats. We reconstructed the full carbonate system of an estuarine seagrass habitat for a summer period of 2.5 months utilizing a combination of time-series observations and mechanistic modeling, and quantified the roles of aerobic metabolism, mixing, and gas exchange in the observed dynamics. The anthropogenic CO2 burden in the habitat was estimated for the years 1765–2100 to quantify changes in observed high-frequency carbonate chemistry dynamics. The addition of anthropogenic CO2 alters the thermodynamic buffer factors (e.g., the Revelle factor) of the carbonate system, decreasing the seagrass habitat’s ability to buffer natural carbonate system fluctuations. As a result, the most harmful carbonate system indices for many estuarine organisms [minimum pHT, minimum Ωarag, and maximum pCO2(s.w.)] change up to 1.8×, 2.3×, and 1.5× more rapidly than the medians for each parameter, respectively. In this system, the relative benefits of the seagrass habitat in locally mitigating ocean acidification increase with the higher atmospheric CO2 levels predicted toward 2100. Presently, however, these mitigating effects are mixed due to intense diel cycling of CO2 driven by aerobic metabolism. This study provides estimates of how high-frequency pHT, Ωarag, and pCO2(s.w.) dynamics are altered by rising atmospheric CO2 in an estuarine habitat, and highlights nonlinear responses of coastal carbonate parameters to ocean acidification relevant for water quality management.

A decision-making framework for sediment contamination.

PubMed

Chapman, Peter M; Anderson, Janette

2005-07-01

A decision-making framework for determining whether or not contaminated sediments are polluted is described. This framework is intended to be sufficiently prescriptive to standardize the decision-making process but without using "cook book" assessments. It emphasizes 4 guidance "rules": (1) sediment chemistry data are only to be used alone for remediation decisions when the costs of further investigation outweigh the costs of remediation and there is agreement among all stakeholders to act; (2) remediation decisions are based primarily on biology; (3) lines of evidence (LOE), such as laboratory toxicity tests and models that contradict the results of properly conducted field surveys, are assumed incorrect; and (4) if the impacts of a remedial alternative will cause more environmental harm than good, then it should not be implemented. Sediments with contaminant concentrations below sediment quality guidelines (SQGs) that predict toxicity toless than 5% of sediment-dwelling infauna and that contain no quantifiable concentrations of substances capable of biomagnifying are excluded from further consideration, as are sediments that do not meet these criteria but have contaminant concentrations equal to or below reference concentrations. Biomagnification potential is initially addressed by conservative (worst case) modeling based on benthos and sediments and, subsequently, by additional food chain data and more realistic assumptions. Toxicity (acute and chronic) and alterations to resident communities are addressed by, respectively, laboratory studies and field observations. The integrative decision point for sediments is a weight of evidence (WOE) matrix combining up to 4 main LOE: chemistry, toxicity, community alteration, and biomagnification potential. Of 16 possible WOE scenarios, 6 result in definite decisions, and 10 require additional assessment. Typically, this framework will be applied to surficial sediments. The possibility that deeper sediments may be uncovered as a result of natural or other processes must also be investigated and may require similar assessment.

Factors controlling the geochemical evolution of fumarolic encrustations, Valley of Ten Thousand Smokes, Alaska

USGS Publications Warehouse

Kodosky, L.G.; Keith, T.E.C.

1993-01-01

Factor and canonical correlation analysis of geochemical data from eight fossil fumaroles suggest that six major factors controlled the formation and evolution of fumarolic encrustations on the 1912 ash-flow sheet in the Valley of Ten Thousand Smokes (VTTS). The six-factor solution model explains a large proportion (low of 74% for Ni to high of 99% for Si) of the individual element data variance. Although the primary fumarolic deposits have been degraded by secondary alteration reactions and up to 75 years of weathering, the relict encrustations still preserve a signature of vapor-phase element transport. This vapor-phase transport probably occurred as halide or oxyhalide species and was significant for As, Sb and Br. At least three, and possibly four, varied temperature leaching events affected the fumarolic deposits. High-temperature gases/liquids heavily altered the ejecta glass and mineral phases adjacent to the fumarolic conduit. As the fumaroles cooled. Fe-rich acidic condensate leached the ejecta and primary fumarolic deposits and resulted in the subsequent precipitation of Fe-hydroxides and/or Fe-oxides. Low- to ambient-temperature leaching and hydration reactions generated abundant hydrated amorphous phases. Up to 87% of the individual element data variance is apparently controlled by the chemistry of the ejecta on which the relict encrustations are found. This matrix chemistry factor illustrates that the primary fumarolic minerals surrounding the active VTTS vents observed by earlier workers have been effectively removed by the dissolution reactions. Element enrichment factors calculated for the VTTS relict encrustations support the statistical factor interpretations. On the average, the relict encrustations are enriched, relative to visibly unaltered matrix protolith, in As, Br, Cr, Sb, Cu, Ni, Pb, Fe, and LOI (an indirect measure of sample H2O content). ?? 1993.

Wetlands in Changed Landscapes: The Influence of Habitat Transformation on the Physico-Chemistry of Temporary Depression Wetlands

PubMed Central

Bird, Matthew S.; Day, Jenny A.

2014-01-01

Temporary wetlands dominate the wet season landscape of temperate, semi-arid and arid regions, yet, other than their direct loss to development and agriculture, little information exists on how remaining wetlands have been altered by anthropogenic conversion of surrounding landscapes. This study investigates relationships between the extent and type of habitat transformation around temporary wetlands and their water column physico-chemical characteristics. A set of 90 isolated depression wetlands (seasonally inundated) occurring on coastal plains of the south-western Cape mediterranean-climate region of South Africa was sampled during the winter/spring wet season of 2007. Wetlands were sampled across habitat transformation gradients according to the areal cover of agriculture, urban development and alien invasive vegetation within 100 and 500 m radii of each wetland edge. We hypothesized that the principal drivers of physico-chemical conditions in these wetlands (e.g. soil properties, basin morphology) are altered by habitat transformation. Multivariate multiple regression analyses (distance-based Redundancy Analysis) indicated significant associations between wetland physico-chemistry and habitat transformation (overall transformation within 100 and 500 m, alien vegetation cover within 100 and 500 m, urban cover within 100 m); although for significant regressions the amount of variation explained was very low (range: ∼2 to ∼5.5%), relative to that explained by purely spatio-temporal factors (range: ∼35.5 to ∼43%). The nature of the relationships between each type of transformation in the landscape and individual physico-chemical variables in wetlands were further explored with univariate multiple regressions. Results suggest that conservation of relatively narrow (∼100 m) buffer strips around temporary wetlands is likely to be effective in the maintenance of natural conditions in terms of physico-chemical water quality. PMID:24533161

Stratospheric Dynamical Response and Ozone Feedbacks in the Presence of SO2 Injections

NASA Astrophysics Data System (ADS)

Richter, Jadwiga H.; Tilmes, Simone; Mills, Michael J.; Tribbia, Joseph J.; Kravitz, Ben; MacMartin, Douglas G.; Vitt, Francis; Lamarque, Jean-Francois

2017-12-01

Injections of sulfur dioxide into the stratosphere are among several proposed methods of solar radiation management. Such injections could cool the Earth's climate. However, they would significantly alter the dynamics of the stratosphere. We explore here the stratospheric dynamical response to sulfur dioxide injections ˜5 km above the tropopause at multiple latitudes (equator, 15°S, 15°N, 30°S and 30°N) using a fully coupled Earth system model, Community Earth System Model, version 1, with the Whole Atmosphere Community Climate Model as its atmospheric component (CESM1(WACCM)). We find that in all simulations, the tropical lower stratosphere warms primarily between 30°S and 30°N, regardless of injection latitude. The quasi-biennial oscillation (QBO) of the tropical zonal wind is altered by the various sulfur dioxide injections. In a simulation with a 12 Tg yr-1 equatorial injection, and with fully interactive chemistry, the QBO period lengthens to ˜3.5 years but never completely disappears. However, in a simulation with specified (or noninteractive) chemical fields, including O3 and prescribed aerosols taken from the interactive simulation, the oscillation is virtually lost. In addition, we find that geoengineering does not always lengthen the QBO. We further demonstrate that the QBO period changes from 24 to 12-17 months in simulations with sulfur dioxide injections placed poleward of the equator. Our study points to the importance of understanding and verifying of the complex interactions between aerosols, atmospheric dynamics, and atmospheric chemistry as well as understanding the effects of sulfur dioxide injections placed away from the Equator on the QBO.

Ectopic Terpene Synthase Expression Enhances Sesquiterpene Emission in Nicotiana attenuata without Altering Defense or Development of Transgenic Plants or Neighbors1[W

PubMed Central

Schuman, Meredith C.; Palmer-Young, Evan C.; Schmidt, Axel; Gershenzon, Jonathan; Baldwin, Ian T.

2014-01-01

Sesquiterpenoids, with approximately 5,000 structures, are the most diverse class of plant volatiles with manifold hypothesized functions in defense, stress tolerance, and signaling between and within plants. These hypotheses have often been tested by transforming plants with sesquiterpene synthases expressed behind the constitutively active 35S promoter, which may have physiological costs measured as inhibited growth and reduced reproduction or may require augmentation of substrate pools to achieve enhanced emission, complicating the interpretation of data from affected transgenic lines. Here, we expressed maize (Zea mays) terpene synthase10 (ZmTPS10), which produces (E)-α-bergamotene and (E)-β-farnesene, or a point mutant ZmTPS10M, which produces primarily (E)-β-farnesene, under control of the 35S promoter in the ecological model plant Nicotiana attenuata. Transgenic N. attenuata plants had specifically enhanced emission of target sesquiterpene(s) with no changes detected in their emission of any other volatiles. Treatment with herbivore or jasmonate elicitors induces emission of (E)-α-bergamotene in wild-type plants and also tended to increase emission of (E)-α-bergamotene and (E)-β-farnesene in transgenics. However, transgenics did not differ from the wild type in defense signaling or chemistry and did not alter defense chemistry in neighboring wild-type plants. These data are inconsistent with within-plant and between-plant signaling functions of (E)-β-farnesene and (E)-α-bergamotene in N. attenuata. Ectopic sesquiterpene emission was apparently not costly for transgenics, which were similar to wild-type plants in their growth and reproduction, even when forced to compete for common resources. These transgenics would be well suited for field experiments to investigate indirect ecological effects of sesquiterpenes for a wild plant in its native habitat. PMID:25187528

Variability of Ecosystem State in Rivers Containing Natural Dams: A Chemical Analysis

NASA Astrophysics Data System (ADS)

Reynolds, Z. A.

2015-12-01

Flooding, and the resulting economic damage to roads and property, is associated with natural dams such as beaver dams or log jams. For this reason, humans often remove natural dams; however, river reaches with natural dams provide very different ecosystem services in comparison with free-flowing river reaches. Therefore, the goal of this project is to assess the differences in ecosystem state between these different river reach types in the northeastern United States. We focused on differences in basic chemistry (e.g., dissolved oxygen, pH, temperature, and organic carbon) to assess the impact of natural dams on river ecosystem state. Study sites include rivers in the White Mountains and southeastern New Hampshire at locations with beaver dams, beaver ponds, beaver meadows, log jams, and free-flowing reaches. Dissolved oxygen, ORP, pH, temperature, and conductivity were measured in the field with a YSI Professional Plus meter. Water samples were collected for subsequent laboratory analysis of total organic carbon with a Shimadzu TOC-L. Preliminary results show that the chemistry of river water varies with feature type. Most significantly, dissolved oxygen concentrations are highest in free-flowing reaches and lowest in beaver ponds. Although beaver ponds are often associated with lower pH, due the increased concentration of organic acids, some beaver ponds can increase pH when compared to free-flowing reaches on the same river. Early results also show that water chemistry returns quickly to the chemistry typical of the free-flowing river reaches after being altered by a natural dam. Overall, natural dams create a river system that has more heterogeneity, and therefore has opportunities to provide more ecosystem functions, than a purely free-flowing river; this can increase the number of supported instream and riparian species. By increasing the understanding of how natural dams affect the chemistry of river water, river engineers can improve their decisions on how to remove problematic natural dams that increase flooding risks; they can also investigate possibilities to mimic the ecosystem state generated by natural dams in places where these dams are regularly removed.

Characterization of meltwater 'ingredients' at the Haig Glacier, Canadian Rockies: the importance of glaciers to regional water resources

NASA Astrophysics Data System (ADS)

Miller, K.; Marshall, S.

2017-12-01

With rising temperatures, Alberta's glaciers are under stresses which change and alter the timing, amount, and composition of meltwater contributions to rivers that flow from the Rocky Mountains. Meltwater can be stored within a glacier or it can drain through the groundwater system, reducing and delaying meltwater delivery to glacier-fed streams. This study tests whether the glacier meltwater is chemically distinct from rain or snow melt, and thus whether meltwater contributions to higher-order streams that flow from the mountains can be determined through stream chemistry. Rivers like the Bow, North Saskatchewan, and Athabasca are vital waterways for much of Alberta's population. Assessing the extent of glacier meltwater is vital to future water resource planning. Glacier snow/ice and meltwater stream samples were collected during the 2017 summer melt season (May- September) and analyzed for isotope and ion chemistry. The results are being used to model water chemistry evolution in the melt stream through the summer season. A chemical mixing model will be constructed to determine the fractional contributions to the Haig meltwater stream from precipitation, surface melt, and subglacial meltwaters. Distinct chemical water signatures have not been used to partition water sources and understand glacier contributions to rivers in the Rockies. The goal of this work is to use chemical signatures of glacial meltwater to help assess the extent of glacier meltwater in Alberta rivers and how this varies through the summer season.

Thiolated DNA-based chemistry and control in the structure and optical properties of plasmonic nanoparticles with ultrasmall interior nanogap.

PubMed

Oh, Jeong-Wook; Lim, Dong-Kwon; Kim, Gyeong-Hwan; Suh, Yung Doug; Nam, Jwa-Min

2014-10-08

The design, synthesis and control of plasmonic nanostructures, especially with ultrasmall plasmonically coupled nanogap (∼1 nm or smaller), are of significant interest and importance in chemistry, nanoscience, materials science, optics and nanobiotechnology. Here, we studied and established the thiolated DNA-based synthetic principles and methods in forming and controlling Au core-nanogap-Au shell structures [Au-nanobridged nanogap particles (Au-NNPs)] with various interior nanogap and Au shell structures. We found that differences in the binding affinities and modes among four different bases to Au core, DNA sequence, DNA grafting density and chemical reagents alter Au shell growth mechanism and interior nanogap-forming process on thiolated DNA-modified Au core. Importantly, poly A or poly C sequence creates a wider interior nanogap with a smoother Au shell, while poly T sequence results in a narrower interstitial interior gap with rougher Au shell, and on the basis of the electromagnetic field calculation and experimental results, we unraveled the relationships between the width of the interior plasmonic nanogap, Au shell structure, electromagnetic field and surface-enhanced Raman scattering. These principles and findings shown in this paper offer the fundamental basis for the thiolated DNA-based chemistry in forming and controlling metal nanostructures with ∼1 nm plasmonic gap and insight in the optical properties of the plasmonic NNPs, and these plasmonic nanogap structures are useful as strong and controllable optical signal-generating nanoprobes.

Microstructure and properties of thermomechanically strengthened reinforcement bars: A comparative assessment of plain-carbon and low-alloy steel grades

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

Ray, A.; Mukerjee, D.; Sen, S.K.

1997-06-01

An extensive investigation has been carried out to study structure-property characteristics and corrosion behavior in three varieties of thermomechanically treated (TMT) reinforcement bars (rebars) produced in an integrated steel plant under the Steel Authority of India Limited. Three experimental steel heats--one of plain-carbon and two of low-alloy chemistry--were chosen for the study. Of the two low-alloy heats, one was copper-bearing and the other contained both copper and chromium for improved corrosion resistance. Hot-rolled bars for each specific chemistry were subjected to in-line thermomechanical treatment, where quenching parameters were altered to achieve different yield strength levels. All the TMT rebars, regardlessmore » of chemistry and strength level, exhibited a composite microstructure consisting of ferrite-pearlite at the core and tempered martensite at the rim. Although a tendency toward formation of Widmanstaetten ferrite was evident in bars of 500 and 550 MPa yield strength levels, no adverse effect on their strength and ductility was observed. From the standpoint of mechanical properties, the rebars not only conformed to minimum yield strength requirements, but also exhibited high elongation values (21 to 28%) and excellent bendability. Corrosion studies of both TMT and cold-twisted and deformed (CTD) rebars subjected to different laboratory tests indicated that corrosion resistance increased in this order: CTD, plain-carbon TMT, copper-bearing TMT, and copper/chromium-bearing TMT.« less

Sense codon emancipation for proteome-wide incorporation of noncanonical amino acids: rare isoleucine codon AUA as a target for genetic code expansion.

PubMed

Bohlke, Nina; Budisa, Nediljko

2014-02-01

One of the major challenges in contemporary synthetic biology is to find a route to engineer synthetic organisms with altered chemical constitution. In terms of core reaction types, nature uses an astonishingly limited repertoire of chemistries when compared with the exceptionally rich and diverse methods of organic chemistry. In this context, the most promising route to change and expand the fundamental chemistry of life is the inclusion of amino acid building blocks beyond the canonical 20 (i.e. expanding the genetic code). This strategy would allow the transfer of numerous chemical functionalities and reactions from the synthetic laboratory into the cellular environment. Due to limitations in terms of both efficiency and practical applicability, state-of-the-art nonsense suppression- or frameshift suppression-based methods are less suitable for such engineering. Consequently, we set out to achieve this goal by sense codon emancipation, that is, liberation from its natural decoding function - a prerequisite for the reassignment of degenerate sense codons to a new 21st amino acid. We have achieved this by redesigning of several features of the post-transcriptional modification machinery which are directly involved in the decoding process. In particular, we report first steps towards the reassignment of 5797 AUA isoleucine codons in Escherichia coli using efficient tools for tRNA nucleotide modification pathway engineering. © 2014 The Authors. FEMS Microbiology Letters published by John Wiley & Sons Ltd on behalf of the Federation of European Microbiological Societies.

Insights Into Atmospheric Aqueous Organic Chemistry Through Controlled Experiments with Cloud Water Surrogates

NASA Astrophysics Data System (ADS)

Turpin, B. J.; Ramos, A.; Kirkland, J. R.; Lim, Y. B.; Seitzinger, S.

2011-12-01

There is considerable laboratory and field-based evidence that chemical processing in clouds and wet aerosols alters organic composition and contributes to the formation of secondary organic aerosol (SOA). Single-compound laboratory experiments have played an important role in developing aqueous-phase chemical mechanisms that aid prediction of SOA formation through multiphase chemistry. In this work we conduct similar experiments with cloud/fog water surrogates, to 1) evaluate to what extent the previously studied chemistry is observed in these more realistic atmospheric waters, and 2) to identify additional atmospherically-relevant precursors and products that require further study. We used filtered Camden and Pinelands, NJ rainwater as a surrogate for cloud water. OH radical (~10-12 M) was formed by photolysis of hydrogen peroxide and samples were analyzed in real-time by electrospray ionization mass spectroscopy (ESI-MS). Discrete samples were also analyzed by ion chromatography (IC) and ESI-MS after IC separation. All experiments were performed in duplicate. Standards of glyoxal, methylglyoxal and glycolaldehyde and their major aqueous oxidation products were also analyzed, and control experiments performed. Decreases in the ion abundance of many positive mode compounds and increases in the ion abundance of many negative mode compounds (e.g., organic acids) suggest that precursors are predominantly aldehydes, organic peroxides and/or alcohols. Real-time ESI mass spectra were consistent with the expected loss of methylglyoxal and subsequent formation of pyruvate, glyoxylate, and oxalate. New insights regarding other potential precursors and products will be provided.

Nanoparticle growth by particle-phase chemistry

NASA Astrophysics Data System (ADS)

Apsokardu, Michael J.; Johnston, Murray V.

2018-02-01

The ability of particle-phase chemistry to alter the molecular composition and enhance the growth rate of nanoparticles in the 2-100 nm diameter range is investigated through the use of a kinetic growth model. The molecular components included are sulfuric acid, ammonia, water, a non-volatile organic compound, and a semi-volatile organic compound. Molecular composition and growth rate are compared for particles that grow by partitioning alone vs. those that grow by a combination of partitioning and an accretion reaction in the particle phase between two organic molecules. Particle-phase chemistry causes a change in molecular composition that is particle diameter dependent, and when the reaction involves semi-volatile molecules, the particles grow faster than by partitioning alone. These effects are most pronounced for particles larger than about 20 nm in diameter. The modeling results provide a fundamental basis for understanding recent experimental measurements of the molecular composition of secondary organic aerosol showing that accretion reaction product formation increases linearly with increasing aerosol volume-to-surface-area. They also allow initial estimates of the reaction rate constants for these systems. For secondary aerosol produced by either OH oxidation of the cyclic dimethylsiloxane (D5) or ozonolysis of β-pinene, oligomerization rate constants on the order of 10-3 to 10-1 M-1 s-1 are needed to explain the experimental results. These values are consistent with previously measured rate constants for reactions of hydroperoxides and/or peroxyacids in the condensed phase.

Titan's atmosphere and climate

NASA Astrophysics Data System (ADS)

Hörst, S. M.

2017-03-01

Titan is the only moon with a substantial atmosphere, the only other thick N2 atmosphere besides Earth's, the site of extraordinarily complex atmospheric chemistry that far surpasses any other solar system atmosphere, and the only other solar system body with stable liquid currently on its surface. The connection between Titan's surface and atmosphere is also unique in our solar system; atmospheric chemistry produces materials that are deposited on the surface and subsequently altered by surface-atmosphere interactions such as aeolian and fluvial processes resulting in the formation of extensive dune fields and expansive lakes and seas. Titan's atmosphere is favorable for organic haze formation, which combined with the presence of some oxygen-bearing molecules indicates that Titan's atmosphere may produce molecules of prebiotic interest. The combination of organics and liquid, in the form of water in a subsurface ocean and methane/ethane in the surface lakes and seas, means that Titan may be the ideal place in the solar system to test ideas about habitability, prebiotic chemistry, and the ubiquity and diversity of life in the universe. The Cassini-Huygens mission to the Saturn system has provided a wealth of new information allowing for study of Titan as a complex system. Here I review our current understanding of Titan's atmosphere and climate forged from the powerful combination of Earth-based observations, remote sensing and in situ spacecraft measurements, laboratory experiments, and models. I conclude with some of our remaining unanswered questions as the incredible era of exploration with Cassini-Huygens comes to an end.

Effect of subalpine canopy removal on snowpack, soil solution, and nutrient export, Fraser Experimental Forest, CO

USGS Publications Warehouse

Stottlemyer, R.; Troendle, C.A.

1999-01-01

Research on the effects of vegetation manipulation on snowpack, soil water, and streamwater chemistry and flux has been underway at the Fraser Experimental Forest (FEF), CO, since 1982. Greater than 95% of FEF snowmelt passes through watersheds as subsurface flow where soil processes significantly alter meltwater chemistry. To better understand the mechanisms accounting for annual variation in watershed streamwater ion concentration and flux with snowmelt, we studied subsurface water flow, its ion concentration, and flux in conterminous forested and clear cut plots. Repetitive patterns in subsurface flow and chemistry were apparent. Control plot subsurface flow chemistry had the highest ion concentrations in late winter and fall. When shallow subsurface flow occurred, its Ca2+, SO42-, and HCO3- concentrations were lower and K+ higher than deep flow. The percentage of Ca2+, NO3-, SO42-, and HCO3- flux in shallow depths was less and K+ slightly greater than the percentage of total flow. Canopy removal increased precipitation reaching the forest floor by about 40%, increased peak snowpack water equivalent (SWE) > 35%, increased the average snowpack Ca2+, NO3-, and NH4+ content, reduced the snowpack K+ content, and increased the runoff four-fold. Clear cutting doubled the percentage of subsurface flow at shallow depths, and increased K+ concentration in shallow subsurface flow and NO3- concentrations in both shallow and deep flow. The percentage change in total Ca2+, SO42-, and HCO3- flux in shallow depths was less than the change in water flux, while that of K+ and NO3- flux was greater. Relative to the control, in the clear cut the percentage of total Ca2+ flux at shallow depths increased from 5 to 12%, SO42- 5.4 to 12%, HCO3- from 5.6 to 8.7%, K+ from 6 to 35%, and NO3- from 2.7 to 17%. The increases in Ca2+ and SO42- flux were proportional to the increase in water flux, the flux of HCO3- increased proportionally less than water flux, and NO3- and K+ were proportionally greater than water flux. Increased subsurface flow accounted for most of the increase in non-limiting nutrient loss. For limiting nutrients, loss of plant uptake and increased shallow subsurface flow accounted for the greater loss. Seasonal ion concentration patterns in streamwater and subsurface flow were similar.Research on the effects of vegetation manipulation on snowpack, soil water, and streamwater chemistry and flux has been underway at the Fraser Experimental Forest (FEF), CO, since 1982. Greater than 95% of FEF snowmelt passes through watersheds as subsurface flow where soil processes significantly alter meltwater chemistry. To better understand the mechanisms accounting for annual variation in watershed streamwater ion concentration and flux with snowmelt, we studied subsurface water flow, its ion concentration, and flux in conterminous forested and clear cut plots. Repetitive patterns in subsurface flow and chemistry were apparent. Control plot subsurface flow chemistry had the highest ion concentrations in late winter and fall. When shallow subsurface flow occurred, its Ca2+, SO42-, and HCO3- concentrations were lower and K+ higher than deep flow. The percentage of Ca2+, NO3-, SO42-, and HCO3- flux in shallow depths was less and K+ slightly greater than the percentage of total flow. Canopy removal increased precipitation reaching the forest floor by about 40%, increased peak snowpack water equivalent (SWE) > 35%, increased the average snowpack Ca2+, NO3-, and NH4+ content, reduced the snowpack K+ content, and increased the runoff four-fold. Clear cutting doubled the percentage of subsurface flow at shallow depths, and increased K+ concentration in shallow subsurface flow and NO3- concentrations in both shallow and deep flow. The percentage change in total Ca2+, SO42-, and HCO3- flux in shallow depths was less than the change in water flux, while that of K+ and NO3- flux was greater. Relative to the control, in the clear cut the percentage of total Ca

Veneers, rinds, and fracture fills: Relatively late alteration of sedimentary rocks at Meridiani Planum, Mars

USGS Publications Warehouse

Knoll, A.H.; Jolliff, B.L.; Farrand, W. H.; Bell, J.F.; Clark, B. C.; Gellert, Ralf; Golombek, M.P.; Grotzinger, J.P.; Herkenhoff, K. E.; Johson, J.R.; McLennam, S.M.; Morris, Robert; Squyres, S. W.; Sullivan, R.; Tosca, N.J.; Yen, A.; Learner, Z.

2008-01-01

Veneers and thicker rinds that coat outcrop surfaces and partially cemented fracture fills formed perpendicular to bedding document relatively late stage alteration of ancient sedimentary rocks at Meridiani Planum, Mars. The chemistry of submillimeter thick, buff-colored veneers reflects multiple processes at work since the establishment of the current plains surface. Veneer composition is dominated by the mixing of silicate-rich dust and sulfate-rich outcrop surface, but it has also been influenced by mineral precipitation, including NaCl, and possibly by limited physical or chemical weathering of sulfate minerals. Competing processes of chemical alteration (perhaps mediated by thin films of water or water vapor beneath blanketing soils) and sandblasting of exposed outcrop surfaces determine the current distribution of veneers. Dark-toned rinds several millimeters thick reflect more extensive surface alteration but also indicate combined dust admixture, halite precipitation, and possible minor sulfate removal. Cemented fracture fills that are differentially resistant to erosion occur along the margins of linear fracture systems possibly related to impact. These appear to reflect limited groundwater activity along the margins of fractures, cementing mechanically introduced fill derived principally from outcrop rocks. The limited thickness and spatial distribution of these three features suggest that aqueous activity has been rare and transient or has operated at exceedingly low rates during the protracted interval since outcropping Meridiani strata were exposed on the plains surface. Copyright 2008 by the American Geophysical Union.

Transition States and transition state analogue interactions with enzymes.

PubMed

Schramm, Vern L

2015-04-21

Enzymatic transition states have lifetimes of a few femtoseconds (fs). Computational analysis of enzyme motions leading to transition state formation suggests that local catalytic site motions on the fs time scale provide the mechanism to locate transition states. An experimental test of protein fs motion and its relation to transition state formation can be provided by isotopically heavy proteins. Heavy enzymes have predictable mass-altered bond vibration states without altered electrostatic properties, according to the Born-Oppenheimer approximation. On-enzyme chemistry is slowed in most heavy proteins, consistent with altered protein bond frequencies slowing the search for the transition state. In other heavy enzymes, structural changes involved in reactant binding and release are also influenced. Slow protein motions associated with substrate binding and catalytic site preorganization are essential to allow the subsequent fs motions to locate the transition state and to facilitate the efficient release of products. In the catalytically competent geometry, local groups move in stochastic atomic motion on the fs time scale, within transition state-accessible conformations created by slower protein motions. The fs time scale for the transition state motions does not permit thermodynamic equilibrium between the transition state and stable enzyme states. Isotopically heavy enzymes provide a diagnostic tool for fast coupled protein motions to transition state formation and mass-dependent conformational changes. The binding of transition state analogue inhibitors is the opposite in catalytic time scale to formation of the transition state but is related by similar geometries of the enzyme-transition state and enzyme-inhibitor interactions. While enzymatic transition states have lifetimes as short as 10(-15) s, transition state analogues can bind tightly to enzymes with release rates greater than 10(3) s. Tight-binding transition state analogues stabilize the rare but evolved enzymatic geometry to form the transition state. Evolution to efficient catalysis optimized this geometry and its stabilization by a transition state mimic results in tight binding. Release rates of transition state analogues are orders of magnitude slower than product release in normal catalytic function. During catalysis, product release is facilitated by altered chemistry. Compared to the weak associations found in Michaelis complexes, transition state analogues involve strong interactions related to those in the transition state. Optimum binding of transition state analogues occurs when the complex retains the system motions intrinsic to transition state formation. Conserved dynamic motion retains the entropic components of inhibitor complexes, improving the thermodynamics of analogue binding.

Authigenesis/Diagenesis of the Murray Formation Mudstone in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Ming, D. W.; Rampe, E. B.; Grotzinger, J. P.; Hurowitz, J. A.; Morris, R. V.; Yen, A. S.; Blake, D. B.; Geller, R.; Sutter, B.

2016-01-01

The Mars Science Laboratory rover Curiosity has been exploring sedimentary deposits in Gale crater since August, 2012. The rover has traversed up section through approximately 150 m of sedimentary rocks deposited in fluvial, deltaic, and lacustrine environments (Bradbury group and overlying Mount Sharp group). The Murray formation lies at the base of the Mt. Sharp group and has been interpreted to be a finely laminated mudstone likely deposited in a subaqueous lacustrine environment. Four drill samples from several elevations in the Murray fm have been acquired by the rover's sampling system and delivered to the CheMin XRD instrument. The lower section of the Murray fm contains 2:1 phyllosilicate(s), hematite, jarosite, XRD amorphous materials, and primary basaltic minerals. Further up section, the Murray fm contains magnetite, cristobalite, tridymite, abundant Si-rich XRD amorphous materials along with plagioclase and K-feldspars. Murray formation materials appear to have been altered under an open hydrologic system based on the bulk chemistry of these materials measured by the Alpha Particle X-ray Spectrometer (APXS). The 2:1 phyllosilicate only occurs in the lowermost section of the Murray fm and may be detrital or formed during authigenesis of Murray fm materials, similar to the Fe-saponite and magnetite detected in a mudstone in the Yellowknife Bay fm near Curiosity's landing site (stratigraphically at the base of the Bradbury group). The occurrence of jarosite and hematite in the lower section indicates an acidic diagenetic event. These phases may have formed via several acidic alteration mechanisms, including (1) oxidative weathering of mafic igneous rocks containing sulfides; (2) sulfuric acid weathering of Fe-bearing phases; and (3) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity. The transition from abundant hematite in the lowermost Murray fm to magnetite moving up section may indicate changes in lake chemistry, i.e., variable redox conditions, possibly during authigenesis or subsequent diagenetic events. Tridymite, a high temperature mineral, (and possibly cristobalite) is detrital, potentially deposited in a lake from a distal silicic volcanic rock source or from crustal materials present prior to the Gale Crater impact event. Abundant Si-rich XRD amorphous materials in the upper sections of the Murray fm may be detrital or an aqueous alteration product of primary igneous phases and phyllosilicates. Curiosity's science team is still deciphering the authigenesis and diagenetic events that formed the Murray fm. The mineralogy and geochemistry of the formation suggest a complicated history with several (many?) episodes of aqueous alteration under a variety of environmental conditions.

Sedimentary provenance of Maastrichtian oil shales, Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Fathy, Douaa; Wagreich, Michael; Mohamed, Ramadan S.; Zaki, Rafat

2017-04-01

Maastrichtian oil shales are distributed within the Central Eastern Desert in Egypt. In this study elemental geochemical data have been applied to investigate the probable provenance of the sedimentary detrital material of the Maastrichtian oil shale beds within the Duwi and the Dakhla formations. The Maastrichtian oil shales are characterized by the enrichment in Ca, P, Mo, Ni, Zn, U, Cr and Sr versus post-Archean Australian shales (PAAS). The chondrite-normalized patterns of the Maastrichtian oil shale samples are showing LREE enrichment, HREE depletion, slightly negative Eu anomaly, no obvious Ce anomaly and typical shale-like PAAS-normalized patterns. The total REE well correlated with Si, Al, Fe, K and Ti, suggesting that the REE of the Maastrichtian oil shales are derived from terrigenous source. Chemical weathering indices such as Chemical Index of Alteration (CIA), Chemical Proxy of Alteration (CPA) and Plagioclase Index of Alteration (PIA) indicate moderate to strong chemical weathering. We suggest that the Maastrichtian oil shale is mainly derived from first cycle rocks especially intermediate rocks without any significant inputs from recycled or mature sources. The proposed data illustrated the impact of the parent material composition on evolution of oil shale chemistry. Furthermore, the paleo-tectonic setting of the detrital source rocks for the Maastrichtian oil shale is probably related to Proterozoic continental island arcs

Natural analogue studies as supplements to biomineralization research

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

McNeil, M.B.

1995-09-01

Chemical reactions can alter the chemistry and crystal structure of solid objects over archeological or geological times, while preserving external physical shapes. The reactions resulting in these structures offer natural analogues to laboratory experiments in biomineralization and to biologically influenced alteration of nuclear waste packages, and thus, they offer the only available way of validating models that purport waste package behavior over archaeological or geological times. Potential uses of such analogues in the construction and validation of hypothetical mechanisms of microbiological corrosion and biomineralization are reviewed. Evidence from such analogues suggests that biofilms can control materials alteration in ways usuallymore » overlooked. The newly hypothesized mechanisms involve control by biofilms of the cation flow near the solid surface and offer plausible mechanisms for the formation of mixed-cation minerals under conditions that would lead to dealloying in abiotic experiments; they also account for the formation of unusual minerals [such as posnjakite, Cu{sub 4}SO{sub 4}(OH){sub 6{center_dot}}H{sub 2}O] and mineral morphologies unusual in corrosion [malachite, Cu{sub 2}CO{sub 3}(OH){sub 2}, rarely forms botryoidally under corrosion conditions and its occasional presence on archaeological objects that appear to have undergone microbiological corrosion may be related to biofilm phenomena].« less

Groundwater's significance to changing hydrology, water chemistry, and biological communities of a floodplain ecosystem, Everglades, South Florida, USA

USGS Publications Warehouse

Harvey, J.W.; McCormick, P.V.

2009-01-01

The Everglades (Florida, USA) is one of the world's larger subtropical peatlands with biological communities adapted to waters low in total dissolved solids and nutrients. Detecting how the pre-drainage hydrological system has been altered is crucial to preserving its functional attributes. However, reliable tools for hindcasting historic conditions in the Everglades are limited. A recent synthesis demonstrates that the proportion of surface-water inflows has increased relative to precipitation, accounting for 33% of total inputs compared with 18% historically. The largest new source of water is canal drainage from areas of former wetlands converted to agriculture. Interactions between groundwater and surface water have also increased, due to increasing vertical hydraulic gradients resulting from topographic and water-level alterations on the otherwise extremely flat landscape. Environmental solute tracer data were used to determine groundwater's changing role, from a freshwater storage reservoir that sustained the Everglades ecosystem during dry periods to a reservoir of increasingly degraded water quality. Although some of this degradation is attributable to increased discharge of deep saline groundwater, other mineral sources such as fertilizer additives and peat oxidation have made a greater contribution to water-quality changes that are altering mineral-sensitive biological communities. ?? Springer-Verlag 2008.

Baccaurea angulata fruit juice ameliorates altered hematological and biochemical biomarkers in diet-induced hypercholesterolemic rabbits.

PubMed

Ahmed, Idris Adewale; Mikail, Maryam Abimbola; Ibrahim, Muhammad

2017-06-01

Hypercholesterolemia is an important risk factor linked to the alteration of blood hematology and clinical chemistry associated with the development and progression of atherosclerosis. Previous studies have demonstrated the safety and potential health benefits of Baccaurea angulata (BA) fruit. We hypothesized that the oral administration of BA fruit juice could ameliorate the alteration in the hematological and biochemical biomarkers of diet-induced hypercholesterolemic rabbits. The aim of this study was to investigate the effects of different doses of BA juice on the hematological and biochemical biomarkers in normo- and hypercholesterolemic rabbits. Thirty-five healthy adult New Zealand White rabbits were assigned to seven different groups for 90days of diet intervention. Four atherogenic groups were fed a 1% cholesterol diet and 0, 0.5, 1.0, and 1.5mL of BA juice per kg of rabbit daily. The other three normal groups were fed a commercial rabbit pellet diet and 0, 0.5, and 1.0mL of BA juice per kg of rabbit daily. Baseline and final blood samples after 90days of repeated administration BA juice were analyzed for hematological parameters while serum, aortic and hepatic lysates were analyzed for lipid profiles and other biochemical biomarkers. The alteration of the hemopoietic system, physiological changes in serum and tissues lipid profiles and other biochemicals resulting from the consumption of a high-cholesterol diet were significantly (P<.05) ameliorated by the administration of BA juice. Improvements of the biomarkers in rabbits were dose-dependent, markedly enhanced at the highest dose of juice (1.5mL/kg/day). The results suggest potential health benefits of the antioxidant-rich BA fruit juice against hypercholesterolemia-associated hematological and biochemical alterations in the rabbit. Copyright © 2017 Elsevier Inc. All rights reserved.

Anatexis at the roof of an oceanic magma chamber at IODP Site 1256 (equatorial Pacific): an experimental study

NASA Astrophysics Data System (ADS)

Erdmann, Martin; Fischer, Lennart A.; France, Lydéric; Zhang, Chao; Godard, Marguerite; Koepke, Jürgen

2015-04-01

Replenished axial melt lenses at fast-spreading mid-oceanic ridges may move upward and intrude into the overlying hydrothermally altered sheeted dikes, resulting in high-grade contact metamorphism with the potential to trigger anatexis in the roof rocks. Assumed products of this process are anatectic melts of felsic composition and granoblastic, two-pyroxene hornfels, representing the residue after partial melting. Integrated Ocean Drilling Program Expeditions 309, 312, and 335 at Site 1256 (eastern equatorial Pacific) sampled such a fossilized oceanic magma chamber. In this study, we simulated magma chamber roof rock anatectic processes by performing partial melting experiments using six different protoliths from the Site 1256 sheeted dike complex, spanning a lithological range from poorly to strongly altered basalts to partially or fully recrystallized granoblastic hornfels. Results show that extensively altered starting material lacking primary magmatic minerals cannot reproduce the chemistry of natural felsic rocks recovered in ridge environments, especially elements sensitive to hydrothermal alteration (e.g., K, Cl). Natural geochemical trends are reproduced through partial melting of moderately altered basalts from the lower sheeted dikes. Two-pyroxene hornfels, the assumed residue, were reproduced only at low melting degrees (<20 vol%). The overall amphibole absence in the experiments confirms the natural observation that amphibole is not produced during peak metamorphism. Comparing experimental products with the natural equivalents reveals that water activity ( aH2O) was significantly reduced during anatectic processes, mainly based on lower melt aluminum oxide and lower plagioclase anorthite content at lower aH2O. High silica melt at the expected temperature (1000-1050 °C; peak thermal overprint of two-pyroxene hornfels) could only be reproduced in the experimental series performed at aH2O = 0.1.

On the imprint of surfactant-driven stabilization of laboratory breaking wave foam with comparison to oceanic whitecaps

NASA Astrophysics Data System (ADS)

Callaghan, A. H.; Deane, G. B.; Stokes, M. D.

2017-08-01

Surfactants are ubiquitous in the global oceans: they help form the materially-distinct sea surface microlayer (SML) across which global ocean-atmosphere exchanges take place, and they reside on the surfaces of bubbles and whitecap foam cells prolonging their lifetime thus altering ocean albedo. Despite their importance, the occurrence, spatial distribution, and composition of surfactants within the upper ocean and the SML remains under-characterized during conditions of vigorous wave breaking when in-situ sampling methods are difficult to implement. Additionally, no quantitative framework exists to evaluate the importance of surfactant activity on ocean whitecap foam coverage estimates. Here we use individual laboratory breaking waves generated in filtered seawater and seawater with added soluble surfactant to identify the imprint of surfactant activity in whitecap foam evolution. The data show a distinct surfactant imprint in the decay phase of foam evolution. The area-time-integral of foam evolution is used to develop a time-varying stabilization function, ϕ>(t>) and a stabilization factor, Θ, which can be used to identify and quantify the extent of this surfactant imprint for individual breaking waves. The approach is then applied to wind-driven oceanic whitecaps, and the laboratory and ocean Θ distributions overlap. It is proposed that whitecap foam evolution may be used to determine the occurrence and extent of oceanic surfactant activity to complement traditional in-situ techniques and extend measurement capabilities to more severe sea states occurring at wind speeds in excess of about 10 m/s. The analysis procedure also provides a framework to assess surfactant-driven variability within and between whitecap coverage data sets.